Patent Application
20100234538
This invention relates to a polyamide having a specific terminal group, a resin composition and fibers.
A wholly aromatic polyamide is a material having a structure formed by connecting rigid aromatic rings together and having excellent heat resistance, mechanical properties, chemical resistance and the like. Accordingly, it is widely used, in the form of fibers or a film, in electrical insulating materials, various reinforcing agents, bulletproof fibers and the like. Although the wholly aromatic polyamide is one of industrially highly valuable materials, it has been increasingly required to have higher properties according to applications in which it is used.
A measure for improving the physical properties of polymer is a method of introducing a cross-link between molecules by a chemical reaction. However, when the polymer is cross-linked, its solubility in solvent is lowered, and the polymer becomes difficult to be formed into fibers, a film or the like. Thus, a method comprising adding a cross-linking agent to a polymer solution in advance and causing the polymer to react and be cross-linked at the time of heat treatment and heat stretching has been proposed.
Nonpatent Document 1 proposes introducing halogen atoms into a polybenzobisthiazole molecular chain and introducing intermolecular bonds by radicals produced at the time of heat treatment.
(Nonpatent Document 1) Journal of Polymer Science: Part A: Polymer Chemistry, vol. 30, 1111 to 1122 (1992)
Thus, an object of the present invention is to provide fibers having excellent heat resistance and excellent mechanical strength such as tensile strength and elastic modulus by introducing a cross-linked structure into a wholly aromatic polyamide. Another object of the present invention is to provide a wholly aromatic polyamide which is used as a raw material of the fibers and a resin composition comprising the wholly aromatic polyamide. Still another object of the present invention is to provide a method for producing fibers having excellent heat resistance and excellent mechanical strength such as tensile strength and elastic modulus.
The present inventor has made intensive studies on a method for introducing a cross-linked structure into a wholly aromatic polyamide. As a result, he has found that when a terminal of the wholly aromatic polyamide is modified with a compound having a specific structure and heat-treated, the terminal is reacted, and a cross-linked structure is formed. Further, he has also found that the moldability of the terminal-modified wholly aromatic polyamide before the heat treatment is good. Further, he has also found that fibers having excellent mechanical strength are obtained by cross-linking. The present invention has been completed based on these findings.
That is, the present invention includes a polyamide (X) which mainly comprises recurring units represented by the following formulae (A) and (B):
has an inherent viscosity measured at 30° C. in 0.5 g/100 ml of concentrated sulfuric acid solution of 0.05 to 20 dl/g and has a substituent represented by the following formula (C):
wherein Ar3 is a trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and Ar4 is a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, at at least some of terminals.
Further, the present invention includes a resin composition (Z) comprising:
(i) 100 parts by weight of polyamide (Y) that mainly comprises recurring units represented by the following formulae (A) and (B):
and has an inherent viscosity measured at 30° C. in 0.5 g/100 ml of concentrated sulfuric acid solution of 0.05 to 20 dl/g, and
(ii) 0.0001 to 100 parts by weight of the polyamide (X).
The present invention includes fibers comprising the polyamide (X) and fibers comprising the resin composition (Z).
The present invention includes dope (X) comprising 100 parts by weight of the polyamide (X) and 300 to 3,000 parts by weight of solvent. Further, the present invention includes dope (Z) comprising 100 parts by weight of the resin composition (Z) and 300 to 3,000 parts by weight of solvent. Further, the present invention includes a method for producing fibers by spinning the dope (X) or dope (Z).
The polyamide (X) of the present invention mainly comprises recurring units represented by the following formulae (A) and (B). That is, the polyamide (X) comprises preferably 80 to 100 mol %, more preferably 90 to 100 mol % of the recurring units represented by the formulae (A) and (B) in all recurring units.
The proportion of the recurring unit represented by the formula (A) in the polyamide (X) is preferably 40 to 60 mol %, more preferably 45 to 55 mol %. The proportion of the recurring unit represented by the formula (B) in the polyamide (X) is preferably 60 to 40 mol %, more preferably 55 to 45 mol %. The recurring units of the formulae (A) and (B) exist randomly in the polyamide (X). The molar ratio {(A)/(B)} of the recurring units represented by the formulae (A) and (B) in the polyamide (X) is preferably 1/0.8 to 1/1.2, more preferably 1/0.9 to 1/1.1.
The polyamide (X) may comprise the other recurring units other than the formulae (A) and (B). The other recurring units include recurring units constituted by the following formulae (D) and (E). They constitute preferably 0 to 20 mol %, more preferably 0 to 10 mol %; of all recurring units.
—OC—Ar1—CO— (D)
—NH—Ar2—NH— (E)
In the formula (D), Ar1 is at least one group selected from a p-phenylene group and an m-phenylene group. In the formula (E), Ar2 is at least one group selected from a p-phenylene group, an m-phenylene group, a 3,4′-diphenylene ether group and a 4,4′-diphenylene ether group.
The polyamide (X) can be produced by polymerizing diamine components represented by the following formulae (a-1) and (a-2), a dicarboxylic acid component represented by the following formula (b) and/or its acid anhydride. The polymerization may be carried out by a conventionally known method such as solution polymerization, interfacial polymerization or melt polymerization.
In the formula (b), X represents OH, a halogen atom or a group represented by OR. R represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms.
The degree of polymerization can be controlled by the ratio of the diamine components to the dicarboxylic acid component. A preferred composition ratio is as follows.
0.8≦(α)/{(β)+(γ)}≦1.2
0<(γ)/(β)≦1.0
wherein (α) represents the number of moles of the diamine components (a-1) and (a-2), (β) represents the number of moles of the dicarboxylic acid component (b), and (γ) represents the number of moles of the acid anhydride component (c).
The polyamide (X) has an inherent viscosity ηinh of 0.05 to 20 dl/g, preferably 0.1 to 5 dl/g, more preferably 0.5 to 2 dl/g. The inherent viscosity ηinh is obtained by measuring a solution prepared by dissolving the polyamide (X) in 98-wt % concentrated sulfuric acid at a concentration of 0.5 g/100 ml at 30° C.
The polyamide (X) of the present invention has a substituent represented by the following formula (C) at at least some of terminal groups.
In the formula (C), Ar3 is a trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and Ar4 is a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.
Illustrative examples of the trivalent aromatic hydrocarbon group Ar3 include groups having a benzene ring or a naphthalene ring. Specific examples thereof include a benzene-triyl group, a toluene-triyl group, a xylene-triyl group, an ethylbenzene-triyl group, and a naphthalene-triyl group.
Illustrative examples of the monovalent aromatic hydrocarbon group Ar4 include a phenyl group and a naphthyl group.
Ar3 and Ar4 may have a substituent. Illustrative examples of the substituent include halogen groups such as fluorine, chlorine and bromine; alkyl groups having 1 to 6 carbon atoms such as a methyl group, ethyl group, propyl group and hexyl group; cycloalkyl groups having 5 to 10 carbon atoms such as a cyclopentyl group and cyclohexyl group; and aromatic groups having 6 to 10 carbon atoms such as a phenyl group.
In particular, Ar3 is preferably a benzene-triyl group, and Ar4 is preferably a phenyl group.
The terminal group represented by the formula (C) is preferably
The concentration of the terminal group represented by the formula (C) in the polyamide (X) is preferably 0.05 to 1,500 eq/ton, more preferably 10 to 1,000 eq/ton, much more preferably 100 to 240 eq/ton. The terminal group concentration can be determined from proton NMR analysis of polyamide dope.
The polyamide (X) preferably has an inherent viscosity of 0.5 to 2 dl/g and a concentration of the terminal group represented by the formula (C) of 100 to 240 eq/ton.
Since the polyamide (X) has the terminal group represented by the formula (C), the terminal group represented by the formula (C) is reacted by heating and a cross-linked structure is formed in the polyamide, whereby the mechanical strength of the polyamide is improved. Since the terminal group represented by the formula (C) does not form the cross-linked structure before heating, the polyamide (X) can be easily formed into fibers, a film or the like.
The resin composition (Z) of the present invention comprises a polyamide (X) and a polyamide (Y). The polyamide (X) is as described above.
The polyamide (Y) mainly comprises recurring units represented by the following formulae (A) and (B). That is, the polyamide (Y) comprises preferably 80 to 100 mol %, more preferably 90 to 100 mol % of the recurring units represented by the formulae (A) and (B) in all recurring units.
The proportion of the recurring unit represented by the formula (A) in the polyamide (Y) is preferably 40 to 60 mol %, more preferably 45 to 55 mol %. The proportion of the recurring unit represented by the formula (B) in the polyamide (Y) is preferably 60 to 40 mol %, more preferably 55 to 45 mol %. The recurring units of the formulae (A) and (B) exist randomly in the polyamide (Y). The molar ratio {(A)/(B)} of the recurring units represented by the formulae (A) and (B) in the polyamide (Y) is preferably 1/0.8 to 1/1.2, more preferably 1/0.9 to 1/1.1.
The polyamide (Y) may comprise recurring units other than the formulae (A) and (B). The other recurring units include recurring units constituted by the following formulae (D) and (E). They constitute preferably 0 to 20 mol %, more preferably 0 to 10 mol % of all recurring units.
—OC—Ar1—CO— (D)
—NH —Ar2—NH— (E)
In the formula (D), Ar1 is at least one group selected from a p-phenylene group and an m-phenylene group. In the formula (E), Ar2 is at least one group selected from a p-phenylene group, an m-phenylene group, a 3,4′-diphenylene ether group and a 4,4′-diphenylene ether group.
The polyamide (Y) can be produced by polymerizing diamine components represented by the following formulae (a-1) and (a-2), a dicarboxylic acid component represented by the following formula (b) and/or its acid anhydride. The polymerization may be carried out by a conventionally known method such as solution polymerization, interfacial polymerization or melt polymerization.
In the formula (b), X represents OH, a halogen atom or a group represented by OR. R represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms.
The degree of polymerization can be controlled by the ratio of the diamine components to the dicarboxylic acid component. A preferred composition ratio is as follows.
0.8≦(α)/{(β)+(γ)}≦1.2
0<(γ)/(β)≦1.0
wherein (α) represents the number of moles of the aromatic diamine components (a-1) and (a-2), (β) represents the number of moles of the aromatic dicarboxylic acid component (b), and (γ) represents the number of moles of the acid anhydride component (c).
The polyamide (Y) has an inherent viscosity ηinh of 0.05 to 20 dl/g, preferably 1 to 20 dl/g, more preferably 1 to 10 dl/g. The inherent viscosity ηinh is obtained by measuring a solution prepared by dissolving the polyamide (Y) in 98-wt % concentrated sulfuric acid at a concentration of 0.5 g/100 ml at 30° C.
The content of the polyamide (X) in the resin composition (Z) is 0.0001 to 100 parts by weight, preferably 0.0001 to 30 parts by weight, more preferably 0.001 to 20 parts by weight, much more preferably 0.01 to 15 parts by weight, based on 100 parts by weight of the polyamide (Y).
The concentration of the terminal group represented by the formula (C) in the resin composition (Z) is preferably 0.05 to 240 eq/ton, more preferably 1 to 50 eq/ton.
The resin composition (Z) can be prepared by a method such as 1) adding the polyamide (X) to the polyamide (Y), 2) mixing the polyamide (Y) with the polyamide (X), 3) adding the polyamide (Y) to the polyamide (X), or 4) carrying out in-situ polymerization of the polyamide (Y) with a solution of the polyamide (X).
The dope (X) of the present invention comprises 100 parts by weight of the polyamide (X) and 300 to 3,000 parts by weight, preferably 500 to 2,500 parts by weight, more preferably 1,000 to 2,000 parts by weight of solvent. The dope (Z) of the present invention comprises 100 parts by weight of the resin composition (Z) and 300 to 3,000 parts by weight, preferably 500 to 2,500 parts by weight, more preferably 1,000 to 2,000 parts by weight of solvent.
Illustrative examples of the solvents include amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone, and acid solvents such as 100% sulfuric acid, phosphoric acid, polyphosphoric acid and methanesulfonic acid. The dope can be prepared by mixing the polyamide (X) or resin composition (Z) with the solvent. Further, the dope can also be obtained directly by carrying out a polymerization reaction of the polyamide in the presence of the solvent.
The present invention includes fibers comprising the polyamide (X). Further, the present invention includes fibers comprising the resin composition (Z).
The strength of the fibers is preferably 20 to 40 CN/dtx, more preferably 22 to 35 CN/dtx. The concentration of the terminal group represented by the formula (C) in the fibers is preferably 0.05 to 240 eq/ton, more preferably 1 to 50 eq/ton.
The molar ratio {(A)/(B)} of the recurring units represented by the formulae (A) and (B) in the fibers is preferably 1/0.8 to 1/1.2, more preferably 1/0.9 to 1/1.1.
The fibers can be produced by spinning the dope (X) or dope (Z).
Spinning can be carried out by wet spinning, dry spinning or a combination of these methods. As described above, by carrying out flow orientation, liquid-crystal orientation, shear orientation or draw orientation in the spinning step, the orientation of the polyamide can be enhanced and mechanical properties can be improved.
After spinning, a heat treatment is preferably carried out. By the heat treatment, the polyamide can be cross-linked. The temperature at the time of the heat treatment is preferably 100 to 800° C., more preferably 200 to 600° C. It is preferable to apply tension to the fibers at the time of the heat treatment. The tension is preferably 1 to 95%, more preferably 3 to 50%, much more preferably 5 to 30% of fiber rupture strength.
At the time of the heat treatment, the fibers may be drawn. The draw ratio is preferably 2 to 40 times, more preferably 5 to 30 times. The draw ratio is desirably as close to the maximum draw ratio (MDR) as possible from the viewpoints of mechanical and physical properties. The draw temperature is preferably 100 to 800° C., more preferably 200 to 600° C. By drawing and orienting the fibers at high temperatures and a high draw ratio, the fibers having excellent mechanical properties can be obtained.
Hereinafter, the present invention will be further described with reference to examples. However, the present invention shall not be limited by these examples in any way.
This was measured at 30° C. in 0.5 g/100 ml of concentrated sulfuric acid (98 wt %) solution.
This was determined from proton NMR analysis of polymer dope by use of JEOL A-600 (600 MHz) of JEOL Ltd.
An obtained single fiber was subjected to a tensile test by use of TENSILON universal tester 1225A of ORIENTEC CO., LTD to determine a modulus of elongation and tensile strength.
To a fully dried three-neck flask equipped with an agitator, 2,152 parts by weight of dehydrated and purified N-methyl-2-pyrrolidone (NMP), 27.04 parts by weight of p-phenylenediamine and 50.06 parts by weight of 3,4′-diaminodiphenyl ether were added at room temperature and dissolved in nitrogen. Then, the mixture was cooled by ice, and 101.51 parts by weight of terephthalic acid dichloride was added to the mixture under agitation. Thereafter, the mixture was gradually heated and eventually reacted at 80° C. for 60 minutes, and 37.04 parts by weight of calcium hydroxide was then added to carry out a neutralization reaction, thereby obtaining dope containing a polyamide (Y). The dope contained 1,513 parts by weight of NMP based on 100 parts by weight of the polyamide (Y). A portion of the dope was reprecipitated in water to obtain the polyamide (Y). The polyamide (Y) had an inherent viscosity of 3.5 dl/g and a molar ratio (A)/(B) of 50/50.
To a fully dried three-neck flask equipped with an agitator, 210 parts by weight of dehydrated and purified NMP, 5.4 parts by weight of p-phenylenediamine and 10 parts by weight of 3,4′-diaminodiphenyl ether were added at room temperature and dissolved in nitrogen. Then, the mixture was cooled by ice, and 20.3 parts by weight of terephthalic acid dichloride and 1.46 parts by weight of 4-phenylethynyl phthalic anhydride represented by the following formula (1):
were added to the mixture under agitation. Thereafter, the mixture was gradually heated and eventually reacted at 80° C. for 60 minutes, and 7.4 parts by weight of calcium hydroxide was then added to carry out a neutralization reaction, thereby obtaining dope containing a polyamide (X). The dope contained 739 parts by weight of NMP based on 100 parts by weight of the polyamide (X). The dope was reprecipitated in water to obtain the polyamide (X). The polyamide (X) had an inherent viscosity of 0.665 dl/g and a molar ratio (A)/(B) of 50/50. The concentration of terminal group derived from the formula (1) was 183 eq/ton.
To 300 parts by weight of the dope of the polyamide (Y) prepared in Reference Example 1, 21 parts by weight of the dope of the terminal-group-modified polyamide (X) prepared in Example 1 was added, and the mixture was agitated at a temperature of 70° C. for 4 hours to obtain mixed dope having a polyamide (Y)/polyamide (X) of 88.5/11.5 (weight ratio). The amount of NMP was 1,425 parts by weight based on 100 parts by weight of the total amount of the polyamide (Y) and the polyamide (X) in the mixed dope. The concentration of terminal group derived from the formula (1) was 12 eq/ton based on the total amount of the polyamide (Y) and the polyamide (X).
The obtained mixed dope was spun into a coagulation bath of 50° C. which was a 30-wt % NMP aqueous solution at a rate of 3 m/min and a cylinder temperature of 30° C. by means of a cap having 5 openings each having a diameter of 0.3 mm and an L/D of 1. The distance between the surface of the cap and the surface of the coagulation bath was 10 mm. Fibers taken out of the coagulation bath were rinsed in a water bath of 50° C., dried by a drying roller of 200° C., and then drawn on a hot plate of 500° C. The maximum draw ratio (MDR) in this drawing step was determined in advance, and the fibers were drawn at a draw ratio of 13 times that was 0.8 times the MDR to obtain fibers. The tensile strength of the obtained fibers was 24.8 cN/dtex.
The tensile strength of the obtained fibers after the fibers were heat-treated at 400° C. for 5 minutes under a tension of 2.2 cN/dtex was 22.82 cN/dtex. Further, the tensile strength of the obtained fibers after the fibers were heat-treated at 450° C. for 5 minutes under a tension of 2.2 cN/dtex was 23.8 cN/dtex.
300 parts by weight of the polyamide dope prepared in Reference Example 1 was spun in the same manner as in Example 1 to obtain fibers. Various physical properties of the fibers are shown in Table 1. The tensile strength of the obtained fibers was 24.55 cN/dtex. The obtained fibers were heat-treated at 400° C. for 3 minutes under a tension of 2.2 cN/dtex. The tensile strength of the fibers after the heat treatment was 17.19 cN/dtex. The obtained fibers were heat-treated at 400° C. for 5 minutes under a tension of 2.2 cN/dtex. The tensile strength of the fibers after the heat treatment was 15.8 cN/dtex. The obtained fibers were heat-treated at 450° C. for 5 minutes under a tension of 2.2 cN/dtex, but the fibers were broken during the heat treatment and mechanical properties could not be measured accordingly.
The polyamide (X) of the present invention has terminals modified with a compound having a specific structure. Accordingly, the polyamide (X) can be easily molded into such a form as fibers, and by heat-treating the polyamide (X) after molding, a cross-linked structure can be introduced into the polyamide (X). As a result, fibers having excellent mechanical strength can be obtained. The fibers of the present invention have excellent heat resistance and excellent mechanical strength such as tensile strength and elastic modulus. Further, the resin composition of the present invention can be used as a raw material of fibers having excellent mechanical strength. Further, according to the production method of the present invention, fibers having excellent mechanical strength such as tensile strength and elastic modulus can be produced.
The fibers of the present invention have excellent heat resistance and mechanical properties. Thus, they can be used in a wide variety of fields such as ropes, belts, insulation cloths, reinforcing materials for thermosetting or thermoplastic resins, and protective clothing materials.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2006-039489 | Feb 2006 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2007/053122 | 2/14/2007 | WO | 00 | 8/15/2008 |
