Claims
- 1. An isocyanate-modified poly(alkylene carbonate) polyahl which is a polymer comprising
- (1) a backbone having
- (a) the residue of at least one polyahl initiator;
- (b) the residue of at least one polyisocyanate;
- (c) a plurality of poly(alkyleneoxy) moieties;
- (d) a plurality of poly(alkylene carbonate) moieties; and
- (2) a plurality of active hydrogen end groups,
- in an amount sufficient to act as reaction sites when the isocyanate-modified poly(alkylene carbonate) polyahls are advanced to higher molecular weights by heating under reduced pressure.
- 2. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 1 wherein the isocyanate is an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic polyisocyanate or a combination thereof.
- 3. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 2 wherein the isocyanate is selected from the group consisting of toluene diisocyanate, methylene bis(4-phenylisocyanate) and prepolymers of methylene bis(4-phenylisocyanate).
- 4. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 1 wherein the poly(alkyleneoxy) moieties are poly(ethyleneoxy) moieties, poly(propyleneoxy) moieties or combinations thereof.
- 5. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 1 wherein the poly(alkylene carbonate) moieties are poly(ethylene carbonate) moieties, poly(propylene carbonate) moieties, poly(butylene carbonate) moieties or combinations thereof.
- 6. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 1 wherein the weight percent of isocyanate used to make the modified polyahl is from 1 to 25 percent.
- 7. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 1 wherein the number average molecular weight is from 400 to 20,000.
- 8. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 1 wherein the active hydrogen end groups are hydroxyl groups.
- 9. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 1 wherein the polyahl is a diahl.
- 10. The isocyanate-modified poly(alkylene carbonate) diahl of claim 9 wherein the diahl is a diol.
- 11. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 1 which is a random polymer corresponding to the formula ##STR7## wherein R.sup.1 is separately in each occurence an n-valent hydrocarbon radical or hydrocarbon radical which can contain one or more heteroatoms of O,N or S;
- R.sup.2 is separately in each occurrence hydrogen, halogen, a nitro group, a cyano group, a C.sub.1-20 hydrocarbyl group or a C.sub.1-20 hydrocarbyl group substituted with one or more halo, cyano, nitro, thioalkyl, tert-amino, alkoxy, aryloxy, aralkoxy, carbonyldioxyalkyl, carbonyldioxyaryl, carbonyldioxyaralkyl, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, alkylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkylsulfinyl, arylsulfinyl, aralkylsulfinyl, alkylsulfonyl, arylsulfonyl, or aralkylsulfonyl group;
- M is separately in each occurrence the residue of an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic polyisocyanate or a combination thereof;
- X is separately in each occurrence S, O, NH, ##STR8## X' is separately in each occurrence S, O or NH; A is separately in each occurrence ##STR9## combinations thereof or a covalent bond; Q is separately in each occurrence O, S or NH provided that all carbonate moieties are internal;
- n is separately in each occurrence an integer of from 1 to 25;
- s is separately in each occurrence an integer of from 1 to 5;
- x is separately in each occurrence an integer of from 1 to 40;
- y is separately in each occurence an integer of from 1 to 120; and
- z is separately in each occurrence an integer of from 0 to 5.
- 12. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 11 wherein
- M is the residue of a polyisocyanate selected from the group consisting of toluene diisocyanate, methylene bis(4-phenylisocyanate), and prepolymers of methylene bis(4-phenylisocyanate), and combinations thereof;
- X is oxygen;
- x is separately in each occurrence an integer from 2 to 10;
- y is separately in each occurrence an integer from 5 to 15; and
- z is an integer from 0 to 2,
- provided that the ratio of y to x is from 1:1 to 3:1.
- 13. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 12 wherein
- R.sup.1 is aliphatic or cycloaliphatic hydrocarbon containing one or more oxygen, nitrogen, or sulfur moieties;
- R.sup.2 is hydrogen, C.sub.1-20 alkyl, C.sub.1-20 haloalkyl, C.sub.1-20 alkenyl or phenyl;
- X is S, O or NH; and
- n is an integer from 1 to 10.
- 14. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 13 wherein
- R.sup.1 is an n-valent alkane or cycloalkane, or an n-valent alkane or cycloalkane containing one or more oxygen, nitrogen or sulfur moieties;
- R.sup.2 is hydrogen, methyl or ethyl;
- X is O;
- X' is O;
- n is an integer from 1 to 5; and
- s is an integer from 1 to 3.
- 15. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 14 wherein
- R.sup.1 is an n-valent C.sub.1-10 alkane or an n-valent C.sub.1-10 alkane substituted with one or more oxygen moieties;
- R.sup.2 is hydrogen or methyl; and
- n is 1 or 2.
- 16. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 15 wherein R.sup.2 is hydrogen.
- 17. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 16 wherein said modifier is selected from the group consisting of diols, triols and polyether polyols containing two or more hydroxy functional groups.
- 18. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 11 wherein the weight percent of isocyanate used to make the modified polyahl is from 1 to 25 percent.
- 19. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 11 wherein the number average molecular weight is from 400 to 20,000.
- 20. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 8 which is a random polymer corresponding to the formula ##STR10## wherein R.sup.3 is R.sup.4 -X'.sub.n ;
- R.sup.2 is separately in each occurrence hydrogen, halogen, a nitro group, a cyano group, a C.sub.1-20 hydrocarbyl group or a C.sub.1-20 hydrocarbyl group substituted with one or more halogen, cyano, nitro, thioalkyl, tert-amino, alkoxy, aryloxy, aralkoxy, carbonyldioxyalkyl, carbonyldioxyaryl, carbonyldioxyaralkyl, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, alkylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkylsulfinyl, arylsulfinyl, aralkylsulfinyl, alkylsulfonyl, arylsulfonyl, or aralkylsulfonyl group;
- R.sup.3 is separately in each occurrence an n-valent hydrocarbon radical or hydrocarbon radical which contains one or more heteroatoms of O, N or S;
- M is separately in each occurrence the residue of an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic polyisocyanate or a combination thereof;
- X' is O, S or NH;
- n is separately in each occurrence an integer of from 1 to 25;
- p is an integer of 1 or greater;
- s is separately in each occurrence an integer of 1 to 5;
- x is 1;
- y is separately in each occurrence 1 to 40; and
- z is separately in each occurrence 1 to 100.
- 21. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 20 wherein
- R.sup.2 is hydrogen, C.sub.1-20 alkyl, C.sub.1-20 haloalkyl, C.sub.1-20 alkenyl or phenyl;
- R.sup.3 is an aliphatic or cycloaliphatic hydrocarbon or an aliphatic or cycloaliphatic hydrocarbon containing one or more oxygen, sulfur or nitrogen moieties;
- X' is S, O or NH;
- n is an integer of 1 to 10, inclusive;
- p is 1 to 10, inclusive;
- y is 5 to 20, inclusive; and
- z is 20 to 50, inclusive.
- 22. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 21 wherein
- R.sup.2 is hydrogen, C.sub.1-3 alkyl, C.sub.2-3 alkenyl or phenyl;
- R.sup.3 is an n-valent alkane or cycloalkane or an n-valent alkane or cycloalkane containing an oxygen, sulfur or nitrogen moiety;
- M is the residue of a polyisocyanate selected from the group consisting of toluene diisocyanate, methylene bis(4-phenylisocyanate) and prepolymers of methylene bis(4-phenylisocyanate);
- n is an integer of 1 to 5, inclusive;
- p is 1 to 5, inclusive; and
- s is an integer of from 1 to 5, inclusive.
- 23. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 22 wherein
- R.sup.2 is hydrogen, methyl or ethyl;
- R.sup.3 is an n-valent C.sub.1-10 alkane containing oxygen moieties; and
- n is 1 or 2.
- 24. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 20 wherein the weight percent modifier is from 1 to 25 percent.
- 25. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 24 wherein the number average molecular weight is from 400 to 20,000.
- 26. An isocyanate-functional prepolymer comprising the reaction product of at least one isocyanate-modified poly(alkylene carbonate) polyahl of claim 1 and at least one organic polyisocyanate; the proportion of said isocyanate-modified poly(alkylene carbonate) polyahl to said polyisocyanate being such that all polyahl moieties are reacted with isocyanate moieties and isocyanate moieties are present in excess.
- 27. A urethane/urea polymer comprising the residue of at least one isocyanate-functional prepolymer of claim 26 and the residue of at least one polyahl selected from the group consisting of aromatic, aliphatic, arylaliphatic, alkylaromatic and cycloaliphatic polyamines, polymercaptans and polyfunctional hydroxyl compounds.
- 28. A urethane/urea polymer comprising the residue of one or more of the isocyanate-modified poly(alkylene carbonate) polyahls of claim 1 and one or more organic polyisocyanates.
- 29. The isocyanate-modified poly(alkylene carbonate) polyahl of claim 1 wherein
- (1) the poly(alkylene carbonate) moieties are present in sufficient amount to provide a sufficient proportion of carbonate moieties to enable the isocyanate-modified polyahl to react under heating at reduced pressure to increase the molecular weight of the isocyanate-modified polyahl; and
- (2) the poly(alkyleneoxy) moieties are present in sufficient amount to increase the flexibility of polyurethane/urea polymers made from the isocyanate-modified poly(alkylene carbonate) polyahl.
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. patent application Ser. No. 850,788 filed Apr. 11, 1986, now U.S. Pat. No. 4,709,069, and is a related application to U.S. patent applications Ser. No. 831,761 filed Feb. 21, 1986, now U.S. Pat. No. 4,689,353; Ser. No. 931,597 filed Nov. 16, 1986, now U.S. Pat. No. 4,795,810; and Ser. No. 931,498 filed Nov. 16, 1986, now U.S. Pat. No. 4,816,529.
US Referenced Citations (13)
Non-Patent Literature Citations (1)
Entry |
Kohler et al., J. Am. Chem. Soc., 49, 3181-3188 (1927). |
Continuation in Parts (1)
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Number |
Date |
Country |
Parent |
850788 |
Apr 1986 |
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