Claims
- 1. An ester-modified poly(alkylene carbonate) polyahl comprising
- (a) a backbone comprising
- (1) the residue of at least one polyahl initiator:
- (2) a plurality of poly(alkyleneoxy) moieties; and
- (3) a plurality of poly(alkylene carbonate) moieties;
- (b) a plurality of active hydrogen end groups; and
- (c) the residue of at least one modifier which resides in the polymer backbone and/or is present as an end group; wherein the ester modifier is selected from the group consisting of
- (1) polyester polyahls:
- (2) polyacids:
- (3) acid esters of polyacids and C.sub.1-8 monofunctional alcohols; and
- (4) cyclic acid anhydrides;
- said ester-modified poly(alkylene carbonate) polyahls having a number average molecular weight higher than the number average molecular weight of any known poly(alkylene carbonate) polyahl comprising the same monomeric components.
- 2. The ester-modified poly(alkylene carbonate) polyahl of claim 1 wherein the modifier is an aliphatic, aryl aliphatic or cycloaliphatic polyester polyahl.
- 3. The ester-modified poly(alkylene carbonate) polyahl of claim 2 wherein the modifier is a polyester polyol.
- 4. The ester-modified poly(alkylene carbonate) polyahl of claim 3 wherein the polyester polyol is a diol selected from the group consisting of monoethylene glycol adipate, diethylene glycol adipate, 1,4-butanediol adipate, 1,6-hexanediol adipate, monopropylene glycol adipate and poly(caprolactone) diol.
- 5. The ester-modified poly(alkylene carbonate) polyahl of claim 3 wherein the polyester polyol is a triol selected from the group consisting of glycerine-containing and trimethylol propane-containing adipates and terephthalates.
- 6. The ester-modified poly(alkylene carbonate) polyahl of claim 3 wherein the polyester polyol is a poly(caprolactone) triol.
- 7. The ester-modified poly(alkylene carbonate) polyahl of claim 1 wherein the modifier is a polycarboxylic acid selected from the group consisting of succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, dodecanedioic acid and octadecanedioic acid.
- 8. The ester-modified poly(alkylene carbonate) polyahl of claim 1 wherein the modifier is an ester of a C.sub.1-8 monofunctional alcohol and a polycarboxylic acid selected from the group consisting of succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, dodecanedioic acid, octadecanedioic acid, terephthalic acid and phthalic acid.
- 9. The ester-modified poly(alkylene carbonate) polyahl of claim 1 wherein the modifier is a cyclic acid anhydride, selected from the group consisting of succinic anhydride, maleic anhydride and phthalic anhydride.
- 10. The ester-modified poly(alkylene carbonate) polyahl of claim 1 wherein the weight percent modifier is from 5 to 80 percent.
- 11. The ester-modified poly(alkylene carbonate) polyahl of claim 10 wherein the weight percent modifier is from 7 to 65 percent.
- 12. The ester-modified poly(alkylene carbonate) polyahl of claim 1 wherein the weight percent carbon dioxide is from 5 to 25 percent.
- 13. The ester-modified poly(alkylene carbonate) polyahl of claim 1 wherein the number average molecular weight is from 500 to 20,000.
- 14. The ester-modified poly(alkylene carbonate) polyahl of claim 1 wherein the active hydrogen end groups are hydroxyl groups.
- 15. The ester-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 occurrence 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, alkyoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, alkylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkylsulfinyl, arylsulfinyl, aralkylsulfinyl, alkylsulfonyl, arylsulfonyl, or aralkylsulfonyl group;
- M is separately in each occurrence the residue of a polyester polyahl or the residue of a polycarboxylic acid;
- m is separately in each occurrence an integer from 1 to 40 when M is the residue of a polyester polyahl and m is 1 when M is the residue of a polycarboxylic acid;
- X is separately in each occurrence S, O, NH ##STR8## 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 because terminal carbonate moieties are unstable and form OH moieties by the elimination of CO.sub.2 ;
- 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 10;
- x is separately in each occurrence an integer of from 1 to 40;
- y is separately in each occurrence an integer of from 1 to 120; and
- z is separately in each occurrence an integer of from 0 to 5.
- 16. The modified poly(alkylene carbonate) polyahl of claim 15 wherein
- X is oxygen:
- m is an integer from 1 to 20;
- 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.
- 17. The modified poly(alkylene carbonate) polyahl of claim 16 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:
- M is the residue of a polyester polyahl;
- X is S, O or NH; and
- n is an integer from 1 to 10.
- 18. The modified poly(alkylene carbonate) polyahl of claim 17 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;
- n is an integer from 1 to 5; and
- s is an integer from 1 to 5.
- 19. The modified poly(alkylene carbonate) polyahl of claim 18 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 ore more oxygen moieties;
- R.sup.2 is hydrogen or methyl; and
- n is 1 or 2.
- 20. The modified poly(alkylene carbonate) polyahl of claim 19 wherein R.sup.2 is hydrogen.
- 21. The modified poly(alkylene carbonate) polyahl of claim 15 wherein M is the residue of an aliphatic, aryl aliphatic or cycloaliphatic polyester polyol.
- 22. The modified poly(alkylene carbonate) polyahl of claim 21 wherein the polyester polyol is selected from the group consisting of monoethylene glycol adipate, diethylene glycol adipate, 1,4-butanediol adipate, 1,6-hexanediol adipate, monopropylene glycol adipate, poly(caprolactone) diol and poly(caprolactone) triol.
- 23. The modified poly(alkylene carbonate) polyahl of claim 15 wherein said modified poly(alkylene carbonate) polyahl includes
- about 90 percent by weight of said poly(alkylene carbonate) polyahl; and
- about 10 percent by weight of said modifier.
- 24. The modified poly(alkylene carbonate) polyahl of claim 15 wherein said modified poly(alkylene carbonate) polyahl includes
- about 75 percent by weight of said poly(alkylene carbonate) polyahl; and
- about 25 percent by weight of said modifier.
- 25. The modified poly(alkylene carbonate) polyahl of claim 15 wherein said modifier poly(alkylene carbonate) polyahl includes
- about 50 percent by weight of said poly(alkylene carbonate) polyahl: and
- about 50 percent by weight of said modifier.
- 26. The modified poly(alkylene carbonate) polyahl of claim 15 wherein said modified poly(alkylene carbonate) polyahl includes
- about 25 percent by weight of said poly(alkylene carbonate polyahl; and
- about 75 percent by weight of said modifier.
- 27. The ester-modified poly(alkylene carbonate) polyahl of claim 15 wherein the number average molecular weight is from 500 to 20,000.
- 28. The ester-modified poly(alkylene carbonate) polyahl of claim 15 wherein the weight percent carbon dioxide is from 5 to 25 percent.
- 29. The modified poly(alkylene carbonate) polyahl of claim 1, obtained by reacting at least one poly(alkylene carbonate) polyahl with a modifier to form a poly(alkylene carbonate) polyahl having an increased molecular weight, and removing at least one gaseous compound other than a monoalkylene glycol from said reaction, said gaseous compound being at least as volatile as tetraethylene glycol and said modifier (1) having a plurality of moieties that are reactive with the carbonate and/or active hydrogen moieties of the poly(alkylene carbonate) polyahl and (2) being about as volatile or less volatile than the major gaseous compound removed.
- 30. The modified poly(alkylene carbonate) polyol of claim 14 which is a random polymer corresponding to the formula ##STR10## wherein R.sup.1 is R.sup.3 -X.sup.1.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;
- X.sup.1 is O, S or NH;
- M is separately in each occurrence the residue of a polyester polyol or the residue of a polycarboxylic acid;
- m is separately in each occurrence an integer of from 1 to 40 when M is the residue of a polyester polyol and m is 1 when M is the residue of a polycarboxylic acid;
- 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 10;
- x is 1;
- y is separately in each occurrence 1 to 40; and
- z is separately in each occurrence 1 to 100.
- 31. The modified poly(alkylene carbonate) polyol of claim 30 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.sup.1 is S, O, or NH;
- m is separately in each occurrence an integer of from 1 to 20 when M is the residue of a polyester polyol and m is 1 wherein M is the residue of a polycarboxylic acid;
- 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.
- 32. The modified poly(alkylene carbonate) polyol of claim 31 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 moieties;
- M is separately in each occurrence the residue of a polyester polyol:
- m is an integer from 1 to 10, inclusive;
- n is an integer from 1 to 5, inclusive,
- p is 1 to 5, inclusive; and
- s is an integer from 1 to 5, inclusive.
- 33. The modified poly(alkylene carbonate) polyol of claim 32 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.
- 34. The modified poly(alkylene carbonate) polyol of claim 30 wherein the weight percent modifier is from 5 percent to 80 percent.
- 35. The modified poly(alkylene carbonate) polyol of claim 30 wherein the number average molecular weight is from 500 to 20,000.
- 36. The poly(alkylene carbonate) polyahl of claim 1 obtained by exposing at least one poly(alkylene carbonate) polyahl to elevated temperatures, wherein the initiator has about the same or greater volatility as the dialkylene glycol, trialkylene glycol, or initiator segments are abstracted from the poly(alkylene carbonate) polyahl, at a pressure wherein the dialkylene glycol, trialkylene glycol or initiator is volatile, and removing the volatile dialkylene glycol, trialkylene glycol or initiator from the mass of the poly(alkylene carbonate) polyahl, under conditions such that the molecular weight of the poly(alkylene carbonate) polyahl is increased.
- 37. The modified poly(alkylene carbonate) polyahl of claim 1, prepared by contacting at least one poly(alkylene carbonate) polyahl with at least one modifier including at least one active hydrogen moiety, optionally in the presence of a catalytic amount of a catalyst for the reaction of an active moiety of the poly(alkylene carbonate) polyahl with reactive moiety of the modifier under conditions sufficient to cause reaction between said active moiety of said poly(alkylene carbonate) polyahl and said reactive moiety of said modifier to form a modified poly(alkylene carbonate) polyahl wherein the modifier is chemically bonded to the poly(alkylene carbonate) polyahl.
- 38. The modified poly(alkylene carbonate) polyahl of claim 37 wherein said modifier is a polyester polyol.
- 39. The modified poly(alkylene carbonate) polyahl of claim 38 wherein said polyester polyol is selected from the group consisting of monoethylene glycol adipate, diethylene glycol adipate, 1,4-butanediol adipate, 1,6-hexanediol adipate, monopropylene glycol adipate, poly(caprolactone) diol and poly(caprolactone) triol.
CROSS-REFERENCE TO RELATED APPLICATIONS
This is a divisional of application Ser. No. 931,498, filed Nov. 17, 1986, now U.S. Pat. No. 4,795,810, which is a continuation-in-part of U.S. patent applications Ser. No. 799,211 filed on Nov. 18, 1985, now U.S. Pat. No. 4,686,273, and Ser. No. 809,675 filed On Dec. 16, 1985, now U.S. Pat. No. 4,686,274; and is a related application to U.S. patent applications Ser. No. 750,362 filed on July 1, 1985 now abandoned; Ser. No. 850,788 filed on Apr. 11, 1986 now U.S. Pat. No. 4,709,069 and Ser. No. 931,597 filed on Nov. 17, 1986.
US Referenced Citations (12)
Divisions (1)
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931498 |
Nov 1986 |
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Continuation in Parts (1)
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799211 |
Nov 1985 |
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