Polyimide composition

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a thermoplastic resin composition having improved melt-processability and particularly relates to a melt-processable aromatic polyimide resin composition and a readily melt-processable aromatic polysulfone resin composition, aromatic polyetherimide resin composition, aromatic polyamideimide resin composition and aromatic polyetherketone resin composition. More particularly, the invention relates to a thermoplastic resin composition having improved melt-processability obtained by mixing liquid crystal type aromatic polyimide with aromatic polyimide having excellent heat resistance, chemical resistance and mechanical strength, aromatic polysulfone having excellent mechanical strength, aromatic polyetherimide having excellent heat resistance, aromatic polyamideimide having excellent heat resistance and mechanical strength, or aromatic polyetherketone having excellent heat resistance and mechanical strength.
2. Prior Art of the Invention
Many thermoplastic resins having excellent heat resistance have been conventionally developed. In these resins, polyimide is excellent in mechanical strength and dimensional stability in addition to high heat resistance, and also has flame retardance and electrical insulation property. Thus, polyimide has been used in the fields of electric and electronic appliances, space ,and aeronautic equipment and transport machinery and is expected in the future to be used in various fields where heat resistance is required.
Various polyimides having excellent characteristics have been conventionally developed. Proger et al. have disclosed in U.S. Pat. No. 4,065,345 polyimide having recurring structural units of the formula (A): ##STR2##
The polyimide is excellent in mechanical property, thermal property, electrical property, solvent resistance and heat resistance, and has also been known as polyimide having melt-flowability. However, extrusion forming and injection molding of the polyimide is difficult because the polyimide has higher melt viscosity as compared with other common engineering plastics which can be extruded or injection molded.
The present inventors have also found polyimide which is excellent in mechanical properties, thermal property, electrical property and solvent resistance, has heat resistance, and has recurring structural units represented by the formula (B): ##STR3## wherein X is a radical selected from the group consisting of a direct bond, divalent hydrocarbon having 1.about.10 carbon atoms, hexafluorinated isopropylidene, carbonyl, thio and sulfonyl, and R is a tetravalent radical selected from the group consisting of an aliphatic radical having 2.about.27 carbon atoms, alicyclic radical, monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected each other with a direct bond or bridge member (Japanese Laid-Open Patent Sho 61-143478, 62-68817, 62-86021, 62-235381 and 63-128025).
The above polyimide resins are novel thermoplastic resins having good properties which are essential for polyimide.
For example, in the polyimide of the formula (B), polyimide having recurring structural units of the formula (6): ##STR4## has a glass transition temperature (hereinafter referred to simply as Tg) of 260.degree. C., crystallization temperature (hereinafter referred to simply as Tc) of 310.degree..about.340.degree. C. and crystal melting point (hereinafter referred to simply as Tm) of 367.degree..about.385.degree. C., and is crystalline polyimide which is melt processable and excellent in chemical resistance. However, a high temperature close to 400.degree. C. is required for processing the polyimide because of high Tm of 367.degree..about.385.degree. C.
Polyimide is much superior in heat resistance and other properties and still inferior in processability to common engineering plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polysulfone, polyphenylene sulfide, polyether ether ketone and polyetherimide.
Some known polyimide has no distinct glass transition temperature though excellent in heat resistance and hence must be processed by such means as sinter molding when the polyimide is used for a molding material. Other known polyimide has a low glass transition temperature and is soluble in halogenated hydrocarbon solvent though excellent in processability and hence is unsatisfactory in view of resistance to heat and solvent. Both merits and drawbacks have thus been found in the properties of known polyimide.
Further, aromatic polysulfone, aromatic polyetherimide, aromatic polyamideimide and aromatic polyether ketone are excellent in mechanical strength and dimensional stability in addition to high heat resistance and also have flame retardance and electrical insulation property. Thus, these plastics are used in the field of electric and electronic appliances, space and aeronautic equipment and transport machinery and are expected to be used in various fields in the future where heat resistance is required. Aromatic polysulfone is an engineering plastic having good processability. However, aromatic polyetherimide, aromatic polyamideimide and aromatic polyether ketone which are called super engineering plastics have problems in processability and are desired to have good processability while maintaining high heat resistance.
On the other hand, liquid crystal type high polymers are classified into thermotropic liquid crystal and lyotropic liquid crystal. Conventionally known liquid crystal type high polymers are polyester, polyesteramide and polyazomethine which are thermotropic liquid crystals and polyamide and polybenzothiazole which are lyotropic liquid crystals. However, polyimide exhibiting liquid crystal property has been quite unknown.
Consequently, a resin composition obtained by mixing liquid crystal type polyimide with polyimide or other thermoplastic resins has been quite unknown.
SUMMARY OF THE INVENTION
The object of the invention is to provide a resin composition having improved processability without impairing essentially excellent characteristics of thermoplastic resin.
Practically, the first object of the invention is to provide an aromatic polyimide based thermoplastic resin composition having improved processability without impairing essentially excellent heat resistance of aromatic polyimide by adding liquid crystal type aromatic polyimide having good flowability to conventional aromatic polyimide.
The second object of the invention is to provide an aromatic polysulfone based thermoplastic resin composition having improved processability without impairing essentially excellent heat resistance of aromatic polysulfone by adding liquid crystal type aromatic polyimide having good flowability to conventional aromatic polysulfone.
The third object of the invention is to provide an aromatic polyetherimide based thermoplastic resin composition having improved processability without impairing essentially excellent heat resistance of aromatic polyetherimide by adding liquid crystal type aromatic polyimide having good flowability to conventional aromatic polyetherimide.
The fourth object of the invention is to provide an aromatic polyamideimide based thermoplastic resin composition having improved processability without impairing essentially excellent heat resistance and mechanical properties of aromatic polyamideimide by adding liquid crystal type aromatic polyimide having good flowability to conventional aromatic polyamideimide.
The fifth object of the invention is to provide an aromatic polyether ketone based thermoplastic composition having improved processability without impairing essentially excellent heat resistance and mechanical properties of aromatic polyether ketone by adding liquid crystal type aromatic polyimide having good flowability to conventional aromatic polyether ketone.
As a result of an intensive investigation in order to achieve these objects, the present inventors have found that a thermoplastic resin composition obtained by mixing liquid crystal type aromatic polyimide with aromatic polyimide, aromatic polysulfone, aromatic polyetherimide, aromatic polyamideimide or aromatic polyether ketone has improved processability without impairing essentially excellent properties of each resin, and thus have completed the invention.
That is, the present inventors have developed an aromatic polyimide having recurring structural units of the formula (4) : ##STR5## (Japanese Laid-Open Patent Hei 03-160024.)
Thereafter, the inventors have found that the aromatic polyimide exhibits liquid crystal property in the temperature range of 270.degree..about.300.degree. C. The liquid crystal property of the aromatic polyimide could be confirmed by observation under a polarization microscope. When the above aromatic polyimide was heated at a temperature increase rate of 10.degree. C./min on a hot plate equipped with a polarization microscope, Model BHS-751P (Trade Mark of OLYMPUS OPTICAL Co.), polarized light was observed in the temperature range 270.degree..about.300.degree. C.
When the above polyimide was measured by DSC(Differential Scanning Calorimetry) with a DT-series, DSC-41M (Trade Mark of Shimadzu Co.) at a temperature increase rate of 10.degree. C./min, two heat absorption peaks were observed at around 275.degree. C. and around 295.degree. C. It was confirmed that the liquid crystal property was exhibited in the temperature range between the two heat absorption peaks. Further, the aromatic polyimide which has a temperature between the two heat absorption peaks exhibits liquid crystal property and additionally has a very low melt viscosity in a molten state and is excellent in processability.
As a result of mixing the aromatic polyimide which exhibits liquid crystal property with aromatic polyimide or other thermoplastic resin which is required to improve processability, the present inventors have found that processability of these resins can be improved, and have completed the invention.
That is, the present invention is a melt-processable thermoplastic resin composition comprising a liquid crystal type aromatic polyimide and other aromatic polyimide or other thermoplastic resin.
The present invention includes the following aspects.
1. A thermoplastic resin composition having good processability, comprising 99.9.about.50 parts by weight of one or more thermoplastic resin and 0.1.about.50 parts by weight of one or more liquid crystal type aromatic polyimide.
2. A thermoplastic resin composition having good processability, comprising 99.9.about.50 parts by weight of one or more thermoplastic resin and 0.1.about.50 parts by weight of one or more liquid crystal type aromatic polyimide having recurring structural units represented by the formula (1): ##STR6## wherein R.sub.1 .about.R.sub.5 is a hydrogen atom, fluorine atom, trifluoromethyl, methyl, ethyl or cyano and may be the same or different, and R is a tetravalent radical having 6.about.27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected each other with a direct bond or a bridge member.
3. The thermoplastic resin composition as described in 2. wherein the liquid crystal type aromatic polyimide has a fundamental skeleton having recurring structural units of the formula (4): ##STR7##
4. The thermoplastic resin composition as described in 1. wherein the liquid crystal type aromatic polyimide is a copolymer comprising 1.about.99% by mol of the fundamental skeleton having recurring structural units of the formula (4): ##STR8## and 1.about.99% by mol of the fundamental skeleton having recurring structural units of formula (1) [formula (4), exclusive]: wherein R.sub.1 .about.R.sub.5 is a hydrogen atom, fluorine atom, trifluoromethyl, methyl, ethyl or cyano and may be the same or different, and R is a tetravalent radical having 6.about.27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected each other with a direct bond or a bridge member.
5. The thermoplastic resin composition as described in 1 wherein the thermoplastic resin is one or more resin selected from the group consisting of aromatic polyimide, aromatic polyetherimide, aromatic polyamideimide, aromatic polyethersulfone and aromatic polyether ketone.
6. The thermoplastic resin composition as described in 5 wherein the aromatic polyimide comprises a fundamental skeleton having recurring structural units represented by the formula (5): ##STR9## wherein X is a divalent radical selected from the group consisting of a direct bond, isopropylidene, hexafluorinated isopropylidene, carbonyl, thio and sulfonyl, and R is a tetravalent radical having 6.about.27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected each other with a direct bond or a bridge member.
7. The thermoplastic resin composition as described in 5 wherein the aromatic polyimide comprises a fundamental skeleton having recurring structural units of the formula (6): ##STR10##
8. The thermoplastic resin composition as described in 5 wherein the aromatic polyimide comprises a fundamental skeleton having recurring structural units of the formula (7): ##STR11##
9. The thermoplastic resin composition as described in 5 wherein the aromatic polyimide is a copolymer comprising 99.about.1% by mol of a fundamental skeleton having recurring structural units of the formula (6): ##STR12## and 1.about.99% by mol of a fundamental skeleton having recurring structural units of the formula (8) [the formula (6), exclusive]: ##STR13## wherein n is an integer of 0, 1, 2, or 3; Q is a direct bond, --O--, --S--, --CO--, --SO.sub.2 --, --CH.sub.2 --, --C(CH.sub.3).sub.2 --or --C(CF.sub.3).sub.2 -- and may be the same or different when two or more Q connects three or more aromatic rings each other; and R" is one or more tetravalent radicals selected from the group consisting of ##STR14## wherein M is one or more divalent radicals selected from the group consisting of ##STR15## and particularly a thermoplastic resin composition wherein the fundamental skeleton having recurring structural units of the formula (8) comprises recurring structural units represented by the following formula [the formula (6), exclusive]: ##STR16## wherein R is the same as above.
10. The thermoplastic resin composition as described in 5 wherein the aromatic polysulfone comprises a fundamental skeleton having one or more recurring structural units represented by the formula (11): ##STR17## wherein X is a direct bond, ##STR18##
11. The thermoplastic resin composition as described in 5 wherein the aromatic polyimide is an aromatic polyetherimide comprising a fundamental skeleton having one or more recurring structural units represented by the formula (12): ##STR19## wherein X is ##STR20## and Y is ##STR21##
12. The thermoplastic resin composition as described in 5 wherein the aromatic polyamideimide comprises a fundamental skeleton having one or more recurring structural units represented by the formula(D). ##STR22## wherein Y is a divalent radical having 6.about.27 carbon stoms, and particularly one or more recurring structural units of the formulas (13): ##STR23## and/or the formula (14): ##STR24##
13. The thermoplastic resin composition as described in 5 wherein the aromatic polyaether ketone comprises a fundamental skeleton having recurring structural units of the formula (15): ##STR25## and/or the formula (16): ##STR26##
14. A thermoplastic resin composition as described in 1 to 9 wherein the aromatic polyimide and/or the liquid crystal type aromatic polyimide are capped at the polymer chain end thereof with aromatic dicarboxylic anhydride of the formula (2): ##STR27## wherein Z is a divalent radical having 6.about.15 carbon atoms and being selected from a monoaromatic radical, condensed polyaromatic radical, and noncondensed aromatic radical connected each other with a direct bond or a bridge member and/or aromatic amine of the formula (3):
V--NH.sub.2 ( 3)
wherein V is a monovalent radical having 6.about.15 carbon atoms and being selected from a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected each other with a direct bond or a bridge member, and preferably by capping the polymer chain end with phthalic anhydride and/or aniline.
The present invention can provide thermoplastic resin compositions which have remarkably good processability and excellent thermal stability in addition to essentially excellent properties of each resin.
DETAILED DESCRIPTION OF THE INVENTION
The liquid crystal type polyimide used in the invention exhibits liquid crystal property such as thermotropic liquid crystal and lyotropic liquid crystal.
The liquid crystal type polyimide includes, for example, whole aromatic polyimide which exhibits liquid crystal property and is represented by the formula (1): ##STR28## wherein R.sub.1 .about.R.sub.5 are a hydrogen atom, fluorine atom, trifluoromethyl, methyl, ethyl or cyano and may be the same or different, and R is a tetravalent radical having 2.about.27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected to each other with a direct bond or a bridge member.
Preferred liquid crystal type polyimide includes liquid crystal type aromatic polyimide of the formula (4): ##STR29## or a liquid crystal type aromatic polyimide copolymer comprising 1.about.99% by mol of the fundamental skeleton having recurring structural units of the formula (4): ##STR30## and 1.about.99% by mol of the fundamental skeleton having recurring structural units of the formula (1) [formula (4); exclusive]: ##STR31## wherein R.sub.1 .about.R.sub.5 are a hydrogen atom, fluorine atom, trifluoromethyl, methyl, ethyl or cyano and may be the same or different, and R is a tetravalent radical having 6.about.27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected to each other with a direct bond or a bridge member.
Other preferred polymers include liquid crystal type aromatic polyimide and a liquid crystal type aromatic polyimide copolymer which are obtained by capping the polymer chain end of homopolymer or copolymer of liquid crystal type aromatic polyimide with aromatic dicarboxylic anhydride of the formula (2): ##STR32## wherein Z is a divalent radical having 6.about.15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected to each other with a direct bond or a bridge member, and/or aromatic monoamine of the formula (3):
V--NH.sub.2 ( 3)
wherein V is a monovalent radical having 6.about.15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected each a direct bond or a bridge member.
Such liquid crystal type aromatic polyimide can be prepared by reacting one or more aromatic diamine represented by the formula (17) below with one or more aromatic tetracarboxylic dianhydride represented by the formula (19) and by thermally or chemically imidizing the resultant polyamic acid.
The aromatic diamines used in the process are represented by the formula (17): ##STR33## wherein R.sub.1 .about.R.sub.5 are the same as in the formula (1), and include, for example,
1,3- or 1,4-bis[4-(4-aminophenoxy)-.alpha.,.alpha.-dimethylbenzyl]benzene,
1,3- or 1,4-bis[4-(3-aminophenoxy)-.alpha.,.alpha.-dimethylbenzyl]benzene,
1,3- or 1,4-bis[4-(4-amino-6-methylphenoxy)-.alpha.,.alpha.-dimethylbenzyl]benzene
1,3- or 1,4-bis[4-(4-amino-6-fluorophenoxy)-.alpha.,.alpha.-dimethylbenzyl]benzene
1,3- or 1,4-bis[4-(4-amino-6-trifluoromethylphenoxy)-.alpha.,.alpha.-dimethylbenzyl] benzene,
1,3- or 1,4-bis[4-(4-aminophenoxy)-3-dimethyl-.alpha.,.alpha.-dimethylbenzyl]benzene,
1,3- or 1,4-bis[4-(4-amino-6-methylphenoxy)-3-dimethyl-.alpha.,.alpha.-dimethylbenzyl]benzene,
1,3- or 1,4-bis[4-(3-amino-6-methylphenoxy)-3-dimethyl-.alpha.,.alpha.-dimethylbenzyl]benzene,
1,3- or 1,4-bis[4-(4-amino-6-trifluoromethylphenoxy)-3,5-dimethyl-.alpha.,.alpha.-dimethylbenzyl]benzene and
1,3- or 1,4-bis[4-(4-amino-6-cyanophenoxy)-.alpha.,.alpha.-dimethylbenzyl]benzene.
These diamines are used singly or as a mixture.
Particular preferred diamine is 1,3-bis[4-(4-aminophenoxy)-2,2-dimethylbenzyl]benzene having the formula (18): ##STR34##
When two or more diamines are used as a mixture, the above liquid crystal type aromatic polyimide copolymer can be obtained by simultaneously using the diamine of the formula (18) and other diamines.
These aromatic diamines can be prepared by conducting usual reduction of corresponding nitro compounds, respectively, in the presence of a base in an aprotic polar solvent.
Tetracarboxylic acid dianhydrides used in the invention are represented by the formula (19): ##STR35## wherein R is a tetravalent radical having 6.about.27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected to each other with a direct bond or a bridge member.
Exemplary dianhydrides include
pyromellitic dianhydride,
3,3',4,4'-benzophenonetetracarboxylic dianhydride,
2,2',3,3'-benzophenonetetracarboxylic dianhydride,
3,3',4,4'-biphenyltetracarboxylic dianhydride,
2,2',3,3'-biphenyltetracarboxylic dianhydride,
2,2-bis(3,4-dicarboxyphenyl)propane dianhydride,
2,2-bis(2,3-dicarboxyphenyl)propane dianhydride,
2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride,
2,2-bis(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride,
bis(2,3-dicarboxyphenyl)ether dianhydride,
bis(3,4-dicarboxyphenyl)ether dianhydride,
bis(2,3-dicarboxyphenyl)sulfone dianhydride,
bis(2,3-dicarboxyphenyl)methane dianhydride,
bis(3,4-dicarboxyphenyl)methane dianhydride.
1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride,
1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride,
1,2-bis(2,3-dicarboxyphenyl)ethane dianhydride,
1,2-bis(3,4-dicarboxyphenyl)ethane dianhydride,
2,3,6,7-naphthalenetetracarboxylic dianhydride,
1,4,5,8-naphthalenetetracarboxylic dianhydride,
1,2,5,6-naphthalenetetracarboxylic dianhydride,
1,2,3,4-benzenetetracarboxylic dianhydride,
3,4,9,10-perylenetetracarboxylic dianhydride,
2,3,6,7-anthracenetetracarboxylic dianhydride,
1,2,7,8-phenanthrenetetracarboxylic dianhydride,
2,2-bis[4- {3-(1,2-dicarboxy)phenoxy} phenyl]propane dianhydride,
bis[4- {(4-(1,2-dicarboxy)phenoxy} phenyl]ketone dianhydride,
bis[4- {(3-(1,2-dicarboxy)phenoxy} phenyl]ketone dianhydride,
bis[4- {4-(1,2-dicarboxy)phenoxy} phenyl]sulfone dianhydride,
bis[4- {3-(1,2-dicarboxy)phenoxy} phenyl]sulfone dianhydride,
4,4-bis[4-(1,2-dicarboxy)phenoxy] biphenyl dianhydride,
4,4-bis[3-(1,2-dicarboxy)phenoxy] biphenyl dianhydride,
2,2-bis[4- {4-(1,2-dicarboxy)phenoxy} phenyl]sulfide dianhydride,
2,2-bis[4- {3-(1,2-dicarboxy)phenoxy} phenyl]sulfide dianhydride,
2,2-bis[4- {4-(1,2-dicarboxy)phenoxy} phenyl]-1,1,1,3,3,3-hexafluoropropane dianhydride,
2,2-bis[4- {3-(1,2 dicarboxy)phenoxy} phenyl]-1,1,1,3,3,3-hexafluoropropane dianhydride,
1,3-bis[4-(1,2-dicarboxy)phenoxy]benzene dianhydride,
1,3-bis[3-(1,2-dicarboxy)phenoxy]benzene dianhydride,
1,4-bis[4-(1,2-dicarboxy)phenoxy]benzene dianhydride,
1,4-bis3-(1,2-dicarboxy)phenoxy]benzene dianhydride,
1,3-bis[4- {(1,2-dicarboxy)-.alpha.,.alpha.-dimethyl} benzyl]benzene dianhydride,
1,3-bis[3- {(1,2-dicarboxy)-.alpha.,.alpha.-dimethyl} benzyl]benzene dianhydride,
1,4-bis[4- {(1,2-dicarboxy)-.alpha.,.alpha.-dimethyl} benzyl]benzene dianhydride and
1,4-bis[3- {(1,2-dicarboxy)-.alpha.,.alpha.-dimethyl} benzyl]benzene dianhydride.
These aromatic tetracarboxylic dianhydrides can be used singly or as a mixture. Pyromellitic dianhydride is preferred in particular.
The liquid crystal type aromatic polyimide for use in the invention can be prepared by using the diamines of the formula (17) and the tetracarboxylic acid dianhydrides of the formula (19) as main components.
One or more of other diamines and tetracarboxylic acid dianhydrides can also be added to the polymerization reaction in the range giving no adverse effect on the liquid crystal property and other physical properties of resultant liquid crystal type aromatic polyimide.
Other diamines which can be used in combination include, for example, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, o-aminobenzylamine, 3-chloro-1,2-phenylenediamine, 4-chloro-1,2-phenylenediamine, 2,3-diaminotoluene, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 3,5-diaminotoluene, 2-methoxy-1,4-phenylenediamine, 4-methoxy-1,2-phenylenediamine, 4-methoxy-1,3-phenylenediamine, benzidine, 3,3-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminobenzoyl)benzene, 1,4-bis(3-aminobenzoyl)benzene, 1,3-bis(4-aminobenzoyl)benzene, 1,4-bis(4-aminobenzoyl)benzene, 1,3-bis(3-amino-.alpha.,.alpha.-dimethylbenzoyl)benzene, 1,4-bis(3-amino-.alpha.,.alpha.-dimethylbenzoyl)benzene, 1,3-bis(4-amino-.alpha.,.alpha.-dimethylbenzoyl)benzene, 1,4-bis(4-amino-.alpha.,.alpha.-dimethylbenzoyl)benzene, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]methane, 1,1-bis[4-(3-aminophenoxy)phenyl]ethane, 1,1-bis[4-(4-aminophenoxy)phenyl]ethane, 1,2-bis[4-(3-aminophenoxy)phenyl]ethane, 1,2-bis[4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[4-(3-aminophenoxy)phenyl]propane, 1,1-bis[4-(4-aminophenoxy)phenyl]propane, 1,2-bis[4-(3-aminophenoxy)phenyl]propane, 1,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis[4-(3-aminophenoxy)phenyl]propane, 1,3-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,1-bis[4-(3-aminophenoxy)phenyl]butane, 1,1-bis[4-(4-aminophenoxy)phenyl]butane, 1,2-bis[4-(3-aminophenoxy)phenyl]butane, 1,2-bis[4-(4-aminophenoxy)phenyl]butane, 1,3-bis[4-(3-aminophenoxy)phenyl]butane, 1,3-bis[4-(4-aminophenoxy)phenyl]butane, 1,4-bis[4-(3-aminophenoxy)phenyl]butane, 1,4-bis[4-(4-aminophenoxy)phenyl]butane, 2,2-bis[4-(3-aminophenoxy)phenyl]butane, 2,2-bis[4-(4-aminophenoxy)phenyl]butane, 2,3-bis[4-(3-aminophenoxy)phenyl]butane, 2,3-bis[4-(4-aminophenoxy)phenyl]butane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[ 4-(3-aminophenoxy)phenyl]sulfone and bis[4-(4-aminophenoxy)phenyl]sulfone. These diamines can be used singly or as a mixture.
The liquid crystal type aromatic polyimide used in the invention is a homopolymer having the recurring structural units of the formula (1) or the formula (4) which is prepared as above by using the aromatic diamine and the aromatic tetracarboxylic dianhydride as monomer components and a copolymer having a combination of the recurring structural units of the formula (1) and the formula (4). Also included is polyimide having at the polymer chain end thereof an aromatic ring which is unsubstituted or substituted with a radical having no reactivity for amine and dicarboxylic anhydride.
The liquid crystal type aromatic polyimide having at the polymer chain end thereof an aromatic ring which is unsubstituted or substituted with a radical having no reactivity for amine and dicarboxylic anhydride can be prepared by reacting aromatic diamine represented by the formula (18): ##STR36## wherein R.sub.1 .about.R.sub.5 are the same as above, for example, 1,3-bis[4-(4 aminophenoxy)-.alpha., .alpha.-dimethylbenzol]benzene with aromatic tetracarboxylic dianhydride of the formula (19): ##STR37## wherein R is the same as above, for example, pyromellitic dianhydride in the presence of aromatic dicarboxylic anhydride Of the formula (2): ##STR38## wherein Z is the same as above, and/or aromatic monoamine of the formula (3):
V--NH.sub.2 ( 3)
wherein V is the same as above.
Exemplary aromatic dicarboxylic anhydrides of the formula (2) include phthalic anhydride, 2,3-benzophenonedicarboxylic anhydride, 3,4-benzophenonedicarboxylic anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyldicarboxylic anhydride, 3,4-dicarboxyphenyl phenyl sulfone anhydride, 2,3-dicarboxyphenyl phenyl sulfide anhydride, 3,4-dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 1,2-anthracenedicarboxylic anhydride, 2,3-anthracenedicarboxylic anhydride and 1,9-anthracenedicarboxylic anhydride. These dicarboxylic acid anhydrides can be substituted with a radical having no reactivity for amine and dicarboxylic anhydride and can be used singly or as a mixture. Phthalic anhydride is most preferred in view of properties and utility of polyimide and liquid crystal type polyimide to be obtained.
The amount of aromatic dicarboxylic anhydride used is 0.001.about.1.0 mol per mol of the diamine of the formula (18). An amount less than 0.001 mol leads to viscosity increase processing at high temperatures and causes deterioration of processability. On the other hand, an amount exceeding 1.0 mol results in lowered mechanical properties. Preferred amount is in the range of 0.01 to 0.5 mol.
Aromatic monoamines of the formula (3) includes, for example, aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, 2,6-xylidine, 3,4-xylidine, 3,5-xylidine, o-chloro-aniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, o-aminophenol, m-aminophenol, p-aminophenol, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine, p-phenetidine, o-aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehyde, o-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminophenyl phenyl ether, 3-aminophenyl phenyl ether, 4-aminophenyl phenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenyl phenyl sulfide, 3-aminophenyl phenyl sulfide, 4-aminophenyl phenyl sulfide, 2-aminophenyl phenyl sulfone, 3-aminophenyl phenyl sulfone, 4-aminophenyl phenyl sulfone, .alpha.-naphthylamine, .beta.-naphhylamine, 1-amino-2-naphthol, 2-amino-1-naphthol, 4-amino-1-naphthol, 5-amino-1-naphthol, 5-amino-2-naphthol, 7-amino-2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, and 9-aminoanthracene. These aromatic monoamines can be substituted with a radical having no reactivity for amine or dicarboxylic anhydride, and can be used singly or as a mixture.
The amount of aromatic monoamine is 0.001.about.1.0 mol per mol of the aromatic tetracarboxylic dianhydride of the above formula (19). An amount less than 0.001 mol leads to viscosity increase in processing at high temperatures and causes deterioration of processability. On the other hand, an amount exceeding 1.0 mol results in lowered mechanical properties. Preferred amount is in the range of 0.0.about.10.5 mol.
The liquid crystal type aromatic used in the invention can be prepared by any known processes. Following processes can be exemplified.
(A) A process for preparing aromatic polyamic acid in an organic solvent, isolating the aromatic polyamic acid by removing the solvent under reduced pressure or by pouring the resulting aromatic polyamic acid solution into a lean solvent, and imidizing the polyamic acid by heating to obtain liquid crystal type aromatic polyimide.
(B) A process for preparing an aromatic polyamic acid solution by the same procedures as (A), chemically imidizing polyamic acid by addition of a dehydrating agent such as acetic anhydride optionally in the presence of a catalyst, successively isolating resultant aromatic polyimide by known procedures and if desired, washing and drying the aromatic polyimide.
(C) A process for preparing an aromatic polyamic acid solution by the same procedures as (A) and successively conducting solvent removal and thermal imidization at the same time by heating under reduced pressure.
(D) A process for mixing raw material and solvents, and simultaneously conducting preparation of aromatic polyamic acid and imidization reaction thereof by heating optionally in the presence of a catalyst, azeotropic agent or dehydrating agent.
In preparing the liquid crystal type aromatic polyimide by these processes, it is particularly preferred to carry out the reaction in an organic solvent.
Organic solvents which can be used include, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethyl urea, hexamethylphosphoramide, phenol, o-cresol, m-cresol, p-cresol, m-cresylic acid, p-chlorophenol, xylenols and anisole. These solvents can be used singly or as a mixture.
When the liquid crystal type aromatic polyimide is prepared in the presence of aromatic dicarboxylic anhydride or aromatic monoamine in order to cap the polymer chain end, aromatic diamines, aromatic tetracarboxylic dianhydride, and aromatic dicarboxylic anhydride or aromatic monoamine are charged and reacted in the organic solvent by the following methods.
(1) A method for reacting aromatic tetracarboxylic dianhydride with aromatic diamine and successively adding dicarboxylic anhydride or aromatic monoamine to continue the reaction.
(2) A method for reacting aromatic diamine with aromatic dicarboxylic anhydride and successively adding aromatic tetracarboxylic dianhydride to continue the reaction. Alternatively, a method for reacting aromatic tetracarboxylic dianhydride with aromatic monoamine and successively adding aromatic diamine to continue the reaction.
(3) A method for simultaneously charging aromatic tetracarboxylic dianhydride, aromatic diamine and aromatic dicarboxylic anhydride or aromatic monoamine to carry out the reaction.
Any of the above methods can be employed for progressing the reaction.
In these methods, the reaction temperature for polymerization and imidization is 300.degree. C. or less. No particular limitation is imposed upon the reaction pressure and the reaction can be sufficiently carried out under atmospheric pressure.
The reaction time differs depending upon aromatic diamine, aromatic tetracarboxylic dianhydride, solvent and reaction temperature.
The reaction time of 4.about.24 hours is usually sufficient.
Aromatic tetracarboxylic dianhydride can be reacted with aromatic diamine by the above methods in the presence of aromatic dicarboxylic anhydride and/or aromatic monoamine such as phthalic anhydride and/or aniline to prepare liquid crystal type aromatic polyimide capped at the polymer chain end with an unsubstituted aromatic ring such as ##STR39## or an aromatic ring substituted with a radical having no reactivity for amine or carboxylic acid anhydride.
Next, the thermoplastic resin which can be used in the invention will be illustrated.
Aromatic polyimide used in the invention comprises a fundamental skeleton having recurring structural units of the formula (5): ##STR40## wherein X is a divalent radical selected from the group consisting of a direct bond, isopropylidene, hexafluorinated isopropylidene, carbonyl, thio and sulfonyl, and R is a tetravalent radical having 6.about.27 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected to each other with a direct bond or a bridge member.
In the aromatic polyimide of the formula (5), often used in particular are aromatic polyimide having recurring structural units of the formula (6): ##STR41## wherein X is a direct bond in the formula (5), and aromatic polyimide having recurring structural units of the formula (20): ##STR42## wherein X is --SO.sub.2 -- in the formula (5).
Also effective is another aromatic polyimide having recurring structural units of the formula (7): ##STR43##
The present inventors have developed the following aromatic polyimide copolymer in order to improve processability of polyimide of the formula (B). The aromatic polyimide copolymer is also effective for the invention.
The aromatic polyimide of the formula (B) is crystalline polyimide which has Tg of 260.degree. C., Tc of 310.degree..about.340.degree. C. and Tm of 367.degree..about.385.degree. C., and is melt processable and excellent in chemical resistance However, high Tm of 367.degree..about.385.degree. C. requires high processing temperature close to 400.degree. C.
In the case of comparing highly heat-resistant engineering plastics having similar levels of Tg, it has been generally known that crystalline resin having high crystallinity is excellent in chemical resistance and mechanical properties such as elastic modulus and amorphous resin having low crystallinity is excellent in processability.
Thus, crystalline resin and amorphous resin individually have both merits and drawbacks.
Consequently, it is further desired to improve processability of the crystalline polyimide having recurring structural units of the formula (B) while maintaining the essentially excellent heat resistance thereof.
As a result of investigation in order to improve such aromatic polyimide, the present inventors have provided a crystalline aromatic polyimide copolymer comprising 99.about.1% by mol of a fundamental skeleton having recurring structural units of the above formula (B) and 1.about.99% by mol of a fundamental skeleton having recurring structural units of the formula (8) [the formula (B) exclusive]: ##STR44## wherein R is ##STR45## wherein n is an integer of 0, 1, 2 or 3; Q is a direct bond, --O--, --S--, --CO--, --SO.sub.2 --, --CH.sub.2 --, --C(CH.sub.3).sub.2 -- or --C(CF.sub.3).sub.2 -- and may be the same or different when two or more A connects three or more aromatic rings each other; and R" is one ore more tetravalent radicals selected from the group consisting of ##STR46## wherein M is one or more divalent radicals selected from the group consisting of ##STR47##
The aromatic polyimide copolymers thus provided and particularly an aromatic polyimide copolymer wherein the recurring structural units of the formula (8) is represented by the following formula [the formula (B), exclusive]: ##STR48## wherein R is the same as above; have been found to improve processability in an amorphous state at high temperature, to provide polyimide having high heat resistance by forming a crystalline state in use after processing, and alternatively to improve processability by maintaining an amorphous state both in processing and in use, and to provide heat resistance even in an amorphous state. Thus, a highly heat-resistant engineering plastic having good processability, excellent chemical resistance and high elastic modulus has been provided.
The aromatic polyimide copolymer thus provided can be preferably used for the resin composition of the invention having improved melt-processability.
Aromatic polyimide homopolymers and copolymers which can be used in the invention also include a capped aromatic polyimide homopolymer and copolymer obtained by capped the above aromatic polyimide homopolymer and copolymer with aromatic dicarboxylic anhydride of the formula (2): ##STR49## wherein Z is a divalent radical having 6.about.15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected each other with a direct bond or a bridge member, and/or with aromatic monoamine of the formula (3):
V--NH.sub.2 ( 3)
wherein V is a monovalent radical having 6.about.15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected each other with a direct bond or a bridge member.
The homopolymers and copolymers of aromatic polyimide can be obtained by reacting one or more aromatic diamine with one or more aromatic tetracarboxylic dianhydride and thermally or chemically imidizing the resultant polyamic acid.
That is, for example, the aromatic polyimide of the formula (5) can be obtained by reacting one or more aromatic diamine of the formula (21): ##STR50## wherein X is a divalent radical selected from the group consisting of a direct bond, isopropylidene, hexafluorinated isopropylidene, carbonyl, thio and sulfonyl, or aromatic diamine of the formula (22): ##STR51## with one or more aromatic tetracarboxylic dianhydride.
Aromatic diamine which can be used for the reaction includes, for example,
bis[4-(3-aminophenoxy)phenyl]methane,
1,1-bis[4-(3-aminophenoxy)phenyl]ethane,
1,2-bis[4-(3-aminophenoxy)phenyl]ethane,
1,1-bis[4-(3-aminophenoxy)phenyl]propane,
1,2-bis[4-(3-aminophenoxy)phenyl]propane,
1,3-bis[4-(3-aminophenoxy)phenyl]propane,
2,2-bis[4-(3-aminophenoxy)phenyl]propane,
1,1-bis[4-(3-aminophenoxy)phenyl]butane,
1,2-bis[4-(3-aminophenoxy)phenyl]butane,
1,3-bis[4-(3-aminophenoxy)phenyl]butane,
1,4-bis[4-(3-aminophenoxy)phenyl]butane,
2,2-bis[4-(3-aminophenoxy)phenyl]butane,
2,3-bis[4-(3-aminophenoxy)phenyl]butane,
2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane,
4,4'-bis(3-aminophenoxy)biphenyl,
bis[4-(3-aminophenoxy)phenyl]ketone,
bis[4-(3-aminophenoxy)phenyl]sulfide and
bis[4-(3-aminophenoxy)phenyl]sulfone.
These aromatic diamines can be used singly or as a mixture. Preferred aromatic diamines are 4,4'-bis(3-aminophenoxy)biphenyl or bis [4-(3-aminophenoxy)phenyl]sulfone wherein X is a direct bond or a sulfone radical in the formula (21). 3,3'-Diaminobenzophenone of the formula (22) is also preferred.
Aromatic tetracarboxylic dianhydrides used for the reaction are represented by the formula (19): ##STR52## wherein R is a tetravalent radical having 6.about.27 carbon atoms and being selected from the group consisting of a monoaromatic aromatic radical connected to each other with a direct bond or a bridge member.
Exemplary aromatic tetracarboxylic dianhydrides include those used for the preparation of the liquid crystal type aromatic polyimide and have been already enumerated above. These aromatic tetracarboxylic dianhydrides can be used singly or as a mixture. Pyromellitic dianhydride is preferred.
The aromatic polyimide copolymer comprising a fundamental skeleton consisting of recurring structural units of the formula (6) and recurring structural units of the formula (8) can be obtained by reacting 4,4'-bis(3-aminophenoxy)biphenyl of the formula (23): ##STR53## in the presence of one or more diamine represented by the formula (24)
H.sub.2 N--R--NH.sub.2 ( 24)
wherein R is ##STR54## wherein n is an integer of 0, 1, 2 or 3; Q is a direct bond, --O--, --S--, --CO--, --SO.sub.2 --, --CH.sub.2 --, --C(CH.sub.3).sub.2 -- or --C(CF.sub.3).sub.2 -- and may be the same or different when two or more Q connects three or more aromatic rings each other; with one or more aromatic tetracarboxylic dianhydride of the formula (25): ##STR55## wherein R" is a tetravalent radical selected from the group consisting of ##STR56## wherein M is a divalent radical selected from the group consisting of ##STR57##
Exemplary aromatic diamines used in the reaction and represented by the formula (26): ##STR58## include m-phenylenediamine, o-phenylenediamine and p-phenylenediamine.
Exemplary aromatic diamines used in the reaction and represented by the formula (27): ##STR59## include benzidine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2'-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, and 2-(3-aminophenyl)-2-(4-aminophenyl)propane.
Exemplary aromatic diamines used in the reaction and represented by the formula (28): ##STR60## include 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminobenzoyl)benzene, 1,3-bis(4-aminobenzoyl)benzene, 1,4-bis(4-aminobenzoyl)benzene. 1,3-bis(3-amino-.alpha.,.alpha.-dimethylbenzyl)benzene, 1,3-bis(4-amino-.alpha.,.alpha.-dimethylbenzyl)benzene, 1,4-bis(3-amino-.alpha.,.alpha.-dimethylbenzyl)benzene and 1,4-bis(4-amino-.alpha.,.alpha.-dimethylbenzyl)benzene.
Exemplary aromatic diamines used in the reaction and represented by the formula (29): ##STR61## include 4,4'-bis(4-aminophenoxy)biphenyl, 3,3'-bis(4-aminophenoxy)biphenyl, 3,4'-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]ketone, bis[3-(3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[3-(4-aminophenoxy)phenyl]sulfide, bis[3-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis3-(4-aminophenoxy)phenyl]sulfone, bis[3-(3-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, bis[3-(4-aminophenoxy)phenyl]ether, bis[3-(3-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]methane, bis[3-(3-aminophenoxy)phenyl]methane, bis[3-(4-aminophenoxy)phenyl]methane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, and 2,2-bis[3-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane. These aromatic diamines can be used singly or as a mixture.
Representative aromatic tetracarboxylic dianhydrides which can be used as another monomer include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis[4-(1,2-dicarboxy)phenoxy]benzene dianhydride, 1,4-bis[4-(1,2-dicarboxy)phenoxy]benzene dianhydride, 4,4'-bis[4-(1,2-dicarboxy)phenoxy]biphenyl dianhydride, 4,4'-bis[4-(1,2-dicarboxy)phenoxy]benzophenone dianhydride, bis[4- {4-(1,2-dicarboxy)phenoxy} phenyl]sulfone dianhydride, 2,2-bis[4- {4-(1,2-dicarboxy)phenoxy} phenyl]sulfone dianhydride, and 2,2-bis[4- {4-(1,2-dicarboxy)phenoxy} phenyl]-1,1,1,3,3,3-hexafluoropropane dianhydride.
The aromatic polyimide having the formula (5),(6),(20) or (7) and the aromatic polyimide copolymer comprising the fundamental skeleton having recurring structural units consisting of 99% by mol of the formula (6) and 1.about.99% by mol of the formula (8) are individually prepared from corresponding monomers above. In addition to the requisite aromatic diamine and aromatic dicarboxylic dianhydride, other aromatic diamines or aromatic tetracarboxylic dianhydrides can be used in combination so long as giving no adverse effect on the good properties of the resulting homopolymer and copolymer of aromatic polyimide.
Aromatic diamines which can be used in combination include those exemplified in preparing the liquid crystal type aromatic polyimide as aromatic diamines capable of being used simultaneously, and can be selected from these exemplified diamines depending upon the object.
Aromatic tetracarboxylic dianhydride which can be used in combination can be suitably selected from the group exemplified in the aromatic tetracarboxylic dianhydride having the above formula (19).
The aromatic polyimide homopolymer and aromatic polyimide copolymer obtained by using one or more aromatic diamines and one or more aromatic tetracarboxylic dianhydrides as monomer components also include a capped aromatic polyimide homopolymer and capped aromatic polyimide copolymer which have at the polymer chain end thereof an aromatic ring which is unsubstituted or substituted with a radical having no reactivity for amine and dicarboxylic anhydride.
The capped homopolymer and capped copolymer can be prepared by reacting aromatic diamines of the above formulas (21), (22), (23), (24), (26), (27), (28), and (29) with tetracarboxylic dianhydrides of the above formula (19) and (25) in the presence of aromatic dicarboxylic anhydride of the formula (2): ##STR62## wherein Z is a divalent radical having 6.about.15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected each other with a direct bond or a bridge member, and/or aromatic monoamine of the formula (3):
V--NH.sub.2 ( 3)
wherein V is a monovalent radical having 6.about.15 carbon atoms and being selected form the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected to each other with a direct bond or a bridge member.
The aromatic dicarboxylic anhydride and aromatic monoamine which can be used in the process include those which can be used for preparing homopolymers and copolymers of liquid crystal type aromatic polyimide.
Any known process can be used for preparation of the above homopolymers and copolymers of aromatic polyimide and also for preparing the capped homopolymers and capped copolymers of aromatic polyimide which have an unsubstituted or substituted aromatic ring at the polymer chain end thereof.
For example, these known processes can react aromatic tetracarboxylic dianhydrides with aromatic diamines in the presence of aromatic dicarboxylic anhydride such as phthalic anhydride and/or aromatic monoamine such as aniline to prepare aromatic polyimide having at the polymer chain end an unsubstituted aromatic ring and/or an aromatic ring substituted with a radical having no reacting for amine and dicarboxylic anhydride, that is ##STR63##
When the melt-processable resin composition of the invention comprises liquid crystal type aromatic polyimide and aromatic polyimide, both or either one of these polymers can be capped at the polymer chain end thereof. Radicals derived from phthalic anhydride and aniline are preferred for the capping in particular.
Next, aromatic polyether sulfone which can be used in the invention comprises a fundamental skeleton having one or more recurring structural units of the formula (11): ##STR64## wherein X is a direct bond, ##STR65##
Representative aromatic polysulfones having following recurring structural units. ##STR66##
Other aromatic polyether sulfones having following recurring structural units. ##STR67##
Particularly typical aromatic polysulfones which have been marketed include polyether sulfone VICTREX PES (Trade Mark of ICI LTD.) having recurring structural units of the formula (30): ##STR68## and polysulfone DUEL POLYSULFONE (Trade Mark of Union Carbide Corp.) having recurring structural units of the formula (31): ##STR69## and polyaryl sulfone RADEL POLYSULFONE (Trade Mark of Union Carbide Corp.) having recurring structural units of the formula (32): ##STR70##
Polymerization degree of these aromatic polysulfones can be freely selected. Thus aromatic polysulfone having suitable melt viscosity for the desired blend can be arbitrarily selected.
Next, aromatic polyetherimide which can be used in the invention comprises a fundamental skeleton having one or more recurring structural units represented by the formula (12): ##STR71## wherein X is: ##STR72## and Y is: ##STR73##
Exemplary aromatic polyetherimide include those having recurring structural units of the following formulas: ##STR74##
The aromatic polyetherimide is marketed from G.E.Co. under the trade mark of Ultem-1000, Ultem-4000, Ultem-6000 etc.
Next, aromatic polyamideimide which can be used in the invention comprises a fundamental skeleton having one or more recurring structural units of the formula (D): ##STR75## wherein Y is divalent radical having 6.about.27 carbon atoms, and is particularly preferred to comprise a fundamental skeleton having recurring structural units of the formula (13): ##STR76## and/or the formula (14): ##STR77##
The aromatic polyamideimide is marketed from Amoco Corp. under the trade mark of TORLON.
Polymerization degree of the aromatic polyamideimide can be freely selected and thus the aromatic polyamideimide having suitable melt viscosity for the desired blend can be arbitrarily selected.
Further, aromatic polyether ketone which can be used in the invention comprises a fundamental skeleton having one or more recurring structural units of the formula (15): ##STR78## and/or the formula (16): ##STR79##
The melt-processable thermoplastic resin composition of the invention comprises one or more liquid crystal type aromatic polyimide selected from the group consisting of the liquid crystal type aromatic polyimide having recurring structural units of the above formula (1), the liquid crystal type aromatic polyimide having recurring structural units of the formula (4), the liquid crystal type aromatic polyimide copolymer comprising a fundamental skeleton having 1.about.99% by mol of the recurring structural units of the formula (1) and 99.about.1% by mol of the recurring structural units of the formula (4), and the liquid crystal type capped aromatic polyimide and the liquid crystal type capped aromatic polyimide copolymer which have at the polymer chain end an aromatic ring unsubstituted or substituted with a radical having no reactivity for amine and dicarboxylic anhydride, and one or more thermoplastic resin selected from the group consisting of other kinds of aromatic polyimide, aromatic polysulfone, aromatic polyetherimide, aromatic polyamideimide and aromatic polyether ketone.
The thermoplastic resin composition comprises 0.1.about.50% by weight of the liquid crystal type aromatic polyimide and 99.9.about.50% by weight of the thermoplastic resin.
The thermoplastic resin composition of the invention has extremely low melt viscosity in a high temperature range of 300.degree. C. or more. The fluidization effect of the liquid crystal type aromatic polyimide in the invention is good even in a small amount. The lower limit of the polyimide in the resin composition is 0.1% by weight, preferably 0.5% by weight.
The liquid crystal type aromatic polyimide has very excellent chemical resistance, flame retardance and mechanical strengths as compared with other heat resistant resin. On the other hand, the polyimide has disadvantages such as high anisotropy of mechanical strengths. Consequently, a high content of the liquid crystal type aromatic polyimide in the thermoplastic resin composition leads to unfavorably impaired essential characteristics of polyimide. The amount of the liquid crystal type aromatic polyimide has an upper limit in the composition and is usually 50% by weight or less, preferably 30% by weight or less, more preferably 10% by weight or less.
On preparing the thermoplastic resin composition of the invention, thermoplastic resin and liquid crystal type and the liquid crystal type aromatic polyimide can be blended by usually known methods, following methods are preferred.
1 The thermoplastic resin and liquid crystal type aromatic polyimide are preblended with a mortar, Henschel mixer, drum blender, tumbling mixer, ball mill and ribbon blender.
2 Thermoplastic resin is previously dissolved or suspended in an organic solvent, the liquid crystal type aromatic polyimide is added to the resulting solution or suspension and uniformly dissolved or suspended, and the solvent is successively removed from the mixture.
3 When thermoplastic resin is aromatic polyimide, the liquid crystal type aromatic polyimide is suspended or dissolved in an organic solvent solution of polyamic acid which is a precursor of polyimide, the resulting mixture is heat-treated 100.degree..about.400.degree. C. or chemically imidized with a common imidizing agent, and thereafter the solvent is removed by a known method.
4 When thermoplastic resin is aromatic polyimide, an organic solvent solution of polyamic acid which is a precursor of the aromatic polyimide is mixed with an organic solvent solution of polyamic acid which is the precursor of the liquid crystal type aromatic polyimide, the resulting mixture heat-treated at 100.degree..about.400.degree. C. or chemically imidized with common imidizing agent, and thereafter the solvent removed by a known method.
The mixture of the liquid crystal type aromatic polyimide and thermoplastic resin thus obtained is used as intact for various processing methods such as injection molding, compression molding, transfer molding and extrusion forming. It is more preferred to used the mixture after melt kneading.
Particularly in the preparation of the above composition, it is also a simple and effective method to mix powder and powder, pellet and pellet, or powder and pellet.
Melt kneading can be conducted with equipment commonly used for melt-kneading rubber and plastic, for example, hot rolls, Banbury mixer, Brabender and extruder. The melt-kneading temperature is set above the melt-flow temperature of the formulation and below the decomposition initiating temperature of the formulation. The temperature is usually 250.degree..multidot.420.degree. C., preferably 300.degree..about.400.degree. C.
The melt-processable resin composition of the invention can be preferably processed by injection molding or extrusion forming which provided a uniformly blended product and have high productivity. Other processing methods such as compression molding, transfer molding and sinter forming can also be employed.
Other resins can also be formulated in a suitable amount depending upon the use of product so long as giving no adverse effect on the object of the invention.
Other resins include, for example, thermoplastic resins such as polystyrene, polypropylene, polycarbonate, polyarylate, polyamide, polysulfone, polyether ketone, polyphenylene sulfide, polyamideimide, polyetherimide, modified polyphenylene oxide and other kinds of polyimide, and thermosetting resins.
One or more solid lubricants such as molybdenum disulfide, graphite, boron nitride, lead monoxide and lead powder can be added to the polyimide resin composition of the invention.
One or more reinforcements, for example, glass fiber, carbon fiber, aromatic polyamide fiber, potassium titanate fiber and glass beads can also be added to the composition.
Further, other additives such as antioxidants, heat stabilizers, ultraviolet absorbers, flame retardants, flame retarding adjuvants, antistatic agents and colorants can also be added to the composition.
The present invention will hereinafter be described in detail by way of examples.
In these examples, properties were measured by the following methods.
Inherent viscosity: 0.5 g of polyimide powder was dissolved by heating in 100 ml of a p-chlorophenol/phenol mixture in a weight ratio of 90/10. The solution was cooled to 35.degree. C. and viscosity was measured.
Glass transition temperature (Tg): Measured by DSC (Shimadzu DT-40 series, DSC-41M).
5% weight loss temperature: Measured by DTA-Tg (Shimadzu DT-40 series, DSC-40M) in the air.

SYNTHESIS EXAMPLE 1
To a reaction vessel equipped with a stirrer, reflux condenser, water separator and nitrogen inlet tube, 5.29 kg (10.0 mols) of 1,3-bis[4-(4-aminophenoxy)-.alpha., .alpha.-dimethylbenzyl)benzene, 2.094 kg (9.6 moles) of pyromellitic dianhydride, 138 g (1.5 mols) of .gamma.-picoline and 23.0 kg of m-cresol were charged. The mixture was heated to 145.degree. C. with stirring in a nitrogen atmosphere while distilling out about 340 g of water. The reaction was further continued at 140.degree.-150.degree. C. for 4 hours. The reaction mixture was cooled to the room temperature and poured into 81.2 kg of methyl ethyl ketone.
The precipitated polyimide was filtered, washed with methyl ethyl ketone, predried in a nitrogen atmosphere at 50.degree. C. for 24 hours, and dried at 200.degree. C. for 6 hours to obtain 6.85 kg (97.3% yield) of polyimide powder.
The polyimide powder had an inherent viscosity of 0.49 dl/g and 5% weight loss temperature of 525.degree. C. in the air. Two heat absorption peaks were observed at 274.degree. C. and 294.degree. C. in DSC measurement.
SYNTHESIS EXAMPLES 2.about.6
The same procedures as described in Synthesis Example 1 were carried out by using various diamines and tetracarboxylic dianhydrides which are illustrated in Table 1 to obtain various kinds of polyimide powder.
Table 1 illustrates synthesis conditions, inherent viscosity, glass transition temperature and 5% weight loss temperature of the polyimide powder.
TABLE 1______________________________________Synthesis Aromatic Tetracarboxylic Td 5%Example diamine *1 dianhydride *2 .eta. *3 Tg *4 *5No. kg (mol) kg (mol) (dl/g) (.degree.C.) (.degree.C.)______________________________________2 m-BP PMDA 0.45 245 560 3.68 2.072 (10.0) (9.5)3 m-BS PMDA 0.50 256 540 4.32 2.094 (10.0) (9.6)4 mBAPP PMDA 0.55 218 528 4.11 2.116 (10.0) (9.7)5 m-APS BTDA 0.49 195 524 4.01 3.093 (10.0) (9.6)6 m-BP OPDA 0.43 199 542 3.68 2.947 (10.0) (9.5)______________________________________ *1 mBP: 4,4bis(3-aminophenoxy)biphenyl mBS: bis[4(3-aminophenoxy)phenyl]sulfone mBAPP: 2,2bis[4(3-aminophenoxy)phenyl]sulfone]propane mAPS: bis[4(3-aminophenoxy)phenyl]sulfide *2 PMDA: pyromellitic dianhydride BTDA: 3,3',4,4benzophenone tetracarboxylic dianhydride ODPA: Bis(3,4dicarboxyphenyl)ether dianhydride *3 inherent viscosity *4 Glass transition temperature *5 5% weight loss temperature
SYNTHESIS EXAMPLE 7
The same procedures as described in Synthesis Example 1 were carried out except that 118.49 g(0.80 g) of phthalic anhydride was added in the reaction.
The polyimide powder thus obtained was 6.93 kg (97.0% yield) and had an inherent viscosity of 0.49 dl/g and 5% weight loss temperature of 536.degree. C. in the air. Two heat absorption peaks were observed at 274.degree. C. and 295.degree. C. by DSC measurement.
SYNTHESIS EXAMPLE 8
The same procedures as described in Synthesis Example 1 were carried out except that 158.54 g (0.80 mol) of 1,8-naphthalene dicarboxylic anhydride was added in the reaction.
The polyimide powder thus obtained was 7.02 kg (97.0% yield) and had an inherent viscosity of 0.50 dl/g and 5% weight loss temperature of 538.degree. C. in the air. Two heat absorption peaks were observed at 275.degree. C. and 297.degree. C. by DSC measurement.
SYNTHESIS EXAMPLE 9
The same procedures as described in Synthesis Example 2 were carried out except that 148.11 g (1.00 mol) of phthalic anhydride was added in the reaction to obtain polyimide powder.
Table 2 illustrates synthesis conditions, inherent viscosity, glass transition temperature and 5% weight loss temperature of the polyimide powder obtained.
SYNTHESIS EXAMPLE 10
The same procedures as described in Synthesis Example 3 were carried out except that 118.49 g (0.80 mol) of phthalic anhydride was added in the reaction to obtain polyimide powder.
Table 2 illustrates synthesis conditions, inherent viscosity, glass transition temperature, and 5% weight loss temperature of the polyimide powder obtained.
SYNTHESIS EXAMPLE 11
The same procedures as described in Synthesis Example 4 were carried out except that 88.87 g (0.60 mol) of phthalic anhydride was added in the reaction to obtain polyimide powder.
Table 2 illustrates synthesis conditions, inherent viscosity, glass transition temperature, and 5% weight loss temperature of the polyimide powder obtained.
SYNTHESIS EXAMPLE 12
The same procedures as described in Synthesis Example 2 were carried out except that 198.18 g (1.00 mol) of 1,8-naphthalenedicarboxy lic anhydride was added in the reaction to obtain polyimide powder.
Table 2 illustrates synthesis conditions, inherent viscosity, glass transition temperature, and 5% weight loss temperature of the polyimide powder obtained.
TABLE 2______________________________________Synthesis Aromatic Tetracarboxylic Td 5%Example Diamine *1 dianhydride *2 .eta. *3 Tg *4 *5No. kg (mol) kg (mol) (dl/g) (.degree.C.) (.degree.C.)______________________________________ 9 m-BP PMDA 0.46 244 562 3.68 2.072 (10.0 (9.5)10 m-BS PMDA 0.49 254 548 4.32 2.094 (10.0) (9.6)11 mBAPP PMDA 0.54 218 534 4.11 2.116 (10.0) (9.7)12 m-BP PMDA 0.47 245 560 3.68 2.072 (10.0) (9.5)______________________________________ *1 mBP: 4,4Bis(3-aminophenoxy)biphenyl mBS: bis[4(3-aminophenoxy)phenyl]sulfone mBAPP: 2,2bis[4(3-aminophenoxy)phenyl]propane *2 PMDA: Pyromellitic dianhydride *3 Inherent viscosity *4 Glass transition temperature *5 5% weight loss temperature
SYNTHESIS EXAMPLE 13
To a reaction vessel equipped with a stirrer, reflux condenser, water separator and nitrogen inlet tube, 3.50 kg(9.5 mols) of 4,4'-bis(3-aminophenoxy)biphenyl, 2.18 kg (10.0 mols) of pyromellitic dianhydride, 140 g (1.5 mols) of .gamma.-picoline, 93.0 g (1.0 mol) of aniline and 23.0 kg of m-cresol were charged. The mixture was heated to 145.degree. C. with stirring in a nitrogen atmosphere while distilling out about 360 g of water. The reaction was further continued at 140.degree..about.150.degree. C. for 4 hours. The reaction mixture was cooled to the room temperature and poured into 81.2 kg of methyl ethyl ketone.
The precipitated polyimide was filtered, washed with methyl ethyl ketone, predried at 50.degree. C. for 24 hours in a nitrogen atmosphere and dried at 200.degree. C. for 6 hours to obtain 5.25 kg (97.0% yield) of polyimide powder.
The polyimide obtained had an inherent viscosity of 0.46 dl/g, glass transition temperature of 247.degree. C. and 5% weight loss temperature of 555.degree. C. in the air.
SYNTHESIS EXAMPLE 14
The same procedures as described in Synthesis Example 13 were carried out by using 107.15 g (1.0 mol) of p-toluidine in place of 93.0 g (1.0 mol) of aniline to obtain 52.6 kg (97.0% yield) of polyimide powder.
The polyimide powder had an inherent viscosity of 0.47 dl/g, glass transition temperature of 247.degree. C. and 5% weight loss temperature of 552.degree. C. in the air.
SYNTHESIS EXAMPLE 15
The same procedures as described in Synthesis Example 13 were carried out by using 5.07 kg (9.6 mol) of 1,3-bis[4-(4-aminophenoxy)-.alpha., .alpha.-dimethylbenzyl]benzene in place of 3.50 kg (9.5 mol) of 4,4'-bis(3-aminophenoxy)biphenyl to obtain 6.76 kg (97.0% yield) of polyimide powder. The polyimide powder had an inherent viscosity of 0.47 dl/g and 5% weight loss temperature of 532.degree. C. Two heat absorption peaks were observed at 274.degree. C. and 295.degree. C. by DSC measurement.
SYNTHESIS EXAMPLE 16
The same procedures as described in Synthesis Example 15 were carried out by using 85.72 g (0.8 mol) of p-toluidine in place of 74.4 g (0.8 mol) of aniline to obtain 6.77 kg (97.0% yield) of polyimide powder. The polyimide powder had an inherent viscosity of 0.48 dl/g and 5% weight loss temperature of 535.degree. C. Two heat absorption peaks were observed at 274.degree. C. and 297.degree. C. by DSC measurement.
SYNTHESIS EXAMPLE 17
The same procedures as described in Synthesis Example 13 were carried out by using 3.98 kg (9.7 mol) of 2,2-bis[4-(3-aminophenoxy) phenyl]propane in place of 3.50 kg (9.5 mol) of 4,4'-bis(3-aminophenoxy) biphenyl to obtain 5.70 kg (97.3% yield) of polyimide powder. The polyimide powder had an inherent viscosity of 0.54 dl/g, glass transition temperature of 217.degree. C. and 5% weight loss temperature of 534.degree. C. in the air.
SYNTHESIS EXAMPLE 18
To a reaction vessel equipped with a stirrer, reflux condenser, water separator and nitrogen inlet tube, 2.123 kg (10.0 mol) of 3,3'-diaminobenzophenone, 3.093 kg (9.6 mol) of 3,3',4,4'-benzophenonetetrac arboxylic dianhydride, 138 g (1.5 mol) of .gamma.-picoline and 20.9 kg of m-cresol were charged. The mixture was heated to 145.degree. C. with stirring in a nitrogen atmosphere while distilling out about 340 g of water. The reaction was further carried out at 140.degree..about.150.degree. C. for 4 hours.
The reaction mixture was cooled to the room temperature and poured into 81.2 kg of methyl ethyl ketone.
Precipitated polyimide was filtered, washed with methyl ethyl ketone, predried at 50.degree. C. for 24 hours in a nitrogen atmosphere and dried at 200.degree. C. for 6 hours to obtain 4.74 kg (97.3% yield) of polyimide powder. The polyimide powder had an inherent viscosity of 0.4 dl/g, glass transition temperature of 240.degree. C. and 5% weight loss temperature of 532.degree. C. in the air.
SYNTHESIS EXAMPLE 19
The same procedures as described in Synthesis Example 18 were carried out except that 118.49 g (0.80 mol) of phthalic anhydride was added in the reaction to obtain 4.88 kg (98.0% yield) of polyimide powder. The polyimide powder had an inherent viscosity of 0.48 dl/g, glass transition temperature of 245.degree. C. and 5% weight loss temperature of 550.degree. C.
SYNTHESIS EXAMPLE 20
The same procedures as described in Synthesis Example 18 were carried out except that 158.54 (0.80 g ) of 1,8-naphthalenedicarboxylic anhydride wa added in the reaction to obtain 4.86 kg (97.0% yield) of polyimide powder. The polyimide powder had on inherent viscosity of 0.49 dl/g, glass transition temperature of 247.degree. C. and 5% weight loss temperature of 538.degree. C. in the air.
SYNTHESIS EXAMPLE 21
To a reaction vessel equipped with a stirrer, reflux condenser, water separator and nitrogen inlet tube, 2.038 kg (9.6 mol) of 3,3'-diaminobenzophenone, 3.222 kg (10.0 mol) of 3,3',4,4'-benzophenonetetrac arboxylic dianhydride, 138 g (1.5 mol) of .gamma.-picoline, 74.50 g (0.8 mol) of aniline and 20.9 kg of m-cresol were charged. The mixture was heated to 145.degree. C. with stirring in a nitrogen atmosphere while distilling out about 340 g of water. The reaction was further carried out at 140.degree..about.150.degree. C. for 4 hours. The reaction mixture was cooled to the room temperature and poured into 81.2 kg of methyl ethyl ketone.
Precipitated polyimide was filtrated, washed with methyl ethyl ketone, predried at 50.degree. C. for 24 hours in a nitrogen atmosphere and dried at 200.degree. C. for 6 hours to obtain 4.74 Kg (97.3% yield) of polyimide powder.
The polyimide powder had an inherent viscosity of 0.48 dl/g, glass transition temperature of 240.degree. C. and 5% weight loss temperature of 548.degree. C. in the air.
SYNTHESIS EXAMPLE 22
The same procedures as described in Synthesis Example 21 were carried out by using 85.72 g (0.8 mol) of p-toluidine in place of 74.50 g (0.8 mol) of aniline to obtained 4.85 kg (97.5% yield) of polyimide powder. The polyimide powder had an inherent viscosity of 0.49 dl/g, glass transition temperature of 244.degree. C. and 5% weight loss temperature of 545.degree. C. in the air.
SYNTHESIS EXAMPLE 23
To a reaction vessel equipped with a stirrer, reflux condenser, water separator and nitrogen inlet tube, 3.316 kg (9.00 mol) of 4,4'-bis(3-aminophenoxy)biphenyl, 0.200 kg (1.00 mol) of 4,4'-diaminodiphenylether, 2.072 kg (9.50 mol) of pyromellitic dianhydride, 140 g (1.5 mol) of .gamma.-picoline and 22.4 kg of m-cresol were charged. The mixture was heated to 145.degree. C. with stirring in a nitrogen atmosphere while distilling out about 340 g of water. The reaction was further continued for 4 hours at 140.degree..about.150.degree. C. Thereafter, the reaction mixture was cooled to the room temperature and poured into 56.1 Kg of methyl ethyl ketone.
The precipitated powder was filtered, washed with methyl ethyl ketone, predried at 50.degree. C. for 24 hours in a nitrogen atmosphere and dried at 200.degree. C. for 6 hours to obtain 5.09 kg (97.0 & yield) of polyimide powder. The polyimide powder had an inherent viscosity of 0.50 dl/g, glass transition temperature of 250.degree. C. and 5% weight loss temperature of 542.degree. C. in the air. Tc and Tm were not observed.
SYNTHESIS EXAMPLE 24
The same procedures as described in Synthesis Example 23 were carried out except that 3.316 Kg (9.00 mols) of 4,4'-bis(3-aminophenoxy) biphenyl, 0.200 kg (1.00 mol) of 4,4'-diaminodiphenyl ether and 2.072 kg (9.50 mols) of pyromellitic dianhydride were replaced by 2.579 kg (7.00 mols) of 4,4'-bis(3-aminophenoxy)biphenyl, 1.297 kg (3.00 mols) of bis[4-(3-aminophenoxy)phenyl]sulfone and 2.094 kg (9.60 mols) of pyromellitic dianhydride. Polyimide powder thus obtained was 5.51 kg (98.0% yield) and had an inherent viscosity of 0.51 dl/g, glass transition temperature of 253.degree. C. and 5% weight loss temperature of 539.degree. C. in the air. Tc and Tm were not observed.
SYNTHESIS EXAMPLE 25
The same procedures as described in Synthesis Example 23 were carried out except that 148.11 kg (1.00 mol) of phthalic anhydride was added to the reaction. Polyimide powder thus obtained was 5.26 kg (97.8% yield) and had an inherent viscosity of 0.50 dl/g, glass transition temperature of 254.degree. C. and 5% weight loss temperature of 546.degree. C. in the air. Tc and Tm were not observed.
SYNTHESIS EXAMPLE 26
The same procedures as described in Synthesis Example 23 were carried out except that 195.68 kg (1.00 mol) of 1,8-naphthalenedicarboxylic anhydride was added to the reaction. Polyimide powder thus obtained was 5.31 kg (98.0% yield) and had an inherent viscosity of 0.49 dl/g, glass transition temperature of 250.degree. C. and 5% weight loss temperature of 543.degree. C. in the air. Tc and Tm were not observed.
SYNTHESIS EXAMPLE 27
To a reaction vessel equipped with a stirrer, reflux condenser and nitrogen inlet tube, 3.150 kg (8.55 mols) of 4,4'-bis(3-aminophenoxy) biphenyl, 0.190 kg (0.95 mol) of 4,4'-diaminodiphenyl ether, 2.18 kg (10.0 mols) of pyromellitic dianhydride, 140 g (1.5 mols) of .gamma.-picoline and 93.12 g of aniline and 23.0 kg m-cresol were charged. The mixture was heated to 145.degree. C. with stirring in a nitrogen atmosphere while distilling out about 360 g of water. The reaction was further continued for 4 hours at 140.degree..about.150.degree. C. Thereafter, the reaction mixture was cooled to the room temperature and poured into 81.2 kg of methyl ethyl ketone.
The precipitated powder was filtered, washed with methyl ethyl ketone, predried at 50.degree. C. for 24 hours in a nitrogen atmosphere and dried at 200.degree. C. for 6 hours to obtain 5.16 kg (98.2% yield) of polyimide powder. The polyimide powder had an inherent viscosity of 0.49 dl/g, glass transition temperature of 256.degree. C. and 5% weight loss temperature of 549.degree. C. in the air. Tc and Tm were not observed.
SYNTHESIS EXAMPLE 28
The same procedures as described in Synthesis Example 27 were carried out except that 93.12 g (1.0 mol) of aniline was replaced by 107.15 g (1.0 mol) of p-toluidine. Polyimide powder thus obtained was 5.16 kg (98.0% yield) and had an inherent viscosity of 0.49 dl/g, glass transition temperature of 255.degree. C. and 5% weight loss temperature of 547.degree. C. in the air.
SYNTHESIS EXAMPLE 29
The same procedures as described in Synthesis Example 27 were carried out except that 3.150 kg (8.55 mols) of 4,4'-bis(3-aminophenoxy) biphenyl, 0.190 kg (0.95 mol) of 4,4'-diaminodiphenyl ether and 93.12 g (1.0 mol) of aniline were replaced by 2.476 kg (6.72 mols) of 4,4'-bis(3-aminophenoxy)biphenyl, 1.246 kg (2.88 mols) of bis[4-(3-aminophenoxy)phenyl]sulfone and 74.50 (0.80 mol) of aniline.
Polyimide powder thus obtained was 5.49 kg (97.8% yield) and had an inherent viscosity of 0.50 dl/g, glass transition temperature of 251.degree. C. and 5% weight loss temperature of 544.degree. C. in the air.
SYNTHESIS EXAMPLE 30
The same procedures as described in Synthesis Example 29 were carried out except that 74.50 g (0.80 mol) was replaced by 85.72 g (0.80 mol) of p-toluidine. Polyimide powder thus obtained was 5.52 kg (98.0% yield) and had an inherent viscosity of 0.50 dl/g, glass transition temperature of 252.degree. C. and 5% weight loss temperature of 540.degree. C. in the air.
SYNTHESIS EXAMPLE 31
To a reaction vessel equipped with a thermometer, reflux condenser and a stirrer, 200 g of N,N-dimethylformamide (DMF), 65 g (0.409 mol) of 3,4-difluoronitrobenzene, 69.1 g (0.199 mol) of 1,3-bis(4-hydroxycumyl) benzene and 33.1 g (0.239 mol) of potassium carbonate were charged and warmed to 80.degree. C. with stirring. After aging the mixture at 80.degree. C. for 6 hours, inorganic salts was removed by filtration. The filtrate was mixed with 50 ml of water and cooled to the room temperature. The precipitated crystal was filtered and slugged with isopropyl alcohol to obtain 129.4 g (97% yield) of 1,3-bis[4-(4-nitro-6-fluorophenoxy)-.alpha., .alpha.-dimethylbenzyl]benzene having a melting point of 150.7.degree..about.151.8.degree. C.
Successively, to a reduction vessel equipped with a thermometer, reflux condenser and stirrer, 115 g (0.184 mol) of 1,3-bis[4-(4-nitro-6-fluorophenoxy)-.alpha., .alpha.-dimethylbenzyl]benzene, 250 g of isopropyl alcohol and 4.8 g of 5%-Pd/c having a moisture content of 50% were charged and reacted at 70.degree..about.80.degree. C. for 4 hours in a hydrogen atmosphere. After finishing the reaction, the catalyst was filtered off and the filtrate was concentrated under reduced pressure to obtain 84.2 g (81% yield) of 1,3-bis[4-(4-amino-6-fluorophenoxy)-.alpha., .alpha.-dimethylbenzyl]benzene as a light yellow crystal having a melting point of 130.4.about.132.9.
______________________________________Elemental analyses (C.sub.36 H.sub.34 N.sub.2 O.sub.2 F.sub.2) C H N F______________________________________Calculated (%) 76.52 6.07 5.96 6.73Found (%) 76.55 6.11 5.91 6.77______________________________________
Further, to a reaction vessel equipped with a stirrer, reflux condenser, water separator and nitrogen inlet tube, 56.47 g (0.1 mol) of 1,3-bis[4-(4-amino-6-fluorophenoxy)-.alpha., .alpha.-dimethylbenzyl]benzene, 21.38 (0.098 mol) of pyromellitic dianhydride, 0.592 (0.004 mol) of phthalic anhydride, 1.40 g of .gamma.-picoline and 311.4 g of m-cresol were charged and heated to 150.degree. C. with stirring in a nitrogen atmosphere and reacted at 150.degree. C. for 4 hours while distilling out about 3.6 ml of water.
After finishing the reaction, the reaction mixture was cooled to the room temperature and poured into about 2.0 liter of methyl ethyl ketone. Precipitated powder was filtered, washed with methyl ethyl ketone, and dried at 50.degree. C. for 24 hours in the air and at 180.degree. C. for 4 hours under reduced pressure to obtain 72.56 g (97.0% yield) of polyimide powder. The polyimide powder thus obtained has an inherent viscosity of 0.50 dl/g, glass transition temperature of 186.degree. C. and melting point of 350.degree. C.
Further, 30 parts of weight of the polyimide powder was mixed with 70 parts by weight of marketed polyether sulfone VICTREX PES 4100P (Trade Mark of ICI Ltd.) and measured melt viscosity at 370.degree. C. after residence time of 5 minutes. Following results were obtained.
______________________________________Polyether sulfone 5700 poisePolyether sulfone/Polyimide 3350 poise______________________________________
Melt viscosity was greatly reduced by mixing the thus obtained polyimide with polyether sulfone. The strand obtained was oriented to the direction of extrusion and essential property of liquid crystal type high polymers such as fibrillated structure was observed.
SYNTHESIS EXAMPLE 32
To a reaction vessel equipped with a thermometer, reflux condenser and a stirrer, 200 g of N,N-dimethylformamide (DMF), 10 g of toluene, 80 g (0.466 mol) of 2-chloro-6-nitrotoluene, 78.8 g (0.227 mol) of 1,3-bis(4-hydroxycumyl)benzene and 37.7 g (0.273 mol) of potassium carbonate were charged and heated to 150.degree. C. with stirring. After aging the mixture at 150.degree. C. for 7 hours, the mixture was cooled to 90.degree. C. and inorganic salts was removed by filtration. The filtrate was mixed with 56 ml of water and cooled to the room temperature. The precipitated crystal was filtered and slugged with isopropyl alcohol to obtain 133.9 g (96% yield) of 1,3-bis[4-(4-nitro-6-methylphenoxy)-.alpha., .alpha.-dimethylbenzyl]benzene having a melting point of 116.3.degree..about.117.6.degree. C.
Successively, to a reduction vessel equipped with a thermometer, reflux condenser and stirrer, 120 g (0.195 mol) of 1,3-bis[4-(4-nitro-6-methylphenoxy)-.alpha., .alpha.-dimethylbenzyl]benzene, 400 g of isopropyl alcohol and 5 g of 5%-Pd/c having a moisture content of 50% were charged and reacted at 70.degree..about.80.degree. C. for 4 hours in a hydrogen atmosphere. After finishing the reaction, the catalyst was filtered off and the filtrate was concentrated under reduced pressure to obtain 89.0 g (82% yield) of 1,3-bis[4-(4-amino-6-methylphenoxy)-.alpha., .alpha.-dimethylbenzyl]benzene as a light yellow crystal having a melting point of 118.1.about.118.2.
______________________________________Elemental analyses (C.sub.38 H.sub.40 N.sub.2 O.sub.2 F.sub.2) C H N______________________________________Calculated (%) 81.98 7.24 5.03Found (%) 82.18 7.22 5.15______________________________________
The same procedures as described in Synthesis Example 31 were carried out by using 55.68 g (0.1 mol) of 1,3-bis[4-(4-amino-6-methylphenoxy)-.alpha., .alpha.-dimethylbenzyl]benzene to obtain 71.29 g (96.3% yield) of polyimide powder. The polyimide powder had an inherent viscosity of 0.51 dl/g and glass transition temperature of 185.degree. C.
Further, 30 parts by weight of the polyimide powder was mixed with 70 parts by weight of marketed polyether sulfone VICTREX PES 4100P (Trade Mark of ICI Ltd.) and measured melt viscosity at 370.degree. C. after residence time of 5 minutes. Following results were obtained.
______________________________________Polyether sulfone 5700 poisePolyether sulfone/Polyimide 3230 poise______________________________________
Melt viscosity was greatly reduced by mixing the thus obtained polyimide with polyether sulfone. The strand obtained was oriented to the direction of extrusion and essential property of liquid crystal type high polymers such as fibrillated structure was observed.
SYNTHESIS EXAMPLE 33
To a reaction vessel equipped with a thermometer, reflux condenser and a stirrer, 700 ml of N,N-dimethylformamide (DMF), 30 ml of toluene, 87 g (0.386 mol) of 2-chloro-5-nitrobenzotrifluoride, 63.6 g (0.184 mol) of 1,3-bis(4-hydroxycumyl)benzene and 53.3 g (0.386 mol) of potassium carbonate were charged and heated to 110.degree. C. with stirring. After aging the mixture at 110.degree. C. for 4 hours, the mixture was cooled to 80.degree. C. and inorganic salts was removed by filtration. The filtrate was mixed with 30 ml of water and cooled to the room temperature. The precipitated crystal was filtered and slugged with isopropyl alcohol to obtain 120 g (90% yield) of 1,3-bis[4-(4-nitro-6-trifluoromethylphenoxy)-.alpha., .alpha.-dimethylbenzyl]benzene having a melting point of 127.4.degree..about.128.4.degree. C.
Successively, to a reduction vessel equipped with a thermometer, reflux condenser and stirrer, 90 g (0.124 mol) of 1,3-bis[4-(4-nitro-6-trifluoromethylphenoxy)-.alpha., .alpha.-dimethylbenzyl]benzene, 500 ml of methyl cellosolve and 5 g of 5%-Pd/c having a moisture content of 50% were charged and reacted at 70.degree..about.80.degree. C. for 4 hours in a hydrogen atmosphere. After finishing the reaction, the catalyst was filtered off and the filtrate was concentrated under reduced pressure to obtain 73.4 g (89% yield) of 1,3-bis[4-(4-amino-6-trifluoromethylphenoxy)-.alpha., .alpha.-dimethylbenzyl]benzene as a light yellow crystal having a melting point of 118.5.about.119.2.
______________________________________Elemental analyses (C.sub.38 H.sub.34 N.sub.2 O.sub.2 F.sub.2) C H N F______________________________________Calculated (%) 68.67 5.16 4.21 17.15Found (%) 68.78 5.22 4.15 17.01______________________________________
Further, to a reaction vessel equipped with a stirrer, reflux condenser, water separator and nitrogen inlet tube, 66.47 g (0.1 mol) of 1,3-bis[4-(4-amino-6-trifluoromethylphenoxy)-.alpha., .alpha.-dimethylbenzyl]benz ene, 21.38 (0.098 mol) of pyromellitic dianhydride, 0.592 (0.004 mol) of phthalic anhydride, 1.40 g of .gamma.-picoline and 351.4 g of m-cresol were charged and heated to 150.degree. C. with stirring in a nitrogen atmosphere and reacted at 150.degree. C. for 4 hours while distilling out about 3.6 ml of water.
After finishing the reaction, the reaction mixture was cooled to the room temperature and poured into about 2.0 liter of methyl ethyl ketone. Precipitated powder was filtered, washed with methyl ethyl ketone, and dried at 50.degree. C. for 24 hours in the air and 180.degree. C. for 4 hours under reduced pressure to obtain 83.22 g (98.1% yield) of polyimide powder. The polyimide powder thus obtained had an inherent viscosity of 0.45 dl/g, glass transition temperature of 186.degree. C. and melting point of 196.degree. C.
Following results were obtained on the elemental analyses.
______________________________________ C H N F______________________________________Calculated (%) 68.08 3.82 3.31 13.46Found (%) 67.86 3.75 3.40 13.02______________________________________
A polyimide film having a thickness of 50 .mu.m was prepared by pressing the polyimide power at 350.degree. C. under pressure of 300 psi. The film had dielectric constant of 3.02 at 60 Hz, 2.99 at 3 KHz 2.96 at 1 MHz.
Further, 30 parts by weight of the polyimide powder was mixed with 70 parts by weight of marketed polyether sulfone VICTREX PES 4100P (Trade Mark of ICI Ltd.) and measured melt viscosity at 350.degree. C. and 370.degree. C. after residence time of 5 minutes. Following results were obtained.
______________________________________ 350.degree. C. 370.degree. C.______________________________________Polyether sulfone 12000 poise 5700 poisePolyether sulfone/Polyimide 5250 poise 3350 poise______________________________________
Melt viscosity was greatly reduced by mixing the thus obtained polyimide with polyether sulfone. The strand obtained was oriented to the direction of extrusion and essential property of liquid crystal type high polymers such as fibrillated structure was observed.
EXAMPLES 1.about.8
The polyimide powder obtained in Synthesis Examples 2 and 3 was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 1 in various proportions illustrated in Table 3. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 3.
COMPARATIVE EXAMPLES 1.about.8
Compositions outside the scope of the present invention were prepared and melt viscosity of these compositions was measured by the same procedures as described in Examples 1.about.8. Results are illustrated in Table 3.
TABLE 3______________________________________ L.C. type Flow testerPolyimide polyimide Melt Synthesis Synthesis tempera- vis- Example wt. Example 1 ture cosityNo. No. parts wt. parts (.degree.C.) (poise)______________________________________Comp. 2 100 0 400 5000Example 1Example 1 2 90 10 400 4060Example 2 2 70 30 400 2070Comp. 2 40 60 400 970Example 2Comp. 2 100 0 420 3100Example 3Example 3 2 90 10 420 2510Example 4 2 70 30 420 1220Comp. 2 40 60 420 620Example 4Comp. 3 100 0 400 5500Example 5Example 5 3 90 10 400 4420Example 6 3 70 30 400 2150Comp. 3 40 60 400 980Example 6Comp. 3 100 0 420 3400Example 7Example 7 3 90 10 420 2680Example 8 3 70 30 420 1300Comp. 3 40 60 420 650Example 8______________________________________ Note) L.C. type polyimide: Liquid crystal type polyimide
EXAMPLES 9.about.16
The polyimide powder obtained in Synthesis Examples 4 and 5 was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 1 in various proportions illustrated in Table 4. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 4.
COMPARATIVE EXAMPLES 9.about.16
Compositions outside the scope of the present invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 9.about.16. Results are illustrated in Table 4.
TABLE 4______________________________________ L.C. type Flow testerPolyimide polyimide Melt Synthesis Synthesis tempera- vis- Example wt. Example 1 ture cosityNo. No. part wt. part (.degree.C.) (poise)______________________________________Comp. 4 100 0 380 4240Example 9Example 9 4 90 10 380 3480Example 10 4 70 30 380 1700Comp. 4 40 60 380 820Example 10Comp. 4 100 0 400 2500Example 11Example 11 4 90 10 400 1860Example 12 4 70 30 400 1020Comp. 4 40 60 400 500Example 12Comp. 5 100 0 360 4800Example 13Example 13 5 90 10 360 3920Example 14 5 70 30 360 1860Comp. 5 40 60 360 890Example 14Comp. 5 100 0 380 2600Example 15Example 15 5 90 10 380 1960Example 16 5 70 30 380 1080Comp. 5 40 60 380 520Example 16______________________________________ Note) L.C. type polyimide; Liquid crystal type polyimide
EXAMPLES 17.about.20
The polyimide powder obtained in Synthesis Example 6 was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 1 in various proportions illustrated in Table 5. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 5.
COMPARATIVE EXAMPLES 17.about.20
Compositions outside the scope of the present invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 17.about.20. Results are illustrated in Table 5.
TABLE 5______________________________________ L.C. type Flow testerPolyimide polyimide Melt Synthesis Synthesis tempera- vis- Example wt. Example 1 ture cosityNo. No. part wt. part (.degree.C.) (poise)______________________________________Comp. 6 100 100 380 3820Example 17Example 17 6 90 10 380 2960Example 18 6 70 30 380 1620Comp. 6 40 60 380 730Example 18Comp. 6 100 0 400 2260Example 19Example 19 6 90 10 400 1980Example 20 6 70 30 400 1000Comp. 6 40 60 400 430Example 20______________________________________ Note: L.C. type polyimide Liquid crystal type polyimide
EXAMPLES 21.about.28
The polyimide powder obtained in Synthesis Examples 9 and 10 was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 7 in various proportions illustrated in Table 6. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 6.
COMPARATIVE EXAMPLES 21.about.28
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 21.about.28. Results are illustrated in Table 6.
TABLE 6______________________________________ L.C. type Flow testerPolyimide polyimide Melt Synthesis Synthesis tempera- vis- Example wt. Example 7 ture cosityNo. No. part part (.degree.C.) (poise)______________________________________Comp. 9 100 0 400 4800Example 21Example 21 9 90 10 400 3960Example 22 9 70 30 400 1980Comp. 9 40 60 400 890Example 22Comp. 9 100 0 420 3080Example 23Example 23 9 90 10 420 2490Example 24 9 70 30 420 1280Comp. 9 40 60 420 650Example 24Comp. 10 100 0 400 5300Example 25Example 25 10 90 10 400 4340Example 26 10 70 30 400 2100Comp. 10 40 60 400 950Example 26Comp. 10 100 0 420 3320Example 27Example 27 10 90 10 420 2600Example 28 10 70 30 420 1260Comp. 10 40 60 420 620Example 28______________________________________ Note) L.C. type polyimide: Liquid crystal type polyimide
EXAMPLES 29.about.32
The polyimide powder obtained in Synthesis Examples 11 was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 7 in various proportions illustrated in Table 7. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 7.
COMPARATIVE EXAMPLES 29.about.32
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 29.about.32. Results are illustrated in Table 7.
TABLE 7______________________________________ L.C. type Flow testerPolyimide polyimide Melt Synthesis Synthesis tempera- vis- Example wt. Example 7 ture cosityNo. No. parts wt. parts (.degree.C.) (poise)______________________________________Comp. 11 100 0 380 4110Example 29Example 29 11 90 10 380 3400Example 30 11 70 30 380 1620Comp. 11 40 60 380 780Example 30Comp. 11 100 0 400 2480Example 31Example 31 11 90 10 400 1800Example 32 11 70 30 400 1030Comp. 11 40 60 400 480Example 32______________________________________ Note) L.C. type polyimide: Liquid crystal type polyimide
EXAMPLES 33.about.36
The polyimide powder obtained in Synthesis Example 12 was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 8 in various proportions illustrated in Table 8. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 8.
COMPARATIVE EXAMPLES 33.about.36
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 33.about.36. Results are illustrated in Table 8.
TABLE 8______________________________________ L.C. type Flow testerPolyimide polyimide Melt Synthesis Synthesis tempera- vis- Example wt. Example 8 ture cosityNo. No. parts wt. parts (.degree.C.) (poise)______________________________________Comp. 12 100 0 400 4780Example 33Example 33 12 90 10 400 3950Example 34 12 70 30 400 1950Comp. 12 40 60 400 870Example 34Comp. 12 100 0 420 3090Example 35Example 35 12 90 10 420 2500Example 36 12 70 30 420 1290Comp. 12 40 60 420 660Example 36______________________________________ Note) L.C. type polyimide: Liquid crystal type polyimide
EXAMPLES 37.about.44
The polyimide powder obtained in Synthesis Examples 13 and 17 was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 15 in various proportions illustrated in Table 9. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 9.
COMPARATIVE EXAMPLES 37.about.44
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 37.about.44. Results are illustrated in Table 9.
TABLE 9______________________________________ L.C. type Flow testerPolyimide polyimide Melt Synthesis Synthesis tempera- vis- Example wt. Example 15 ture cosityNo. No. part wt. part (.degree.C.) (poise)______________________________________Comp. 13 100 0 400 5600Example 37Example 37 13 90 10 400 4300Example 38 13 70 30 400 2160Comp. 13 40 60 400 930Example 38Comp. 13 100 0 420 3700Example 39Example 39 13 90 10 420 2760Example 40 13 70 30 420 1360Comp. 13 40 60 420 720Example 40Comp. 17 100 0 380 4300Example 41Example 41 17 90 10 380 3320Example 42 17 70 30 380 1760Comp. 17 40 60 380 850Example 42Comp. 17 100 0 400 2480Example 43Example 43 17 90 10 400 1760Example 44 17 70 30 400 1030Comp. 17 40 60 400 420Example 44______________________________________ Note) L.C. type polyimide: Liquid crystal type polyimide
EXAMPLES 45.about.48
The polyimide powder obtained in Synthesis Examples 14 was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 16 in various proportions illustrated in Table 10. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 10.
COMPARATIVE EXAMPLES 45.about.48
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 45.about.48. Results are illustrated in Table 10.
TABLE 10______________________________________ L.C. typePolyimide polyimide Flow tester Synthesis Synthesis tempera- Melt vis- Example wt. Example 16 ture cosityNo. No. part wt. part (.degree.C.) (poise)______________________________________Comp. 14 100 0 400 5580Example 45Example 45 14 90 10 400 4370Example 46 14 70 30 400 2130Comp. 14 40 60 400 920Example 46Comp. 14 100 0 420 3730Example 47Example 47 14 90 10 420 2790Example 48 14 70 30 420 1380Comp. 14 40 60 420 750Example 48______________________________________ Note) L.C. type polyimide: Liquid crystal type polyimide
EXAMPLES 49.about.56
The polyimide powder obtained in Synthesis Examples 9, 10, 11, and 12 was dryblending with the liquid crystal type polyimide powder obtained in Synthesis Examples 7 and 8 in various proportions illustrated in Table 11. The compositions thus obtained was melt-kneaded and delivered from an extruder having a bore diameter of 40 mm and screw compression ratio of 3:1 and cut into uniform pallets.
The pallets thus obtained were injection molded as usual and the minimum injection pressure was measured.
Results are illustrated in Table 11.
COMPARATIVE EXAMPLES 49.about.56
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 49.about.56
Results are illustrated in Table 11.
TABLE 11______________________________________ Polyimide Minimum Synthesis L.C. type polyimide injection Example wt. Synthesis wt. pressure No part Example No. part (kg/cm.sup.2)*______________________________________Com. Ex. 49 9 100 7 0 650Example 49 9 90 7 10 540Example 50 9 70 7 30 210Com. Ex. 50 9 40 7 60 **Com. Ex. 51 10 100 7 0 680Example 51 10 90 7 10 560Example 52 10 70 7 30 280Com. Ex. 52 10 40 7 60 **Com. Ex. 53 11 100 7 0 550Example 53 11 90 7 10 460Example 54 11 70 7 30 220Com. Ex. 54 11 40 7 60 **Com. Ex. 55 12 100 8 0 660Example 55 12 90 8 10 560Example 56 12 70 8 30 220Com. Ex. 56 12 40 8 60 **______________________________________ *Lower minimum injection pressure indicates lower melt viscosity. **Lower than the detection limit 90 kg/cm.sup. 2.
EXAMPLES 57.about.60
The polyimide powder obtained in Synthesis Example 18 was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 1 in various proportions illustrated in Table 12. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 12.
COMPARATIVE EXAMPLES 57.about.60
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 57.about.60. Results are illustrated in Table 12.
TABLE 12______________________________________ L.C. typePolyimide polyimide Flow tester Synthesis Synthesis tempera- Melt vis- Example 18 Example wt. ture cosityNo. wt. part No. part (.degree.C.) (poise)______________________________________Comp. 100 1 0 380 10200Example 57 90 1 10 380 5900Example 58 70 1 30 380 2500Comp. 40 1 60 380 980Example 58Comp. 100 1 0 400 6200Example 59Example 59 90 1 10 400 3020Example 60 70 1 30 400 1640Comp. 40 1 60 400 800Example 60______________________________________
EXAMPLES 61.about.64
The polyimide powder obtained in Synthesis Example 19 was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 7 in various proportions illustrated in Table 13. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 13.
COMPARATIVE EXAMPLES 61.about.64
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 61.about.64. Results are illustrated in Table 13.
TABLE 13______________________________________ L.C. typePolyimide polyimide Flow tester Synthesis Synth. tempera- Melt vis- Example 19 Example wt. ture cosityNo. wt. part No. part (.degree.C.) (poise)______________________________________Comp. 100 7 0 380 9800Example 61Example 61 90 7 10 380 5640Example 62 70 7 30 380 2320Comp. 40 7 60 380 950Example 62Comp. 100 7 0 400 6120Example 63Example 63 90 7 10 400 2980Example 64 70 7 30 400 1600Comp. 40 7 60 400 760Example 64______________________________________
EXAMPLES 65.about.68
The polyimide powder obtained in Synthesis Example 20 was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 8 in various proportions illustrated in Table 14. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 14.
COMPARATIVE EXAMPLES 65.about.68
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 65.about.68. Results are illustrated in Table 14.
TABLE 14______________________________________ L.C. typePolyimide polyimide Flow tester Synthesis Synth. tempera- Melt vis- Example 20 Example wt. ture cosityNo. wt. part No. part (.degree.C.) (poise)______________________________________Comp. 100 8 0 380 11300Example 65Example 65 90 8 10 380 6100Example 66 70 8 30 380 2750Comp. 40 8 60 380 990Example 66Comp. 100 8 0 400 6520Example 67Example 67 90 8 10 400 3210Example 68 70 8 30 400 1770Comp. 40 8 60 400 890Example 68______________________________________
EXAMPLES 69.about.72
The polyimide powder obtained in Synthesis Example 21 was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 15 in various proportions illustrated in Table 15. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 15.
COMPARATIVE EXAMPLES 69.about.72
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 69.about.72. Results are illustrated in Table 15.
TABLE 15______________________________________ L.C. typePolyimide polyimide Flow tester Synthesis Synth. tempera- Melt vis- Example 21 Example wt. ture cosityNo. wt. part No. part (.degree.C.) (poise)______________________________________Comp. 100 15 0 380 10000Example 69Example 69 90 15 10 380 5880Example 70 70 15 30 380 2440Comp. 40 15 60 380 960Example 70Comp. 100 15 0 400 6180Example 71Example 71 90 15 10 400 2950Example 72 70 15 30 400 1630Comp. 40 15 60 400 840Example 72______________________________________
EXAMPLES 73.about.76
The polyimide powder obtained in Synthesis Example 22 was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 16 in various proportions illustrated in Table 16. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 16.
COMPARATIVE EXAMPLES 73.about.76
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 73.about.76. Results are illustrated in Table 16.
TABLE 16______________________________________ L.C. typePolyimide polyimide Flow tester Synthesis Synth. tempera- Melt vis- Example 22 Example wt. ture cosityNo. wt. part No. part (.degree.C.) (poise)______________________________________Comp. 100 16 0 380 10840Example 73Example 73 90 16 10 380 5880Example 74 70 16 30 380 2480Comp. 40 16 60 380 970Example 74Comp. 100 16 0 400 6180Example 75Example 75 90 16 10 400 3180Example 76 70 16 30 400 1720Comp. 40 16 60 400 830Example 76______________________________________
EXAMPLES 77.about.80
The polyimide powder obtained in Synthesis Example 19 and 21 were dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 7 and 15 in various proportions illustrated in Table 17 and 18. The compositions thus obtained was melt-kneaded and delivered from an extruder having a bore diameter of 40 mm and screw compression ratio of 3:1 and cut into uniform pallets.
The pallets thus obtained were injection molded as usual and the minimum injection pressure was measured. Results are illustrated in Table 17 and 18.
COMPARATIVE EXAMPLES 77.about.80
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 77.about.80. Results are illustrated in Table 17 and 18.
TABLE 17______________________________________ Polyimide Minimum Synthesis L.C. type polyimide injection Example wt. Synthesis wt. pressure* No part Example No. part (kg/cm.sup.2)______________________________________Com. Ex. 77 19 100 7 0 690Example 77 19 90 7 10 520Example 78 19 70 7 30 280Com. Ex. 78 19 40 7 60 **______________________________________
TABLE 18______________________________________ Polyimide Minimum Synthesis L.C. type polyimide injection Example wt. Synthesis wt. pressure* No parts Example No. parts (kg/cm.sup.2)______________________________________Com. Ex. 79 21 100 15 0 650Example 79 21 90 15 10 510Example 80 21 70 15 30 260Com. Ex. 80 21 40 15 60 **______________________________________ *Lower minimum injection pressure indicates lower melt viscosity. **Lower than the detection limit 90 kg/cm.sup.2.
EXAMPLES 81.about.88
The polyimide powder obtained in Synthesis Examples 23 and 24 was dry blended with the liquid crystal type polyimide powder obtained in Synthesis Example 1 in various proportion illustrated in Tables 19 and 20. Melt viscosity of the mixture was measured with a Koka type flow tester CFT-500(Trade Mark of Shimadzu Seisakusho Co.) by using an orifice of 0.1 cm in diameter and 1 cm in length under 100 kg load. Results are illustrated in Table 19 and 20.
Glass transition temperature (Tg) of the strand extruded from the flow tester was measured by DSC and illustrated in Tables 19 and 20.
Mixtures of aromatic polyimide copolymer with the liquid crystal type aromatic polyimide in the proportion of these examples had lower melt viscosity as compared with aromatic polyimide copolymer alone and were almost equal in Tg to that of aromatic polyimide copolymer.
COMPARATIVE EXAMPLES 81.about.88
Compositions outside the scope of the invention were used and melt viscosity was measured by the same procedures as carried out in Examples 81.about.88.
Results are illustrated in Tables 19 and 20.
TABLE 19______________________________________ Liquid Crystal Flow tester Polyimide Polyimide tem- Melt Synthesis Synth. pera- Vis- Example 23 Example (wt. ture cosity Tg (wt. part) No. part) (.degree.C.) (poise) (.degree.C.)______________________________________Comparative 100 1 0 400 16000 254Example 81Example 81 90 1 10 400 8300 250Example 82 70 1 30 400 3200 250Comparative 40 1 60 400 1200 244Example 82Comparative 100 1 0 420 8900 253Example 83Example 83 90 1 10 420 5680 250Example 84 70 1 30 420 2250 251Comparative 40 1 60 420 1050 244Example 84______________________________________
TABLE 20______________________________________ Liquid Crystal Flow tester Polyimide Polyimide tem- Melt Synthesis Synth. pera- Vis- Example 24 Example (wt. ture cosity Tg (wt. part) No. part) (.degree.C.) (poise) (.degree.C.)______________________________________Comparative 100 1 0 400 14200 251Example 85Example 85 90 1 10 400 6320 250Example 86 70 1 30 400 2800 251Comparative 40 1 60 400 980 245Example 86Comparative 100 1 0 420 5600 251Example 87Example 87 90 1 10 420 3900 250Example 88 70 1 30 420 1960 251Comparative 40 1 60 420 870 245Example 88______________________________________
EXAMPLES 89.about.96
The polyimide powder obtained in Synthesis Examples 25 and 29 was dry blended with the liquid crystal type polyimide powder obtained in Synthesis Example 7 in various proportion illustrated in Tables 21 and 22. Melt viscosity of the mixture was measured with a Koka type flow tester CFT-500(Trade Mark of Shimadzu Seisakusho Co.) by using an orifice of 0.1 cm in diameter and 1 cm in length under 100 kg load. Results are illustrated in Table 21 and 22.
Glass transition temperature (Tg) of the strand extruded from the flow tester was measured by DSC and illustrated in Tables 21 and 22.
Mixtures of aromatic polyimide copolymer with the liquid crystal type aromatic polyimide in the proportion of these examples had lower melt viscosity as compared with aromatic polyimide copolymer alone and were almost equal in Tg to that of aromatic polyimide copolymer.
COMPARATIVE EXAMPLES 89.about.96
Compositions outside the scope of the invention were used and melt viscosity was measured by the same procedures as carried out in Examples 89.about.96.
Results are illustrated in Tables 21 and 22.
TABLE 21______________________________________ Liquid Crystal Flow tester Polyimide Polyimide tem- Melt Synthesis Synth. pera- Vis- Example 25 Example (wt. ture cosity Tg (wt. part) No. part) (.degree.C.) (poise) (.degree.C.)______________________________________Comparative 100 7 0 400 15800 253Example 89Example 89 90 7 10 400 8000 251Example 90 70 7 30 400 3100 250Comparative 40 7 60 400 1100 246Example 90ComparativeExample 91 100 7 0 420 8860 254Example 91 90 7 10 420 5500 250Example 92 70 7 30 420 2200 251Comparative 40 7 60 420 980 246Example 92______________________________________
TABLE 22______________________________________ Liquid Crystal Flow tester Polyimide Polyimide tem- Melt Synthesis Synth. pera- Vis- Example 29 Example (wt. ture cosity Tg (wt. part) No. part) (.degree.C.) (poise) (.degree.C.)______________________________________Comparative 100 7 0 400 14600 251Example 93Example 93 90 7 10 400 6400 250Example 94 70 7 30 400 2780 251Comparative 40 7 60 400 990 245Example 94Comparative 100 7 0 420 5700 251Example 95Example 95 90 7 10 420 3860 249Example 96 70 7 30 420 1900 250Comparative 40 7 60 420 900 245Example 96______________________________________
EXAMPLES 97.about.100
The polyimide powder obtained in Synthesis Example 26 was dry blended with the liquid crystal type polyimide powder obtained in Synthesis Example 8 in various proportion illustrated in Table 23. Melt viscosity of the mixture was measured with a Koka type flow tester CFT-500(Trade Mark of Shimadzu Seisakusho Co.) by using an orifice of 0.1 cm in diameter and 1 cm in length under 100 kg load. Results are illustrated in Table 23.
Glass transition temperature (Tg) of the strand extruded from the flow tester was measured by DSC and illustrated in Table 23.
Mixtures of aromatic polyimide copolymer with the liquid crystal type aromatic polyimide in the proportion of these examples had lower melt viscosity as compared with aromatic polyimide copolymer alone and were almost equal in Tg to that of aromatic polyimide copolymer.
COMPARATIVE EXAMPLES 97.about.100
Compositions outside the scope of the invention were used and melt viscosity was measured by the same procedures as carried out in Examples 97.about.100. Results are illustrated in Table 23.
TABLE 23______________________________________ Liquid Crystal Flow tester Polyimide Polyimide tem- Melt Synthesis Synth. pera- Vis- Example 26 Example (wt. ture cosity Tg (wt. part) No. part) (.degree.C.) (poise) (.degree.C.)______________________________________Comparative 100 8 0 400 16100 255Example 97Example 97 90 8 10 400 8400 253Example 98 70 8 30 400 3280 252Comparative 40 8 60 400 1300 248Example 98Comparative 100 8 0 420 8960 253Example 99Example 99 90 8 10 420 5700 252Example 100 70 8 30 420 2400 253Comparative 40 8 60 420 1000 249Example 100______________________________________
EXAMPLES 101.about.108
The polyimide powder obtained in Synthesis Examples 27 and 30 was dry blended with the liquid crystal type polyimide powder obtained in Synthesis Example 15 in various proportion illustrated in Tables 24 and 25. Melt viscosity of the mixture was measured with a Koka type flow tester CFT-500(Trade Mark of Shimadzu Seisakusho Co.) by using an orifice of 0.1 cm in diameter and 1 cm in length under 100 kg load. Results are illustrated in Tables 24 and 25.
Glass transition temperature (Tg) of the strand extruded from the flow tester was measured by DSC and illustrated in Tables 24 and 25.
Mixtures of the aromatic polyimide copolymer with the liquid crystal type aromatic polyimide in the proportion of these examples had lower melt viscosity as compared with aromatic polyimide copolymer alone and were almost equal in Tg to that of aromatic polyimide copolymer.
COMPARATIVE EXAMPLES 101.about.108
Compositions outside the scope of the invention were used and melt viscosity was measured by the same procedures as carried out in Examples 101.about.108.
Results are illustrated in Tables 24 and 25.
TABLE 24______________________________________ Liquid Crystal Flow tester Polyimide Polyimide tem- Melt Synthesis Synth. pera- Vis- Example 27 Example (wt. ture cosity Tg (wt. part) No. part) (.degree.C.) (poise) (.degree.C.)______________________________________Comparative 100 15 0 400 16500 253Example 101Example 101 90 15 10 400 8600 252Example 102 70 15 30 400 3350 253Comparative 40 15 60 400 1240 246Example 102Comparative 100 15 0 420 9000 252Example 103Example 103 90 15 10 420 5860 253Example 104 70 15 30 420 2400 250Comparative 40 15 60 420 1080 249Example 104______________________________________
TABLE 25______________________________________ Liquid Crystal Flow tester Polyimide Polyimide tem- Melt Synthesis Synth. pera- Vis- Example 30 Example (wt. ture cosity Tg (wt. part) No. part) (.degree.C.) (poise) (.degree.C.)______________________________________Comparative 100 15 0 400 14800 250Example 105Example 105 90 15 10 400 6400 251Example 106 70 15 30 400 2880 248Comparative 40 15 60 400 990 247Example 106Comparative 100 15 0 420 5720 251Example 107Example 107 90 15 10 420 3960 250Example 108 70 15 30 420 2000 250Comparative 40 15 60 420 920 246Example 108______________________________________
EXAMPLES 109.about.112
Polyimide powder obtained in Synthesis Examples 28 was dry blended with liquid crystal type polyimide powder obtained in Synthesis Example 16 in various proportions illustrated in Tables 26. Melt viscosity of the mixture was measured with a Koka type flow tester CFT-500(Trade Mark of Shimadzu Seisakusho Co.) by using an orifice of 0.1 cm in diameter and 1 cm in length under 100 kg load. Results are illustrated in Table 26. Glass transition temperature (Tg) of the strand extruded from the flow tester was measured by DSC and illustrated in Table 26.
Mixtures of the aromatic polyimide copolymer with the liquid crystal type aromatic polyimide in the proportion of these examples had lower melt viscosity as compared with aromatic polyimide copolymer alone and were almost equal in Tg to that of aromatic polyimide copolymer.
COMPARATIVE EXAMPLES 109.about.112
Compositions outside the scope of the invention were used and melt viscosity was measured by the same procedures as carried out in Examples 109.about.112. Results are illustrated in Table 26.
TABLE 26______________________________________ Liquid Crystal Flow tester Polyimide Polyimide tem- Melt Synthesis Synth. pera- Vis- Example 28 Example (wt. ture cosity Tg (wt. part) No. part) (.degree.C.) (poise) (.degree.C.)______________________________________Comparative 100 16 0 400 16000 252Example 109Example 109 90 16 10 400 8200 252Example 110 70 16 30 400 3180 252Comparative 40 16 60 400 1180 246Example 110Comparative 100 16 0 420 8860 253Example 111Example 111 90 16 10 420 5480 251Example 112 70 16 30 420 2400 250Comparative 40 16 60 420 960 245Example 112______________________________________
EXAMPLES 113.about.120
Polyimide powder obtained in Synthesis Examples 25, 27, 29 and 30 was dry blended with liquid crystal type polyimide powder obtained in Synthesis Example 7 and 15 in various proportions illustrated in Tables 27 and 28.
The mixture was melt-kneaded with an extruder having a bore diameter of 40 mm and screw compression ratio of 3:1, and extruded to obtain uniform pellets.
The pellets thus obtained were injection molded with common injection molding machine and minimum injection pressure of the molded article was measured. Results are illustrated in Tables 27 and 28.
Mixtures of the aromatic polyimide copolymer with the liquid crystal type aromatic polyimide in the proportion of these examples had lower minimum injection pressure as compared with the aromatic polyimide copolymer alone and were better in processability.
COMPARATIVE EXAMPLES 113.about.120
Compositions outside the scope of the invention were used and minimum injection pressure was measured by the same procedures as carried out in Examples 113.about.120. Results are illustrated in Tables 27 and 28.
Compositions which did not contain liquid crystal type aromatic polyimide at all had high minimum injection pressure. When the amount of the liquid crystal type aromatic polyimide exceeds 50 parts by weight of the aromatic polyimide copolymer, melt viscosity became too low and minimum injection pressure could not be measured.
TABLE 27______________________________________ Minimum Polyimide L.C. type polyimide injection Synthesis wt. Synthesis wt. pressure Example parts Example No. parts (kg/cm.sup.2)*______________________________________Com. Ex. 113 25 100 7 0 680Example 113 25 90 7 10 560Example 114 25 70 7 30 320Com. Ex. 114 25 40 7 60 **Com. Ex. 115 29 100 7 0 670Example 115 29 90 7 10 540Example 116 29 70 7 30 290Com. Ex. 116 29 40 7 60 **______________________________________ *Lower minimum injection pressure indicates lower melt viscosity. **Lower than the detection limit 40 kg/cm.sup.2.
TABLE 28______________________________________ Minimum Polyimide L.C. type polyimide injection Synthesis wt. Synthesis wt. pressure Example parts Example No. parts (kg/cm.sup.2)*______________________________________Com. Ex. 117 27 100 15 0 650Example 117 27 90 15 10 520Example 118 27 70 15 30 280Com. Ex. 118 27 40 15 60 **Com. Ex. 119 30 100 15 0 670Example 119 30 90 15 10 560Example 120 30 70 15 30 270Com. Ex. 120 30 40 15 60 **______________________________________ *Lower minimum injection pressure indicates lower melt viscosity. **Lower than the detection limit 40 kg/cm.sup.2.
EXAMPLES 121 and 122
The pellets which were obtained in Examples 113 and 115 by blending the aromatic polyimide copolymer with the liquid crystal type aromatic polyimide in a ratio of 90:10 were injection molded at an injection temperature of 360.degree..about.400.degree. C. and mold temperature of 150.degree. C. Mechanical properties of molded specimens were measured and results are illustrated in Table 29. Tensile strength, tensile elastic modulus and elongation were measured in accordance with ASTM D-638.
The mixture of the aromatic polyimide copolymer and liquid liquid crystal type aromatic polyimide in a proportion of these examples had mechanical properties equivalent to the aromatic polyimide copolymer alone in Comparative Examples 121 and 122. Thus, mechanical properties were not decreased even though the liquid crystal type aromatic polyimide was mixed in the range of the invention.
COMPARATIVE EXAMPLES 121 and 122
Pellets obtained in Comparative Examples 113 and 115 were injection molded by the same procedures as carried out in Examples 121 and 122. Mechanical properties of molded specimens were measured and results are illustrated in Table 29.
TABLE 29______________________________________ Tensile Pellets Tensile elastic used for strength modulas Elongation molding (kg/cm.sup.2) (kg/cm.sup.2) (%)______________________________________Comparative Comparative 910 290 66example 121 example 113Example 121 Example 113 900 290 64Comparative Comparative 930 270 77example 122 example 115Example 122 Example 115 930 280 78______________________________________
EXAMPLES 123.about.126
Aromatic polysulfone resin powder, VICTOREX PES 4100P (Trade Mark of ICI Ltd.) was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 1 in various proportions illustrated in Table 30. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 30.
COMPARATIVE EXAMPLES 123.about.126
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 123.about.126. Results are illustrated in Table 30.
TABLE 30______________________________________ L.C. type VICTREX polyimide Flow tester PES 4100P Synth. tempera- Melt vis- wt. Example wt. ture cosityNo. part No. part (.degree.C.) (poise)______________________________________Comp. 100 1 0 370 5700Example 123Example 123 90 1 10 370 3540Example 124 70 1 30 370 1720Comp. 40 1 60 370 900Example 124Comp. 100 1 0 390 3300Example 125Example 125 90 1 10 390 2000Example 126 70 1 30 390 1050Comp. 40 1 60 390 540Example 126______________________________________
EXAMPLES 127.about.130
Aromatic polysulfone resin powder, VICTOREX PES 4100P (Trade Mark of ICI Ltd.) was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 7 in various proportions illustrated in Table 31. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 31.
COMPARATIVE EXAMPLES 123, 125, 127, 128
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 127.about.130. Results are illustrated in Table 31.
TABLE 31______________________________________ L.C. type VICTREX polyimide Flow tester PES 4100P Synth. tempera- Melt vis- wt. Example wt. ture cosityNo. part No. part (.degree.C.) (poise)______________________________________Comp. 100 7 0 370 5700Example 123Example 127 90 7 10 370 3580Example 128 70 7 30 370 1800Comp. 40 7 60 370 920Example 127Comp. 100 7 0 390 3300Example 125Example 129 90 7 10 390 2040Example 130 70 7 30 390 1080Comp. 40 7 60 390 580Example 128______________________________________
EXAMPLES 131.about.134
Aromatic polysulfone resin powder, VICTOREX PES 4100P (Trade Mark of ICI Ltd.) was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 15 in various proportions illustrated in Table 32. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 32.
COMPARATIVE EXAMPLES 123, 125, 129 and 130
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 131.about.134. Results are illustrated in Table 32.
TABLE 32______________________________________ L.C. type VICTREX polyimide Flow tester PES 4100P Synth. tempera- Melt vis- wt. Example wt. ture cosityNo. part No. part (.degree.C.) (poise)______________________________________Comp. 100 15 0 370 5700Example 123Example 131 90 15 10 370 3350Example 132 70 15 30 370 1550Comp. 40 15 60 370 820Example 129Comp. 100 15 0 390 3300Example 125Example 133 90 15 10 390 1800Example 134 70 15 30 390 1010Comp. 40 15 60 390 480Example 130______________________________________
EXAMPLES 135.about.138
Aromatic polysulfone resin powder, UDEL POLYSULFONE P-1700 (Trade Mark of Union Carbide Corp.) was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 7 in various proportions illustrated in Table 33. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 33.
COMPARATIVE EXAMPLES 131.about.134
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 135.about.138. Results are illustrated in Table 33.
TABLE 33______________________________________ UDEL POLYS L.C. type Flow tester ULFONE polyimide tem- Melt P-1700 Synth. pera- vis- wt. Example wt. ture cosityNo. part No. part (.degree.C.) (poise)______________________________________Comp. 100 7 0 370 4900Example 131Example 135 90 7 10 370 3020Example 136 70 7 30 370 1580Comp. 40 7 60 370 650Example 132Comp. 100 7 0 390 3020Example 133Example 137 90 7 10 390 1860Example 138 70 7 30 390 1040Comp. 40 7 60 390 420Example 134______________________________________
EXAMPLES 139.about.142
Aromatic polysulfone resin powder, UDEL POLYSULFONE P-1700 (Trade Mark of Union Carbide Corp.) was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 8 in various proportions illustrated in Table 34. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 34.
COMPARATIVE EXAMPLES 131, 133, 135 and 136
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 139.about.142. Results are illustrated in Table 34.
TABLE 34______________________________________ UDEL POLYS L.C. type Flow tester ULFONE polyimide tem- Melt P-1700 Synth. pera- vis- wt. Example wt. ture cosityNo. part No. part (.degree.C.) (poise)______________________________________Comp. 100 8 0 370 4900Example 131Example 139 90 8 10 370 3140Example 140 70 8 30 370 1640Comp. 40 8 60 370 700Example 135Comp. 100 8 0 390 3020Example 133Example 141 90 8 10 390 1890Example 142 70 8 30 390 1050Comp. 40 8 60 390 480Example 136______________________________________
EXAMPLES 143.about.146
Aromatic polysulfone resin powder, UDEL POLYSULFONE P-1700 (Trade Mark of Union Carbide Corp.) was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 15 in various proportions illustrated in Table 35. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 35.
COMPARATIVE EXAMPLES 131, 133, 137 and 138
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 143.about.146. Results are illustrated in Table 35.
TABLE 35______________________________________ UDEL POLYS L.C. type Flow tester ULFONE polyimide tem- Melt P-1700 Synth. pera- vis- wt. Example wt. ture cosityNo. part No. part (.degree.C.) (poise)______________________________________Comp. 100 15 0 370 4900Example 131Example 143 90 15 10 370 3000Example 144 70 15 30 370 1520Comp. 40 15 60 370 600Example 137Comp. 100 15 0 390 3020Example 133Example 145 90 15 10 390 1840Example 146 70 15 30 390 1000Comp. 40 15 60 390 400Example 138______________________________________
EXAMPLES 147.about.150
Aromatic polysulfone resin powder, RADEL POLYSULFONE A-400 (Trade Mark of Union Carbide Corp.) was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 7 in various proportions illustrated in Table 36. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 36.
COMPARATIVE EXAMPLES 139.about.142
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 147.about.150. Results are illustrated in Table 36.
TABLE 36______________________________________ RADEL POLY L.C. type Flow tester SULFONE polyimide tem- Melt A-400 Synth. pera- vis- wt. Example wt. ture cosityNo. part No. part (.degree.C.) (poise)______________________________________Comp. 100 7 0 370 5200Example 139Example 147 90 7 10 370 3020Example 148 70 7 30 370 1500Comp. 40 7 60 370 720Example 140Comp. 100 7 0 390 3120Example 141Example 149 90 7 10 390 1800Example 150 70 7 30 390 1020Comp. 40 7 60 390 500Example 142______________________________________
EXAMPLES 151.about.154
Aromatic polysulfone resin powder, RADEL POLYSULFONE A-400 (Trade Mark of Union Carbide Corp.) was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 15 in various proportions illustrated in Table 37. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 37.
COMPARATIVE EXAMPLES 139, 141, 143 and 144
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 151.about.154. Results are illustrated in Table 37.
TABLE 37______________________________________ RADEL POLY L.C. type Flow tester SULFONE polyimide tem- Melt A-400 Synth. pera- vis- wt. Example wt. ture cosityNo. part No. part (.degree.C.) (poise)______________________________________Comp. 100 15 0 370 5200Exmple 139Example 151 90 15 10 370 3000Example 152 70 15 30 370 1480Comp. 40 15 60 370 700Example 143Comp. 100 15 0 390 3120Exmple 141Example 153 90 15 10 390 1770Example 154 70 15 30 390 1030Comp. 40 15 60 390 480Example 144______________________________________
EXAMPLES 155.about.159
Aromatic polysulfone resin powder, UDEL POLYSULFONE A-400 (Trade Mark of Union Carbide Corp.) was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Example 16 in various proportions illustrated in Table 38. Melt viscosity of the composition obtained was measured with a Koka type flow tester (Shimadzu CFT-500) under 100 kg load by using an orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Table 38.
COMPARATIVE EXAMPLES 139, 141 145 and 146
Compositions outside the scope of the invention were prepared and melt viscosity of these compositions was measured by the same procedures as carried out in Examples 155.about.159.
Results are illustrated in Table 38.
TABLE 38______________________________________ RADEL POLY L.C. type Flow tester SULFONE polyimide tem- Melt A-400 Syn. pera- vis- wt. Example wt. ture cosityNo. part No. part (.degree.C.) (poise)______________________________________Comp. 100 16 0 370 5200Example 139Example 155 90 16 10 370 3080Example 156 70 16 30 370 1520Comp. 40 16 60 370 780Example 145Comp. 100 16 0 390 3120Example 141Example 157 90 16 10 390 1790Example 158 70 16 30 390 1050Comp. 40 16 60 390 520Example 146______________________________________
EXAMPLES 159.about.164
Aromatic polysulfone resin powder, VICTREX PES 4100P (Trade Mark of ICI Ltd.), UDEL POLYSULFONE P-1700 (Trade Mark of Union Carbide Corp.) and UDEL POLYSULFONE A-400 (Trade Mark of Union Carbide Corp.) were dryblended with the crystalline polyimide powder obtained in Synthesis Example 7 and 15 in various proportions illustrated in Table 39, 40 and 41. The compositions thus obtained was melt-kneaded and delivered from an extruder having a bore diameter of 40 mm and screw compression ratio of 3:1 and cut into uniform pellets.
The pellets thus obtained were injection molded as usual and the minimum injection pressure was measured. Results are illustrated in Tables 39, 40 and 41.
COMPARATIVE EXAMPLES 147.about.152
Compositions outside the scope of the invention were prepared and minimum injection pressure of these compositions was measured by the same procedures as carried out in Example 159.about.164. Results are illustrated in Table 39, 40 and 41.
TABLE 39______________________________________ VICTREX PE Minimum S 4100P L.C. type polyimide injection wt. Synthesis wt. pressure parts Example No. parts (kg/cm.sup.2)*______________________________________Com. Ex. 147 100 7 0 680Example 159 90 7 10 540Example 160 70 7 30 270Com. Ex. 148 40 7 60 **______________________________________
TABLE 40______________________________________ UDEL POLYS Minimum ULFONE L.C. type polyimide injection P-1700 Synthesis wt. pressure wt. parts Example No. parts (kg/cm.sup.2)*______________________________________Com. Ex. 149 100 7 0 560Example 161 90 7 10 420Example 162 70 7 30 200Com. Ex. 150 40 7 60 **______________________________________
TABLE 41______________________________________ RADEL POLY Minimum SULFONE L.C. type polyimide injection A-400 Synthesis wt. pressure wt. parts Example No. parts (kg/cm.sup.2)*______________________________________Com. Ex. 151 100 7 0 660Example 163 90 7 10 520Example 164 70 7 30 240Com. Ex. 152 40 7 60 **______________________________________ *Lower minimum injection pressure indicates lower melt viscosity. **Lower than the detection limit 90 kg/cm.sup.2.
EXAMPLES 165.about.184
Aromatic polyether imide ULTEM 1000 (Trade Mark of G E Co.) was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Examples 1, 7, 8, 15 and 16 in various proportions illustrated in Table 42.about.46. Melt viscosity of the compositions obtained was measured with a Koka type flew tester (Shimadzu CFT-500) under 100 kg load by using as orifice of 0.1 cm in diameter and 1 cm in length. Results are illustrated in Tables 42.about.46.
Glass transition temperature (Tg) of the strand extruded from the orifice was measured by DSC. Results are illustrated in Table 42.about.46.
The mixture of aromatic polyether imide and liquid crystal type aromatic polyimide in a proportion of the present example had lower melt viscosity than the aromatic polyether imide alone and was almost equal in Tg to the aromatic polyether imide, The strand obtained from the flow tester was tough as the strand of aromatic polyether imide alone.
COMPARATIVE EXAMPLE 153.about.172
Compositions outside the scope of the invention were prepared and melt viscosity of these composition was measured by the same procedures as carried out in Example 165.about.184. Results are illustrated in Table 42.about.46.
Aromatic polyether imide which does not contain the liquid crystal type aromatic polyimide at all had high melt viscosity. When the proportion of the liquid crystal type aromatic polyimide was 50 parts by weight or more for 50 parts by weight of aromatic polyether imide, melt viscosity was lowered and the strand obtained become brittle.
TABLE 42______________________________________ Liquid Crys- Ultem tal Polyimide Flow tester 1000 Synth. temper- Melt wt. Exam- (wt. ature Viscosity Tg part ple No. part) (.degree.C.) (poise) (.degree.C.)______________________________________Comparative 100 1 0 390 5900 216Example 153Example 165 90 1 10 390 4260 215Example 166 70 1 30 390 2200 215Comparative 40 1 60 390 960 214Example 154Comparative 100 1 0 400 4700 215Example 155Example 167 90 1 10 400 3520 215Example 168 70 1 30 400 1660 216Comparative 40 1 60 420 780 214Example 156______________________________________
TABLE 43______________________________________ Liquid Crys- Ultem tal Polyimide Flow tester 1000 Synth. temper- Melt wt. Exam- (wt. ature Viscosity Tg part ple No. part) (.degree.C.) (poise) (.degree.C.)______________________________________Comparative 100 7 0 390 5880 216Example 157Example 169 90 7 10 390 4200 214Example 170 70 7 30 390 2160 215Comparative 40 7 60 390 950 214Example 158Comparative 100 7 0 400 4680 215Example 159Example 171 90 7 10 400 3480 216Example 172 70 7 30 400 1600 214Comparative 40 7 60 420 740 215Example 160______________________________________
TABLE 44______________________________________ Liquid Crys- Ultem tal Polyimide Flow tester 1000 Synth. temper- Melt wt. Exam- (wt. ature Viscosity Tg part ple No. part) (.degree.C.) (poise) (.degree.C.)______________________________________Comparative 100 8 0 390 6080 215Example 161Example 173 90 8 10 390 4440 214Example 174 70 8 30 390 2320 216Comparative 40 8 60 390 980 215Example 162Comparative 100 8 0 400 4820 214Example 163Example 175 90 8 10 400 3640 218Example 176 70 8 30 400 1780 215Comparative 40 8 60 400 820 216Example 164______________________________________
TABLE 45______________________________________ Liquid Crys- Ultem tal Polyimide Flow tester 1000 Synth. temper- Melt wt. Exam- (wt. ature Viscosity Tg part ple No. part) (.degree.C.) (poise) (.degree.C.)______________________________________Comparative 100 15 0 390 5600 215Example 165Example 177 90 15 10 390 4060 217Example 178 70 15 30 390 2020 214Comparative 40 15 60 390 930 216Example 166Comparative 100 15 0 400 4400 216Example 167Example 179 90 15 10 400 3100 214Example 180 70 15 30 400 1480 215Comparative 40 15 60 420 720 216Example 168______________________________________
TABLE 46______________________________________ Liquid Crys- Ultem tal Polyimide Flow tester 1000 Synth. temper- Melt wt. Exam- (wt. ature Viscosity Tg part ple No. part) (.degree.C.) (poise) (.degree.C.)______________________________________Comparative 100 16 0 390 5920 217Example 169Example 181 90 16 10 390 4280 215Example 182 70 16 30 390 2260 216Comparative 40 16 60 390 980 214Example 170Comparative 100 16 0 400 4780 215Example 171Example 183 90 16 10 400 3600 217Example 184 70 16 30 400 1720 216Comparative 40 16 60 420 780 214Example 172______________________________________
EXAMPLE 185.about.188
Aromatic polyether imide ULTEM 1000 (Trade Mark of G E Co.) was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Examples 7 and 15 in various proportions illustrated in Table 47. The compositions thus obtained was melt-kneaded and delivered from an extruder having a bore diameter of 40 mm and screw compression ratio of 3:1 and cut into uniform pallets.
The pellets thus obtained were injection molded as usual and the minimum injection pressure was measured. Results are illustrated in Table 47.
The mixture of aromatic polyether imide and the liquid crystal type aromatic polyimide in a proportion of the examples had lower minimum injection pressure than better processability.
COMPARATIVE EXAMPLE 173.about.176
Compositions outside the scope of the invention were prepared and the minimum injection pressure was measured by the same procedures as carried out in Example 185.about.188. Results are illustrated in Table 47.
Aromatic polyether imide which does not contain the liquid crystal type aromatic polyimide at all had high minimum injection pressure. When the liquid crystal type aromatic polyimide was 50 parts by weight or more for 50 parts by weight of the aromatic polyether imide, melt viscosity became too low and injection molding was difficult. Thus, minimum injection pressure could not be measured.
TABLE 47______________________________________ L.C. type Minimum Ultem polyimide injection 1000 Synthesis wt. pressure wt. part Example No. part (kg/cm.sup.2)*______________________________________Com. Ex. 173 100 7 0 580Example 185 90 7 10 440Example 186 70 7 30 250Com. Ex. 174 40 7 60 **Com. Ex. 175 100 15 0 560Example 187 90 15 10 420Example 188 70 15 30 240Com. Ex. 176 40 15 60 **______________________________________ *Lower minimum injection pressure indicates lower melt viscosity. **Lower than the detection limit 90 kg/cm.sup.2.
EXAMPLE 189.about.208
Aromatic polyamideimide TORLON 4203 L (Trade Mark of Amoco Co.) was dry blended with the polyimide powder obtained in Synthesis Examples 1, 7, 8, 15 and 16 in various proportions illustrated in Table 48.about.52.
The mixture was melt-kneaded with an extruder having a bore diameter of 40 mm and screw compression ratio of 3:1, and extruded to obtained uniform pellets.
The pellets thus obtained were injection molded with a common injection molding machine and minimum injection pressure of the molded article was measured. Results are illustrated in Table 48.about.52.
The mixture of aromatic polyetheramideimide and liquid crystal type aromatic polyimide in a proportion of the present example had lower melt viscosity than the aromatic polyetheramideimide alone and was almost equal in Tg to the aromatic polyetheramideimide.
COMPARATIVE EXAMPLES 177.about.196
Compositions outside the scope of the invention were used and minimum injection pressure was measured by the same procedures as carried out in Examples 189.about.208.
Results are illustrated in Table 48.about.52.
TABLE 48______________________________________ TOR- Liquid Crys- LON tal Polyimide Flow tester 4203L Synth. temper- Melt wt. Exam- (wt. ature Viscosity Tg part ple No. part) (.degree.C.) (poise) (.degree.C.)______________________________________Comparative 100 1 0 380 72500 275Example 177Example 189 90 1 10 380 45000 274Example 190 70 1 30 380 26400 275Comparative 40 1 60 380 10700 273Example 178Comparative 100 1 0 400 25100 274Example 179Example 191 90 1 10 400 15500 272Example 192 70 1 30 400 9100 275Comparative 40 1 60 400 3700 273Example 180______________________________________
TABLE 49______________________________________ TOR- Liquid Crys- LON tal Polyimide Flow tester 4203L Synth. temper- Melt wt. Exam- (wt. ature Viscosity Tg part ple No. part) (.degree.C.) (poise) (.degree.C.)______________________________________Comparative 100 7 0 380 72200 276Example 181Example 193 90 7 10 380 45500 273Example 194 70 7 30 380 26800 275Comparative 40 7 60 380 11000 274Example 182Comparative 100 7 0 400 26800 274Example 183Example 195 90 7 10 400 16500 275Example 196 70 7 30 400 9700 276Comparative 40 7 60 400 3900 274Example 184______________________________________
TABLE 50______________________________________ TOR- Liquid Crys- LON tal Polyimide Flow tester 4203L Synth. temper- Melt wt. Exam- (wt. ature Viscosity Tg part ple No. part) (.degree.C.) (poise) (.degree.C.)______________________________________Comparative 100 8 0 380 72500 274Example 185Example 197 90 8 10 380 46300 275Example 198 70 8 30 380 27200 272Comparative 40 8 60 380 11000 274Example 186Comparative 100 8 0 400 26800 275Example 187Example 199 90 8 10 400 16600 276Example 200 70 8 30 400 9800 273Comparative 40 8 60 400 4000 275Example 188______________________________________
TABLE 51______________________________________ TOR- Liquid Crys- LON tal Polyimide Flow tester 4203L Synth. temper- Melt wt. Exam- (wt. ature Viscosity Tg part ple No. part) (.degree.C.) (poise) (.degree.C.)______________________________________Comparative 100 15 0 380 73000 274Example 189Example 201 90 15 10 380 43800 276Example 202 70 15 30 380 25700 274Comparative 40 15 60 380 10500 274Example 190Comparative 100 15 0 400 25300 275Example 191Example 203 90 15 10 400 14800 273Example 204 70 15 30 400 8700 275Comparative 40 15 60 400 3500 273Example 192______________________________________
TABLE 52______________________________________ TOR- Liquid Crys- LON tal Polyimide Flow tester 4203L Synth. temper- Melt wt. Exam- (wt. ature Viscosity Tg part ple No. part) (.degree.C.) (poise) (.degree.C.)______________________________________Comparative 100 16 0 380 72800 274Example 193Example 205 90 16 10 380 45000 275Example 206 70 16 30 380 26400 275Comparative 40 16 60 380 10800 274Example 194ComparativeExample 195 100 16 0 400 25800 276Example 207 90 16 10 400 15900 275Example 208 70 16 30 400 9300 273Comparative 40 16 60 400 3800 274Example 196______________________________________
EXAMPLES 209.about.212
Aromatic polyamideimide TORLON 4203 L (Trade Mark of Amoco Co.) was dry blended with the polyimide powder obtained in Synthesis Examples 7 and 15 in various proportions illustrated in Table 53.
The mixture was melt-kneaded with an extruder having a bore diameter of 40 mm and screw compression ratio of 3:1, and extruded to obtained uniform pellets.
The pellets thus obtained were injection molded with a common injection molding machine and minimum injection pressure of the molded article was measured. Results are illustrated in Table 53.
Mixtures of the aromatic polyamideimide with the liquid crystal type aromatic polyimide in the proportion of these examples had lower minimum injection pressure as compared with the aromatic polyamideimide alone and were better in processability.
COMPARATIVE EXAMPLES 197.about.200
Compositions outside the scope of the invention were used and minimum injection pressure was measured by the same procedures as carried out in Examples 209.about.212. Results are illustrated in Table 53.
Composition which did not contain liquid crystal type aromatic polyimide at all had high minimum injection pressure. When the aromatic of the liquid crystal type aromatic polyimide exceeds 50 parts by weight for 50 parts by weight of the aromatic polyamideimide melt viscosity became too low and minimum injection pressure could not be measured.
TABLE 53______________________________________ Minimum TORLON L.C. type polyimide injection 4203L Synthesis wt. pressure wt. part Example No. part (kg/cm.sup.2)*______________________________________Com. Ex. 197 100 7 0 610Example 209 90 7 10 470Example 210 70 7 30 280Com. Ex. 198 40 7 60 **Com. Ex. 199 100 15 0 610Example 211 90 15 10 460Example 212 70 15 30 270Com. Ex. 200 40 15 60 **______________________________________ *Lower minimum injection pressure indicates lower melt viscosity. **Lower than the detection limit 40 kg/cm.sup.2.
EXAMPLE 213
The pellets which were obtained in Example 209 by blending the aromatic polyamideimide with the liquid crystal type aromatic polyimide in a ratio of 90:10 were injection molded at an injection temperature of 360.degree..about.400.degree. C. and mold temperature of 160.degree. C. Mechanical properties of molded specimens were measured and results are illustrated in Table 54. Tensile strength, tensile elastic modulus and elongation were measured in accordance with ASTM D-638.
The mixture of the aromatic polyamideimide and the liquid crystal type aromatic polyimide in a proportion of these examples had mechanical properties equivalent to the aromatic polyamideimide alone in Comparative Example 201. Thus, mechanical properties were not decreased even though the liquid crystal type aromatic polyimide was mixed in the range of the invention.
COMPARATIVE EXAMPLE 201
Pellets obtained in Comparative Example 197 were injection mold by the procedures is carried out in Example 213 and mechanical properties of molded specimens were measured. Results are illustrated in Table 54.
TABLE 54______________________________________ Tensile Tensile elas- Pellets used strength tic modulus Elonga- for molding (Kg/cm.sup.2) (Kg/cm.sup.2) tion (%)______________________________________Comparative Comparative 1910 450 12Example 201 Example 197Example 213 Example 209 1920 450 11______________________________________
EXAMPLES 214.about.233
Aromatic polyether ketone VICTREX PEEK 450 P (Trade Mark of ICI Ltd.) was dry blended with the liquid crystal type polyimide powder obtained in Synthesis Examples 1, 7, 8, 15 and 16 in various proportions illustrated in Table 55.about.59. Melt viscosity of the mixture was measured with a Koka type flow tester CFT-500 (Trade Mark of Shimazu Seisakusho Co.) by using an orifice of 0.1 cm in diameter and 1 cm in length under 100 kg load. Results are illustrated in Table 55.about.59.
Glass transition temperature (Tg) of the strand extruded from the tester was measured by DSC and illustrated in table 55.about.59.
Mixtures of the aromatic polyether ketone with the liquid crystal type aromatic polyimide in the proportion of these examples had lower melt viscosity as compared with aromatic polyether ketone alone and were almost equal in Tg that of aromatic polyether ketone.
COMPARATIVE EXAMPLE 202.about.221
Comparative outside the scope of the invention were used and melt viscosity was measured by the same procedures as carried out in Examples 214.about.233. Results are illustrated in Table 55.about.59.
TABLE 55__________________________________________________________________________ Liquid Crystal Flow tester VICTREX Polyimide Melt PEEK 450P Synth. temperature Viscosity Tg wt. part Example No. (wt. part) (.degree.C.) (poise) (.degree.C.)__________________________________________________________________________Comparative 100 1 0 380 10500 143Example 202Example 214 90 1 10 380 6700 145Example 215 70 1 30 380 4000 144Comparative 40 1 60 380 1560 145Example 203Comparative 100 1 0 400 6100 144Example 204Example 216 90 1 10 400 5180 144Example 217 70 1 30 400 3200 145Comparative 40 1 60 400 1010 143Example 205__________________________________________________________________________
TABLE 56__________________________________________________________________________ Liquid Crystal Flow tester VICTREX Polyimide Melt PEEK 450P Synth. temperature Viscosity Tg wt. part Example No. (wt. part) (.degree.C.) (poise) (.degree.C.)__________________________________________________________________________Comparative 100 7 0 380 11000 144Example 206Example 218 90 7 10 380 6780 146Example 219 70 7 30 380 3980 145Comparative 40 7 60 380 1620 146Example 207Comparative 100 7 0 400 6220 146Example 208Example 220 90 7 10 400 5200 147Example 221 70 7 30 400 3180 144Comparative 40 7 60 400 1200 146Example 209__________________________________________________________________________
TABLE 57__________________________________________________________________________ Liquid Crystal Flow tester VICTREX Polyimide Melt PEEK 450P Synth. temperature Viscosity Tg wt. part Example No. (wt. part) (.degree.C.) (poise) (.degree.C.)__________________________________________________________________________Comparative 100 8 0 380 11800 145Example 210Example 222 90 8 10 380 6820 146Example 223 70 8 30 380 4120 145Comparative 40 8 60 380 1760 147Example 211Comparative 100 8 0 400 6320 145Example 212Example 224 90 8 10 400 5220 147Example 225 70 8 30 400 3430 146Comparative 40 8 60 400 1210 146Example 213__________________________________________________________________________
TABLE 58__________________________________________________________________________ Liquid Crystal Flow tester VICTREX Polyimide Melt PEEK 450P Synth. temperature Viscosity Tg wt. part Example No. (wt. part) (.degree.C.) (poise) (.degree.C.)__________________________________________________________________________Comparative 100 15 0 380 9860 145Example 214Example 226 90 15 10 380 6240 147Example 227 70 15 30 380 3680 145Comparative 40 15 60 380 1460 146Example 215Comparative 100 15 0 400 6020 144Example 216Example 228 90 15 10 400 5000 145Example 229 70 15 30 400 3040 145Comparative 40 15 60 400 1000 145Example 217__________________________________________________________________________
TABLE 59__________________________________________________________________________ Liquid Crystal Flow tester VICTREX Polyimide Melt PEEK 450P Synth. temperature Viscosity Tg wt. part Example No. (wt. part) (.degree.C.) (poise) (.degree.C.)__________________________________________________________________________Comparative 100 16 0 380 10200 143Example 218Example 230 90 16 10 380 6500 145Example 231 70 16 30 380 3880 144Comparative 40 16 60 380 1600 145Example 219Comparative 100 16 0 400 6000 146Example 220Example 232 90 16 10 400 5080 145Example 233 70 16 30 400 3160 146Comparative 40 16 60 400 1000 147Example 221__________________________________________________________________________
TABLE 60__________________________________________________________________________ Liquid Crystal Flow tester VICTREX Polyimide Melt PEK 220G Synth. temperature Viscosity Tg wt. part Example No. (wt. part) (.degree.C.) (poise) (.degree.C.)__________________________________________________________________________Comparative 100 1 0 380 7800 162Example 222Example 234 90 1 10 380 5200 164Example 235 70 1 30 380 3200 165Comparative 40 1 60 380 1240 163Example 223Comparative 100 1 0 400 4600 163Example 224Example 236 90 1 10 400 3480 164Example 237 70 1 30 400 2020 163Comparative 40 1 60 400 860 165Example 225__________________________________________________________________________
TABLE 61__________________________________________________________________________ Liquid Crystal Flow tester VICTREX Polyimide Melt PEK 220G Synth. temperature Viscosity Tg wt. part Example No. (wt. part) (.degree.C.) (poise) (.degree.C.)__________________________________________________________________________Comparative 100 7 0 380 7680 163Example 226Example 238 90 7 10 380 5100 164Example 239 70 7 30 380 3120 164Comparative 40 7 60 380 1200 165Example 227Comparative 100 7 0 400 4480 163Example 228Example 240 90 7 10 400 3360 165Example 241 70 7 30 400 1960 164Comparative 40 7 60 400 840 165Example 229__________________________________________________________________________
TABLE 62__________________________________________________________________________ Liquid Crystal Flow tester VICTREX Polyimide Melt PEK 220G Synth. temperature Viscosity Tg wt. part Example No. (wt. part) (.degree.C.) (poise) (.degree.C.)__________________________________________________________________________Comparative 100 15 0 380 8020 164Example 230Example 242 90 15 10 380 5420 165Example 243 70 15 30 380 3340 164Comparative 40 15 60 380 1320 166Example 231Comparative 100 15 0 400 4750 164Example 232Example 244 90 15 10 400 3600 166Example 245 70 15 30 400 2140 165Comparative 40 15 60 400 980 165Example 233__________________________________________________________________________
EXAMPLES 246.about.253
Aromatic polyether ketone VICTREX PEEK 450 P and VICTREX PEX 220 G (Trade Mark of ICI Ltd.) was dryblended with the liquid crystal type polyimide powder obtained in Synthesis Examples 7 and 15 in various proportions illustrated in Table 63 and 64. The composition thus obtained was melt-Kneaded and delivered from an extruder having a bore of 40 mm and screw compression ration of 3:1 and cut into uniform pellets.
The pellets thus obtained were injection molded as usual and the minimum injection pressure was measured. Results are illustrated in Tables 63 and 64.
The mixture of aromatic polyether ketone and the liquid crystal type aromatic polyimide in proportions of the examples had lower minimum injection pressure than aromatic polyether ketone alone and was proved to have better processability.
COMPARATIVE EXAMPLES 234.about.241
Composition outside the scope of the invention were prepared and the minimum injection pressure was measured by the same procedures as carried out Examples 246.about.253. Results are illustrated in Tables 63 and 64.
Aromatic polyether imide which does not contain the liquid crystal type aromatic polyimide at all had high minimum injection pressure. When the liquid crystal type aromatic polyimide was 50 parts by weight or more for 50 parts by weight of the aromatic polyether imide, melt viscosity become too low and injection molding was different. Thus, minimum injection pressure could not be measured.
TABLE 63______________________________________ Minimum VICTREX L.C. type polyimide injection PEX 220G Synthesis wt. pressure wt. part Example No. part (kg/cm.sup.2)*______________________________________Com. Ex. 234 100 7 0 620Example 246 90 7 10 480Example 247 70 7 30 290Com. Ex. 235 40 7 60 **Com. Ex. 236 100 15 0 660Example 248 90 15 10 470Example 249 70 15 30 260Com. Ex. 237 40 15 60 **______________________________________ *Lower minimum injection pressure indicates lower melt viscosity. **Lower than the detection limit 90 kg/cm.sup.2.
TABLE 64______________________________________ Minimum VICTREX L.C. type polyimide injection PEX 220G Synthesis wt. pressure wt. part Example No. part (kg/cm.sup.2)*______________________________________Com. Ex. 238 100 7 0 570Example 250 90 7 10 430Example 251 70 7 30 220Com. Ex. 239 40 7 60 **Com. Ex. 240 100 15 0 560Example 252 90 15 10 420Example 253 70 15 30 220Com. Ex. 241 40 15 60 **______________________________________ *Lower minimum injection pressure indicates lower melt viscosity **Lower than the detection limit 90 kg/cm.sup.2.
EXAMPLES 254 and 255
The pellets which obtained in Examples 246 and 250 by blending the aromatic polyether ketone with the liquid crystal type aromatic polyimide in a ratio of 90:10 were injection molded at a injection temperature of 360.degree..about.400.degree. C. and mold temperature of 160.degree. C. Mechanical properties of molded specimens were measured and results are illustrated in Table 65. Tensile strength, tensile elastic modulus and elongation were measured in accordance with ASTM D-638.
The mixture of the aromatic polyether ketone and the liquid crystal type aromatic polyimide in a proportion of these examples had mechanical properties equivalent to the aromatic polyether ketone alone in Comparative Examples 242 and 243. Thus, mechanical properties were not decreased even though the liquid crystal type aromatic polyimide was mixed in the range of the invention.
COMPARATIVE EXAMPLES 242 and 243
Pellets obtained in Comparative Examples 234 and 238 were injection molded by the same procedures as carried out in Example 254 and 255, and mechanical properties of molded specimens were measured. Results are illustrated in Table 65.
TABLE 65______________________________________ Tensile Tensile elas- Pellets used strength tic modulus Elonga- for molding (Kg/cm.sup.2) (Kg/cm.sup.2) tion (%)______________________________________Comparative Comparative 930 270 100Example 242 Example 234Example 254 Example 246 930 270 96Comparative Comparative 1070 300 50Example 243 Example 238Example 255 Example 250 1060 300 50______________________________________

Number	Date	Country
4-080210	Apr 1992	JPX
4-102818	Apr 1992	JPX
4-160806	Jun 1992	JPX
4-160807	Jun 1992	JPX
4-275916	Oct 1992	JPX

Number	Name	Date
5041520	Ohta et al.	Aug 1991
5196506	Tamai et al.	Mar 1993
5210174	Tamai et al.	May 1993

Number	Date	Country
61-143478	Jul 1986	JPX
62-68817	Mar 1987	JPX
62-86021	Apr 1987	JPX
62-235381	Oct 1987	JPX
63-128025	May 1988	JPX
3-160024	Jul 1991	JPX

Polyimide composition

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