Claims
- 1. A composition comprising random macrocyclic monomer and oligomer compounds corresponding to the formula ##STR20## wherein the Z.sup.1 radicals are identical linking groups; A.sup.1 is a spiro (bis)indane moiety of the formula ##STR21## about 60% of the R.sup.1 groups are divalent aromatic organic radicals and the balance thereof are divalent aliphatic, alicyclic or aromatic organic radicals; each R.sup.2 is independently C.sub.1-4 primary or secondary alkyl or halo; a is from 1 to about 12, b is from 0 to 90% of total --A.sup.1 --Z.sup.1 --and --R.sup.1 --Z.sup.1 --moieties and n is 0-3.
- 2. A composition according to claim 1 wherein n is 0.
- 3. A composition according to claim 1 wherein the compounds contain at least one --R.sup.1 --Z.sup.1 --group.
- 4. A composition according to claim 3 wherein R.sup.1 is ##STR22##
- 5. A composition according to claim 1 which comprises macrocyclic polyamides.
- 6. A compositon according to claim 5 which comprises structural units of the formula ##STR23## wherein: R.sup.4 is a substituted or unsubstituted C.sub.2-4 alkylene, m-phenylene or p-phenylene radical;
- R.sup.5 is a substituted or unsubstituted alkylene radical or arylene radical other than o-arylene; and
- p is 0 or 1.
- 7. A composition according to claim 6 wherein R.sup.5 is m-phenylene and p is 0.
- 8. A composition according to claim 6 wherein R.sup.4 is m- or p-phenylene; R.sup.5 is A.sup.1, m-phenylene, ##STR24## and p is 1.
Parent Case Info
This applicatation is a continuation-in-part of the following copending applications:
This invention relates to macrocyclic oligomers, and more particularly to their preparation from compounds uniquely capable of conversion thereto.
U.S. Pat. Nos. 4,644,053 and 4,696,998 disclose cyclic polycarbonate oligomers and cyclic heterocarbonates, which are capable of conversion to high molecular weight linear homo- and copolycarbonates under reactive processing conditions. Cyclic polyarylates of similar molecular structure are disclosed in the aforementioned copending application Ser. No. 920,540. While cyclic materials of this kind are often capable of formation from a wide variety of organic dihydroxy compounds, yields are often low because the geometries of said organic dihydroxy compounds are not favorable for cyclization, preferring the formation of linear polymers.
The present invention is based on the discovery that compounds containing spirobiindane moieties are uniquely and generically capable of forming a broad spectrum of macrocyclic oligomers, often in preference to linear polymers. It is possible, however, to convert said oligomers by relatively simple means to linear polymers having a wide scope of utilities.
As broadly defined, therefore, the invention includes compositions comprising random macrocyclic monomer and oligomer compounds corresponding to the formula ##STR1## wherein the Z.sup.1 radicals are identical linking groups; A.sup.1 is a spiro(bis)indane moiety of the formula ##STR2## about 60% of the R.sup.1 groups are divalent aromatic organic radicals and the balance thereof are divalent aliphatic, alicyclic or aromatic organic radicals; each R.sup.2 is independently C.sub.1-4 primary or secondary alkyl or halo; a is from 1 to about 12, b is from 0 to 90% of total --A--Z--and --R.sup.1 --Z.sup.1 --moieties and n is 0-3.
As used herein, the term "macrocyclic oligomer" denotes compounds in which the spiro(bis)indane groups are part of a larger ring structure. Thus, the mere fact that the A.sup.1 moiety is itself cyclic is not significant to the macrocyclic nature of the compound; rather, the presence of a larger ring structure is mandatory.
The spiro(bis)indane units of formula II are obviously derived from 6,6'-difunctional 3,3,3',3'-tetramethylspiro(bis)indanes (hereinafter sometimes simply "spirobiindanes"), which may be substituted or unsubstituted. The R.sup.2 values therein may be alkyl radicals such as methyl, ethyl, 1-propyl or 2-propyl, or halo atoms such as chloro or bromo. Among compounds containing such R.sup.2 values, methyl and chloro are preferred; however, the most preferred compounds are the 6,6'-difunctional 3,3,3',3'-tetramethylspiro(bis)indanes, in which n is 0.
The compositions of the invention include macrocyclic monomers containing only one--A.sup.1 --Z.sup.1 --moiety. Most often, however, said compositions are mixtures of oligomers containing at least two of said moieties. The linking Z.sup.1 moieties, all of which are identical, are usually ether, ester, amide, imide or amic acid precursor thereof, or carbonate moieties or larger organic groups containing such moieties.
The R.sup.1 values, if present, may be different but are usually the same. In general, the tendency to form macrocyclic oligomers decreases with an increase in the proportion of--R.sup.1 --Z.sup.1 --moieties in the molecule. Said proportion, as a percentage of the number of total moieties present, is most often about 10-90% and preferably up to about 50%.
At least about 60% of the total number of R.sup.1 values are aromatic and the balance may be aliphatic, alicyclic, aromatic or mixed; those which are aliphatic or alicyclic generally contain up to about 8 carbon atoms. The R.sup.2 values may contain substituents such as halo, nitro, alkoxy, lactone and the like. Most often, however, all R.sup.1 radicals are hydrocarbon radicals.
Preferably at least about 80% of the total number of R.sup.1 values in the macrocyclic oligomer compositions, and most desirably all of said R.sup.1 values, are aromatic. The aromatic R.sup.1 radicals preferably have the formula
In formula III, the A.sup.2 and A.sup.3 values may be unsubstituted phenylene or substituted derivatives thereof, illustrative substituents (one or more) being alkyl, alkenyl, halo (especially chloro and/or bromo), nitro, alkoxy and the like. Unsubstituted phenylene radicals are preferred. Both A.sup.2 and A.sup.3 are preferably p-phenylene, although both may be o- or m-phenylene or one o- or m-phenylene and the other p-phenylene.
The bridging radical, Y.sup.1, is one in which one or two atoms, preferably one, separate A.sup.2 from A.sup.3. It is most often a hydrocarbon radical and particularly a saturated radical such as methylene, cyclohexylmethylene, 2-[2.2.1]-bicycloheptylmethylene, ethylene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene or adamantylidene, especially a gem-alkylene (alkylidene) radical. Also included, however, are unsaturated radicals and radicals which contain atoms other than carbon and hydrogen; for example, 2,2-dichloroethylidene, carbonyl, phthalidylidene, oxy, thio, sulfoxy and sulfone.
The copolymeric compositions of this invention are random copolymers; that is, the distribution of the--A.sup.1 --Z.sup.1 --and--R.sup.1 --Z.sup.1 --moieties in each molecule is random. In this sense, formula I is only a stylized structural formula since it suggests a block copolymer structure which is not contemplated.
In its broadest sense, therefore, the invention includes a wide variety of macrocyclic oligomers containing spirobiindane moieties. Oligomers containing the following structural units are illustrative; in these structures, A.sup.1 represents the spirobiindane moiety of formula II.
Polycarbonate: ##STR3##
Polyester: ##STR4## wherein R.sup.3 is a divalent aliphatic or m- or p-linked monocyclic aromatic or alicyclic radical.
Polyamide--includes the following: ##STR5## wherein:
R.sup.4 is a substituted or unsubstituted C.sub.2-4 alkylene, m-phenylene or p-phenylene radical;
R.sup.5 is a substituted or unsubstituted alkylene radical or arylene radical other than o-arylene; and
p is 0 or 1; and ##STR6## wherein A.sup.4 is a monocyclic or bicyclic m- or p-linked arylene radical or ##STR7## R.sup.6 is C.sub.1-4 primary or secondary alkyl, phenyl or substituted phenyl and R.sup.3 is as previously defined.
Polyimide and polyamideimide (and polyamic acid precursors thereof) - includes the following: ##STR8## wherein:
Z.sup.2 is a single bond, a divalent aliphatic or alicyclic radical containing about 1-12 carbon atoms, --O--, --CO--, --S--, --SO.sub.2 --, --O-Q-O--, --SO.sub.2 -Q-SO.sub.2 --, ##STR9##
Q is a divalent aliphatic or aromatic radical; and R.sup.4, R.sup.6 and p are as previously defined; and ##STR10## wherein Z.sup.3 is R.sup.3 or --R.sup.4 --Z.sup.4 --R.sup.4 --or has formula VIII, Z.sup.4 is ##STR11## and R.sup.3 and R.sup.4 are previously defined.
Polyetherketone and polyethersulfone:
Consideration will now be given to each of these types of oligomers in detail, with preferred parameters and illustrative methods of preparation.
Polycarbonates
Macrocyclic polycarbonate oligomer compositions corresponding to formula IV, and corresponding copolycarbonates, may be prepared by contacting a composition comprising at least one compound of the formula
It will be apparent from the foregoing that at least one of the compounds of formulas XII and XIII must be a bishaloformate. While the X.sup.1 values therein may be chlorine or bromine, the bischloroformates, in which X.sup.1 is chlorine, are most readily available and their use is therefore preferred. Reference to bischloroformates hereinafter will frequently include all compounds of formulas XII and XIII when the context permits. It should be understood, however, that other bishaloformates may be substituted for the bischloroformates as appropriate.
The bischloroformates comprise a major proportion of the compounds of formulas XII and XIII, at least about 60%, preferably at least about 75% and most preferably at least about 90% of the total number of Y.sup.2 and Y.sup.3 moieties being chloroformate moieties. Any remaining compounds of formulas XII and XIII are dihydroxy compounds, preferably bisphenols.
When the compound of formula XII is free 6,6'-dihydroxy-3,3,3',3'-tetramethylspiro(bis)indane (hereinafter SBI), it may be necessary to employ a minor proportion of a solvent therefor, such as tetrahydrofuran, to ensure its dissolution in the reaction mixture. Most often, however, bischloroformates alone are used.
The proportions of compounds of formulas XII and XIII in the reaction mixture will depend on whether the cyclic composition being prepared is a homopolycarbonate (whereupon only the compound of formula XII will be used) or a copolycarbonate. The copolycarbonates generally comprise at least about 10 mole percent of units of formula IV, and therefore require at least about 10 mole percent of the compound of formula XII in the reaction mixture, the balance having formula XIII.
Any bischloroformates may be employed in substantially pure, isolated form. For this purpose, it is possible to prepare SBI bischloroformate by a variation of the method described in Example 4 of British Pat. 613,280, substituting diethylaniline for the dimethylaniline recited therein.
It is frequently preferred, however, to use one or more crude bischloroformate products. Suitable crude products may be prepared by any known methods for bischloroformate preparation. Typically, at least one bisphenol (and, for the preparation of copolycarbonates, a mixture of bisphenols such as those of bisphenol A and SBI) is reacted with phosgene in the presence of a substantially inert organic liquid, as disclosed in the following United States patents:
In addition to the bisphenol bischloroformate, such crude bischloroformate products may contain oligomer bischloroformates. Most often, a major proportion of the crude product comprises monomer, dimer and trimer bischloroformate. Higher oligomer bischloroformates, and monochloroformates corresponding to any of the aforementioned bischloroformates, may also be present, preferably only in relatively small amounts.
More preferably, the preparation of the crude bischloroformate product takes place in the presence of aqueous alkali. The pH of the reaction mixture may be up to about 12. It is generally found, however, that the proportion of high polymer in the cyclic oligomer mixture is minimized by employing a crude bischloroformate product comprising a major amount of bisphenol bischloroformate and only minor amounts of any oligomer bischloroformates. Such products may be obtained by a variant of the method disclosed in U.S. Pat. No. 4,638,077, the disclosure of which is also incorporated reference herein.
In that method, phosgene is passed into a mixture of a substantially inert organic liquid and a bisphenol, said mixture being maintained at a temperature within the range of about 10-40.degree. C., the phosgene flow rate being at least 0.15 equivalent per equivalent of bisphenol per minute when the temperature is above 30.degree. C. An aqueous alkali metal or alkaline earth metal base solution is simultaneously introduced as necessary to maintain the pH in the range of about 0.5-8.0. By this method, it is possible to prepare bischloroformates of compounds such as bisphenol A in high yield while using a relatively small proportion of phosgene, typically up to about 1.1 equivalent per equivalent of bisphenol.
For the preparation of SBI bischloroformate compositions, the above-described method is not satisfactory since SBI swells and gels in water-methylene chloride mixtures at low pH. The monochloroformate of SBI is, however, apparently soluble in such mixtures (particularly in the methylene chloride phase thereof).
Therefore, it is possible to prepare SBI bischloroformate compositons by passing phosgene into a heterogeneous mixture of solid SBI, a substantially inert organic liquid (e.g., methylene chloride) and an aqueous alkali metal or alkaline earth metal base solution, said mixture being maintained at a temperature within the range of about 10.degree.-40.degree. C. and at a pH of the aqueous phase in the range of about 8-14, until all solids have dissolved, and then continuing phosgene passage as the pH is decreased to a value in the range of 2-8, preferably 2-5. This method is disclosed and claimed in copending, commonly owned application Ser. No. 926,685, filed Nov. 4, 1986.
When one of these methods is employed, it is obvious that the crude bischloroformate product will ordinarily be obtained as a solution in a substantially non-polar organic liquid such as those disclosed hereinafter. Depending on the method of preparation, it may be desirable to wash said solution with a dilute aqueous acidic solution to remove traces of base used in preparation.
The tertiary amines ("tertiary" in this context denoting the absence of N--H bonds) generally comprise those which are oleophilic (i.e., which are soluble in and highly active in organic media, especially those used in the oligomer preparation method of this invention), and more particularly those which are useful for the formation of polycarbonates. Reference is made, for example, to the tertiary amines disclosed in U.S. Pat. Nos. 4,217,438 and 4,368,315, the disclosures of which are incorporated by reference herein. They include aliphatic amines such as triethylamine, tri-n-propylamine, diethyl-n-propylamine and tri-n-butylamine and highly nucleophilic heterocyclic amines such as 4-dimethylaminopyridine (which, for the purposes of this invention, contains only one active amine group). The preferred amines are those which dissolve preferentially in the organic phase of the reaction system; that is, for which the organic-aqueous partition coefficient is greater than 1. This is true because intimate contact between the amine and the compounds of formulas XII and XIII is essential for the formation of the monocyclic oligomer composition. For the most part, such amines contain at least about 6 and preferably about 6-14 carbon atoms.
The most useful amines are trialkylamines containing no branching on the carbon atoms in the 1- and 2-positions. Especially preferred are tri-n-alkylamines in which the alkyl groups contain up to about 4 carbon atoms. Triethylamine is most preferred by reason of its particular availability, low cost, and effectiveness in the preparation of products containing low percentages of linear oligomers and high polymers.
Suitable aqueous alkali or alkaline earth metal hydroxide or carbonate solutions include lithium, sodium, potassium and calcium hydroxide and sodium and potassium carbonate. Lithium, sodium or potassium hydroxide are most often used, with sodium hydroxide being preferred because of its availability and relatively low cost. The concentration of the solution is not critical and may be about 0.1-16 M, preferably about 0.2-10 M.
The fourth essential component in the macrocyclic polycarbonate oligomer preparation method is a substantially non-polar organic liquid which forms a two-phase system with water. The identity of the liquid is not critical, provided it possesses the stated properties. Illustrative liquids are aromatic hydrocarbons such as toluene and xylene; substituted aromatic hydrocarbons such as chlorobenzene, o-dichlorobenzene and nitrobenzene; chlorinated aliphatic hydrocarbons such as chloroform and methylene chloride; and mixtures of the foregoing with ethers such as tetrahydrofuran. Methylene chloride is generally preferred.
To prepare the macrocyclic polycarbonate oligomer composition according to the above-described method, the reagents and components are maintained in contact under conditions whereby the bischloroformates are present in low concentration. Actual high dilution conditions, requiring a large proportion of organic liquid, may be employed but are usually not preferred for cost and convenience reasons. Instead, simulated high dilution conditions known to those skilled in the art may be employed. For example, in one embodiment of the method the bischloroformates (and optionally other reagents) are added gradually to a reaction vessel containing solvent.
Although addition of said bischloroformates neat (i.e., without solvents) is within the scope of this embodiment, it is frequently inconvenient because many bischloroformates are solids. Therefore, they are preferably added as a solution in a portion of the organic liquid, especially when they consist essentially of bischloroformate. The proportion of organic liquid used for this purpose is not critical; about 25-75% by weight, and especially about 40-60%, is preferred.
The reaction temperature is generally in the range of about 0.degree.-50.degree. C. It is most often about 0.degree.-40.degree. C. and preferably 20.degree.-40.degree. C.
For maximization of the yield and purity of macrocyclic polycarbonate oligomers as opposed to high polymer and insoluble and/or intractable by-products, it is preferred to use not more than about 1.5 mole of bischloroformates, calculated as bisphenol bischloroformate, per liter of organic liquid in the reaction system, including any liquid used to dissolve said compounds. Preferably, about 0.003-1 0 mole of said compounds is used when it consists entirely of bischloroformate, and no more than about 0.5 mole is used when it is a bisphenol-bischloroformate mixture. It should be noted that this is not a molar concentration in the organic liquid when said compounds are added gradually, since they are consumed as they are added to the reaction system.
The molar proportions of the reagents constitute another important feature for yield and purity maximization. The preferred molar ratio of amine to compounds of formulas XIV and XV when said compounds consist essentially of bischloroformates is about 0.1-1.0:1 and most often about 0.15-0.6:1, and that of base to said compounds is about 1.5-3:1 and most often about 2-3:1. When a bischloroformate-bisphenol combination is used, the preferred molar ratio for amine is about 0.1-0.5:1.
A highly preferred method for preparing the macrocyclic polycarbonate oligomer compositions of this invention comprises conducting the reaction using as the amine at least one aliphatic or heterocyclic tertiary amine which, under the reaction conditions, dissolves preferentially in the organic phase of the reaction system, and gradually adding the bischloroformates and at least a portion of the amine and base simultaneously to the organic liquid or to a mixture thereof with water, said liquid or mixture being maintained at a temperature in the range of about 0.degree.-50.degree. C.; the amount of bischloroformates used being up to about 0.7 mole for each liter of organic liquid present in the reaction system, and the total molar proportions of amine and base, respectively, to bischloroformates being approximately 0.06-2.0:1 and 2-3:1, respectively; and recovering the cyclic oligomers thus formed.
A factor of some importance in this embodiment is the concentration of available amine, which should be maintained at a level as constant as possible during the entire bischloroformate addition period. If all of the amine is present in the reaction vessel into which the amine is introduced, its concentration steadily decreases, principally by dilution. On the other hand, if the amine is introduced continuously or in equal increments during introduction of bischloroformate, its available concentration is initially low and increases more or less steadily during the addition period. These fluctuations can result in a high and constantly varying proportion of high polymer in the product.
It has been found advantageous to introduce the amine in one initial large portion, usually about 40-95% and preferably about 40-75% by weight of the total amount, followed by incremental or continuous addition of the balance thereof. By this procedure, the concentration of available amine is maintained at a fairly constant level in the organic phase during the entire addition period, and it is possible to minimize the proportion of high polymer in the product. Typically, high polymer content is 10% or less when this mode of addition is used.
Under these conditions, it is usually advantageous for the reactionv essel to initially contain about 5-40% and preferably about 5-30% of total base. The balance thereof is also introduced continuously or incrementally. As in the embodiment previously described, another portion of organic liquid may serve as a solvent for the bischloroformates.
Among the other principal advantages of this preferred embodiment are the non-critically of the degree of dilution of the reagents and the ability to complete the addition and reaction in a relatively short time, regardless of reactions scale. It ordinarily takes only about 25-30 minutes to complete cyclic oligomer preparation by this method, and the cyclic oligomer yield may be 85-90% or more. By contrast, use of a less preferred embodiment may, depending on reaction scale, require an addition period as long as 8-10 hours.
In this preferred embodiment, the pH of the reaction mixture is typically in the range of about 9-14 and preferably about 12. When the bischloroformates (and optionally the amine) are added to all of the base, on the other hand, the initial pH remains on the order of 14 during essentially the entire reaction period.
When the reaction has been completed, impurities may be removed in the necessary amounts by conventional operations such as combining the crude product, as a solid or in solution, with a on-solvent for said impurities. Illustrative non-solvents include esters such as methyl acetate and ethyl acetate.
Recovery of the macrocyclic polycarbonate oligomers normally means merely separating the same from diluent (by known methods such as vacuum evaporation) and, optionally, from high polymer and other impurities. The degree of sophistication of recovery will depend on such variables as the intended end use of the product. Among the macrocyclic copolycarbonates contemplated as part of the invention are macrocyclic polyphenylene ether-polycarbonates containing, in addition to the structural units of formula IV, units corresponding to --R.sup.1 --Z.sup.1 --which have the formula ##STR14## wherein:
each Q.sup.1 is independently halogen, primary or secondary lower alkyl (i.e., alkyl containing up to 7 carbon atoms), phenyl or hydrocarbonoxy;
each Q.sup.2 is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl or hydrocarbonoxy;
each R.sup.8 is independently C.sub.1-8 primary or secondary alkyl, phenyl or halo;
each R.sup.9 is independently hydrogen, methyl, ethyl or phenyl;
m is from 0 to 4;
x is from 1 to about 5; and
p is as previously defined.
The moieties of formula XIV therein may or may not contain a methylene or substituted methylene bridge linking two of the aromatic rings (according as p is 1 or 0). The substituents on said bridge, if any, are methyl, ethyl or phenyl, with methyl being preferred. Especially preferred are the compounds in which each R.sup.9 is methyl, m is 0 and p is 1; that is, compounds derived from bisphenol A.
Also present in the moiety of formula XIV are from 1 to about 5, and preferably from 1 to 3, phenylene ether units. Examples of suitable primary lower alkyl groups suitable for Q.sup.1 and Q.sup.2 therein are methyl, ethyl, n-propyl, n-butyl, isobutyl, n-amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-dimethylbutyl, 2-, 3- or 4-methylpentyl and the corresponding heptyl groups. Examples of secondary lower alkyl groups are isopropyl, sec-butyl and 3-pentyl. Preferably, any such alkyl radicals are straight chain rather than branched. Most often, each Q.sup.1 is alkyl or phenyl, especially C.sub.1-4 alkyl and preferably methyl, and each Q.sup.2 is hydrogen.
The macrocyclic polyphenylene ether-polycarbonates may be prepared by the above-described polycarbonate process, substituting for the compound of formula XIII at least one oligomeric compound of the formula ##STR15## wherein Q.sup.1, Q.sup.2, R.sup.8, R.sup.9, Y.sup.3, m and p are as defined hereinabove, and otherwise varying the process as described hereinafter.
The oligomeric compounds of formula XV are polyphenylene ether-derived bisphenols and their bishaloformate derivatives. They may be prepared by equilibration of a polyphenylene ether with a bisphenol of the formula ##STR16## in the presence of a phenoxy radical which may be generated by a diphenoquinone. A bisphenol containing no more than about 5 polyphenylene ether units is desired, and it may be produced by employing a ratio of moles of bisphenol to units in the polyphenylene ether of at least about 0.1:1 and preferably about 0.1-1.0:1. This method of preparing polyphenylene ether-derived bisphenols is disclosed, for example, in U.S. Pat. No. 3,496,236, the disclosure of which is also incorporated by reference herein.
The molar ratio of the compound of formula XII to that of formula XIV is generally about 5-10:1, and preferably about 7-8:1. The concentration of the base solution is most desirably no higher than about 5 M.
In a preferred embodiment of the preparation method, the compounds of formulas XII and XIV, or a combination thereof with the amine, are added gradually to a mixture of the other materials. It is within the scope of this embodiment to incorporate the amine in the mixture to which said compounds are added, or to add it gradually, either in admixture with said compounds or separately. Continuous or incremental addition of amine is frequently preferred. The reaction temperature is preferably about 40.degree.-50.degree. C.
For maximization of the yield and purity of macrocyclic polyphenylene ether-polycarbonate oligomers, it is preferred to use up to about 0.7 mole and preferably about 0.1-0.6 mole of compounds of formulas XII and XIV per liter of organic liquid in the reaction system, including any liquid used to dissolve said compounds. The preferred molar ratio of amine to said compounds is about 0.05-1.5:1. and most often about 0.1-1.0:1. The molar ratio of base to said compounds is usually about 1-5:1.
Polyesters
The A.sup.5 value in formula V may be a divalent aliphatic, alicyclic or aromatic radical. Suitable aromatic radicals are similar to A.sup.2 and A.sup.3, with the proviso that they are m- or p-linked. The alicyclic radicals are similarly linked and most often contain about 4-8 carbon atoms.
The R.sup.3 may be considered as being derived from a dicarboxylic acid of the formula R.sup.3 (COOH).sub.2. Thus, suitable dicarboxylic acids include adipic, pimelic and cyclohexane-1,3-dicarboxylic acids and the unsubstituted and substituted terephthalic, isophthalic and pyridine-2,6-dicarboxylic acids. The unsubstituted aromatic acids, especially isophthalic and terephthalic and most especially isophthalic acid, are preferred.
The macrocyclic polyester oligomers generally comprise mixtures of oligomers, principally having degrees of polymerization up to about 7. The predominant oligomer is usually the trimer.
Such oligomers may be prepared by adding a dicarboxylic acid chloride of the formula R.sup.3 (COCl).sub.2 to a mixture of an organic liquid as described hereinabove and a salt of the spirobiindane bisphenol, the latter being maintained in low concentration. It is often preferred to employ a di-(alkali metal) salt in a mixed aqueous-organic medium. Also present is a catalyst comprising at least one tertiary amine or quaternary ammonium salt, generally in the amount of about 0.1-15.0 mole percent based on spirobiindane bisphenol.
For the preparation of macrocyclic copolyesters, there may also be employed at least one second salt of a dihydroxy compound of the formula HO--R.sup.1 --OH, where R.sup.1 is as previously defined. Said second salt may be in the same vessel as the spirobiindane bisphenol salt or may be added concurrently with the dicarboxylic acid chloride, with the former method frequently affording somewhat higher yields of macrocyclic copolyesters.
Suitable tertiary amines include those previously described with reference to polycarbonates. In general, the quaternary ammonium salts are somewhat preferred over the tertiary amines. Illustrative quaternary ammonium salts are the tetraalkylammonium halides containing a total of about 15-30 carbon atoms, examples of which are tetra-n-butylammonium bromide and methyltrioctylammonium chloride.
The catalyst is preferably in admixture with said spirobiindane bisphenol salt. Reaction temperatures in the range of about 25.degree.-100.degree. C. and especially about 30.degree.-50.degree. C. are typical.
Anhydrous methods for preparing the macrocyclic polyester oligomers may also be employed. They typically utilize the same organic liquids as diluents and a trialkylammonium salt of the bisphenol.
In a preferred embodiment of the invention, the macrocyclic oligomers are polyamides, polyimides (including polyamideimides), polyetherketones or polyethersulfones. These compositions will now be described.
Polyamides
In the macrocyclic polyamide oligomers corresponding to formula VI, the R.sup.5 values may be considered as derived from dicarboxylic acids of the formula R.sup.5 (COOH).sub.2, and may be substituted or unsubstituted alkylene or arylene (other than o-arylene) radicals. The alkylene radicals generally contain about 2-8 carbon atoms, about 2-4 thereof usually being in a straight chain. They are illustrated by ethylene, trimethylene and tetramethylene, as well as branched isomers thereof. The arylene radicals, which are preferred, generally contain about 6-25 carbon atoms and are illustrated by m-phenylene, p-phenylene, the corresponding tolylene radicals, 4,4'-biphenylene, 1,4-naphthylene, 1,8-naphthylene and divalent phenylindane radicals of the formula ##STR17## wherein R.sup.2 and n are as previously defined. Spirobiindane radicals are also included. Any substituent which does not undergo interfering reactions in the context of this invention may be present thereon. Illustrative substituents are halo, nitro, hydroxy and alkoxy. The arylene hydrocarbon radicals, especially m-phenylene, are most preferred.
The R.sup.4 radicals are most often unsubstituted m- or p-phenylene. The value of p may be 0 or 1; that is, the --O--R.sup.4 --moiety may be present or absent.
Polyamide oligomers corresponding to formula VII are also within the scope of the invention. In that formula, A.sup.4 may be, for example, m-phenylene, p-phenylene or a disiloxane radical of formula VIII, wherein the disiloxane moiety is flanked by two alkylene, cycloalkylene or arylene radicals. Any R.sup.3 alkylene radicals for this purpose generally contain 2-4 carbon atoms. The substituents on silicon may be alkyl, phenyl or substituted phenyl and are most often methyl.
The macrocyclic polyamide oligomer compositions of this invention include oligomers having degrees of polymerization from 1 to about 15. For the most part, said compositions are mixtures of oligomers having varying degrees of polymerization. However, it is frequently possible to isolate individual oligomers, particularly the cyclic "monomer", by conventional means such as preparative scale high pressure liquid chromatography. Higher oligomer species are hereinafter sometimes identified as "dimer", etc.
Said oligomer compositions may be prepared from the corresponding diamines and dicarboxylic acid chlorides, as described hereinafter. The diamines in which R4 is m- or p-phenylene and p is 1, and corresponding nitro compounds, are novel compounds; they are disclosed and claimed in the aforementioned application Ser. No. 20,264.
The nitro compounds (hereinafter sometimes "bisnitrophenoxy ethers") may be prepared by the reaction of halonitrobenzenes or dinitrobenzenes with spirobiindane bisphenol salts under alkaline conditions in a dipolar aprotic solvent. The molar ratio of nitro compound to spirobiindane bisphenol salt is generally about 2.0-2.5:1. The corresponding bis-aminophenoxy ethers may be prepared by reduction of said bis-nitrophenoxy ethers by conventional means such as catalytic hydrogenation.
The preparation of the bis-nitrophenoxy and bis-aminophenoxy ethers is illustrated by the following examples.
US Referenced Citations (10)
Related Publications (4)
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920540 |
Oct 1986 |
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20264 |
Feb 1987 |
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26517 |
Mar 1989 |
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64650 |
Jun 1987 |
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Continuation in Parts (1)
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887503 |
Jul 1986 |
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Patent Grant
4980453
