Claims
- 1. A linear spirobiindane copolyamide comprising structural units of the formula ##STR9## wherein R.sup.1 is an alkylene radical containing a chain of about 2-20 carbon atoms, and spiro(bis)indane amide structural units of the formula
- (III) --Y--(R.sup.3 --O).sub.m 13 A--(O--R.sup.3).sub.m --Y--Z--R.sup.4 --Z--
- wherein:
- A is ##STR10## each R.sup.2 is independently C.sub.1-4 primary or secondary alkyl or halo;
- each of R.sup.3 and R.sup.4 is independently an unsubstituted or substituted alkylene or arylene radical other than o-arylene;
- Y is ##STR11## and Z is NH, or Y is NH and Z is ##STR12## m is 0 or 1; and n is 0-3.
- 2. A copolyamide according to claim 1 wherein n is 0.
- 3. A copolyamide according to claim 2 wherein Y is NH; Z is ##STR13## and R.sup.4 is A, m-phenylene, 4,4'-biphenylene or ##STR14##
- 4. A copolyamide according to claim 3 wherein R.sup.3 is m- or p-phenylene and m is 1.
- 5. A copolyamide according to claim 4 wherein R.sup.4 is m-phenylene.
- 6. A copolyamide according to claim 5 wherein R.sup.1 is (CH.sub.2).sub.5.
- 7. A copolyamide according to claim 3 wherein m is 0 and R.sup.4 is m-phenylene.
- 8. A copolyamide according to claim 7 wherein R.sup.1 is (CH.sub.2).sub.5.
- 9. A copolyamide according to claim 2 wherein Y is ##STR15## Z is NH, R.sup.4 is m- or p-phenylene and m is 0.
- 10. A copolyamide according to claim 9 wherein R.sup.4 is m-phenylene.
- 11. A copolyamide according to claim 10 wherein R.sup.1 is (CH.sub.2).sub.5.
- 12. A method for preparing a copolyamide according to claim 1 which comprises effecting reaction between at least one lactam of the formula ##STR16## and a composition comprising macrocyclic polyamide oligomers of the formula ##STR17## wherein p is from 1 to about 15, in the presence of a basic reagent.
- 13. A method according to claim 12 wherein the basic reagent is an alkali metal hydride.
- 14. A method according to claim 13 wherein the reaction temperature is in the range of about 90.degree.-300.degree. C.
- 15. A method according to claim 13 wherein R.sup.1 is (CH.sub.2).sub.5.
- 16. A method according to claim 15 wherein Y is NH, Z is ##STR18## R.sup.3 is m- or p-phenylene, R.sup.4 is m-phenylene and m is 1.
- 17. A method according to claim 15 wherein Y is NH, Z is ##STR19## R.sup.4 is m-phenylene and m is 0.
- 18. A method according to claim 15 wherein Y is ##STR20## Z is NH, R.sup.4 is m--phenylene and m is 0.
Parent Case Info
This application is a continuation-in-part of copending applications Ser. No. 20,264, filed Feb. 27, 1987, and Ser. No. 146,154, filed Jan. 20, 1988.
This invention relates to spirobiindane copolymers, and more particularly to spirobiindane copolyamides and a method for their preparation.
Polyamides are a valuable class of resinous materials useful in many areas including fiber formation, molding and formation of blends with other polymers. Particularly useful properties of polyamides are high tensile strength and solvent resistance. For the most part, polyamides are prepared either by the reaction of diamines with dicarboxylic acids or their derivatives or by ring-opening polymerization of lactams.
A recent innovation in the preparation of certain linear polymers involves the use of cyclic oligomer compositions as intermediates. For example, cyclic polycarbonate oligomer mixtures, disclosed in U.S. Pat. No. 4,644,053, are readily convertible under very favorable conditions to linear polycarbonates of very high molecular weight. The present invention provides a class of novel copolyamides, and an analogous method for their preparation from cyclic polyamides.
In one of its aspects, the present invention includes linear spirobiindane copolyamides comprising spiro(bis)indane amide structural units and structural units of the formula ##STR1## wherein R.sup.1 is a unsubstituted or substituted alkylene radical containing a chain of about 2-20 carbon atoms.
The R.sup.1 radicals are preferably straight alkylene chains containing about 4-12 carbon atoms. They may be considered as being derived from lactams such as pivalolactam, .delta.-valerolactam, .epsilon.-caprolactam and laurolactam, in which R.sup.1 is CH.sub.2 (CH.sub.3).sub.2, (CH.sub.2).sub.4, (CH.sub.2).sub.5 and (CH.sub.2).sub.11, respectively. .epsilon.-Caprolactam is especially preferred.
The spirobiindane amide structural units are characterized by the presence of an A radical having the formula ##STR2## wherein each R.sup.2 is independently C.sub.1-4 primary or secondary alkyl or halo and n is 0-3. Such A radicals 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 unsubstituted 6,6'-difunctional 3,3,3',3'-tetramethylspiro(bis)indanes, in which n is 0.
Any type of linkage may connect the A radical with the amide portions of the spirobiindane structural unit. Examples are single bonds, imide linkages (as present, for example in cyclic polyamideimides), ether linkages, unsubstituted or substituted alkylene and arylene linkages, and combinations thereof.
The spirobiindane structural units which are often preferred are those having the formula
Z is ##STR3## and Z is NH, or Y is NH and Z is ##STR4## and
m is 0 or 1.
The R.sup.3 radicals may be alkylene or arylene and are most often unsubstituted m- or p-phenylene. The value of m may be 0 or 1; that is, the --O--R.sup.3 -- moiety may be present or absent.
The R.sup.4 values may also be alkylene or arylene. 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 frequently 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 phenylindanol-derived radicals of the formula ##STR5## wherein R.sup.2 and n are as previously defined. The arylene hydrocarbon radicals, especially m-phenylene, are most preferred.
Any substituent which does not undergo interfering reactions in the context of this invention may be present on the R.sup.3 and/or R.sup.4 radicals Illustrative substituents are halo, nitro and alkoxy.
From the definitions hereinabove of Y and Z, it will be apparent that the preferred copolyamides of this invention may be derived from spirobiindane diamines and other dicarboxylic acids, or from spirobiindane dicarboxylic acids and other diamines. They may be prepared by effecting reaction between at least one lactam of the formula ##STR6## and a composition comprising macrocyclic polyamide oligomers of the formula ##STR7## wherein R.sup.3-4, A and m are as previously defined and p is from 1 to about 15, in the presence of a basic reagent. This method of preparation is another aspect of the invention.
For the most part, said macrocyclic polyamide oligomer 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 R.sup.3 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.
US Referenced Citations (1)
| Number |
Name |
Date |
Kind |
|
3725070 |
Hamb et al. |
Apr 1973 |
|
Continuation in Parts (2)
|
Number |
Date |
Country |
| Parent |
20264 |
Feb 1987 |
|
| Parent |
146154 |
Jan 1988 |
|
Patent Grant
4868279
