Novel ester-modified poly(alkylene carbonate) polyahls and polyurethanes therefrom

Claim 2

An isocyanate-functional pre-polymer composition comprising the reaction product of at least one ester-modified poly(alkylene carbonate) polyahl and at least one organic polyisocyanate; the proportion of said ester-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, said 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 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 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.

Claim 3

The isocyanate-functional prepolymer composition of claim 1, having a weight percent isocyanate of 3 percent or greater.

Claim 4

The isocyanate-functional prepolymer composition of claim 1, wherein the ester-modified poly(alkylene carbonate) polyahl is an ester-modified poly(alkylene carbonate) polyol.

Claim 5

The isocyanate-functional prepolymer composition of claim 1 wherein said organic polyisocyanate is selected from the group consisting of aromatic, aliphatic, alkyl aromatic, aryl aliphatic and cycloaliphatic polyisocyanates.

Claim 6

The isocyanate-functional prepolymer composition of claim 4 wherein said polyisocyanate is toluene diisocyanate, methylene bis(4-phenylisocyanate) or their isomers or oligomers.

Claim 7

The isocyanate-functional prepolymer composition of claim 1, wherein the modified poly(alkylene carbonate) polyahl is a random polymer corresponding to the formula ##STR7## wherein R 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 Si; R 2 is separately in each occurrence hydrogen, halogen, a nitro group, a cyano group, a C 1-20 hydrocarbyl group or a C 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 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 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.

Claim 8

The isocyanate-functional prepolymer composition of claim 2, wherein the modified poly(alkylene carbonate) polyahl is a random polymer corresponding to the formula ##STR10## wherein R 1 is R 3 --X 1 n ; R 2 is separately in each occurrence hydrogen, halogen, a nitro group, a cyano group, a C 1-20 hydrocarbyl group or a C 1-20 hydrocarbyl group substituted with one or more halogen, cyano, nitro, thioalkyl, tert-amino, alkoxy, aryloxy, aralkoxy, carbonyldioxyalkyl, carbonyldioxyaryl, carbonyldioxaralkyl, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, alkylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkylsulfinyl, arylsulfinyl, aralkylsulfinyl, alkylsulfonyl, arylsulfonyl, or aralkylsulfonyl group; R 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 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 in 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 and wherein the active hydrogen end groups are hydroxyl groups.

Claim 9

The isocyanate-functional prepolymer composition of claim 7 wherein R 2 is hydrogen, methyl or ethyl; R 3 is an n-valent C 1-10 alkane containing oxygen moieties; X 1 is S, O or NH; M is separately in each occurrence the residue of a polyester polyol; m is an integer from 1 to 10, inclusive n is 1 or 2, inclusive p is 1 to 5, inclusive; y is 5 to 20, inclusive z is 20 to 50, inclusive; and s is an integer from 1 to 5, inclusive.

Claim 10

The isocyanate-functional prepolymer composition of claim 1, prepared by contacting at least one modified poly(alkylene carbonate) polyahl with the organic polyisocyanate under conditions of temperature, pressure, stoichiometry and mixing such that all of the polyahl moieties on the modified poly(alkylene carbonate) polyahl are reacted with the polyisocyanate and that the polyisocyanate is present in excess.

Claim 11

A urethane/urea polymer, comprising the residue of at least one isocyanate-functional prepolymer composition of claim 1; 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.

Claim 12

The urethane/urea polymer of claim 10, wherein said polyfunctional hydroxyl compound is an aliphatic diol selected from the group consisting of monoethylene glycol, diethylene glycol, 1,4-butanediol, monopropylene glycol and dipropylene glycol.

Claim 13

The urethane/urea polymer of claim 11, wherein said polyfunctional hydroxyl compound is a cyclic aliphatic diol selected from the group consisting of cyclohexane diol and cyclohexane dimethylol.

Claim 14

The urethane/urea polymer of claim 10 wherein said aromatic polyamine is an aromatic diamine.

Claim 15

The urethane/urea polymer of claim 13 wherein the aromatic diamine is diethyltoluenediamine.

Claim 16

The urethane/urea polymer of claim 10 formed by reacting approximately stoichiometric amounts of the isocyanate moieties of said isocyanate-functional prepolymer composition with the active hydrogen moieties of said polyahl.

Claim 17

The urethane/urea polymer of claim 15 wherein the equivalent ratio of isocyanate moieties:active hydrogen moieties is between 0.95:1.00 and 1.05:1.00.

Claim 18

The urethane/urea polymer of claim 10 in the form of an elastomer, a film, or a foam.

Claim 19

A urethane/urea polymer, comprising the residue of one or more of an ester-modified poly(alkylene carbonate) polyahl; and one or more organic polyisocyanates, said 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 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 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.

Claim 20

A urethane/urea polymer, comprising the residue of one or more of an ester-modified poly(alkylene carbonate) polyahl; and one or more organic polyisocyanates, said 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 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 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.

Claim 21

The urethane/urea polymer of claim 18 which in addition includes one or more other polyahls.

Claim 22

The urethane/urea polymer of claim 18 or 19 wherein the modified poly(alkylene carbonate) polyahl is a random polymer corresponding to the formula ##STR11## wherein R 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 2 is separately in each occurrence hydrogen, halogen, a nitro group, a cyano group, a C 1-20 hydrocarbyl group or a C 1-20 hydrocarbyl group substituted with one or more halo, cyano, nitro, thialkyl, 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 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 residuee of a polycarboxylic acid; X is separately in each occurrence S, O, NH ##STR12## A is separately in each occurrence ##STR13## 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 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

Claim 23

z is separately in each occurrence an integer of from 0 to 5.

Claim 24

z is separately in each occurrence an integer of from 0 to 5.

Claim 25

The urethane/urea polymer of claim 19 or 19 wherein the modified poly(alkylene carbonate) polyahl is a random polymer corresponding to the formula ##STR14## wherein R 1 is R 3 -X 1 n ; R 2 is separately in each occurrence hydrogen, halogen, a nitro group, a cyano group, a C 1-20 hydrocarbyl group or a C 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 3 is separately in each occurrence an n-valent hydrocarbon radical or hydrocarbon radical which contains one or more heteroatoms of O, N or Si; X 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 and wherein the active hydrogen end groups are hydroxyl groups.

Claim 26

The urethane/urea polymer of claim 18 or 19 wherein said organic polyisocyanate is selected from the group consisting of aromatic, aliphatic, alkylaromatic, arylaliphatic and cycloaliphatic polyisocyanates.

Claim 27

The uretane/urea polymer of claim 22 wherein said aromatic polyisocyanate is toluene diisocyanate, methylene bis(4-phenylisocyanate) or their isomers or oligomers.

Claim 28

The urethane/urea polymer of claim 19 wherein said other polyahls are selected from the group consisting of aromatic, aliphatic, alkylaromatic, arylaliphatic and cycloaliphatic polyamines, polymercaptans and polyfunctional hydroxyl compounds.

Claim 29

The urethane/urea polymer of claim 24 wherein said other aliphatic polyfunctional hydroxyl compound is selected from the group consisting of monoethylene glycol, diethylene glycol, 1,4-butanediol, monopropylene glycol and dipropylene glycol.

Claim 30

The urethane/urea polymer of claim 24 wherein said other cycloaliphatic polyfunctional hydroxyl compound is selected from the group consisting of cyclohexanediol and cyclohexanedimethylol.

Claim 31

The urethane/urea polymer of claim 24 wherein said other aromatic polyamine is an aromatic diamine.

Claim 32

The urethane/urea polymer of claim 27 wherein the aromatic diamine is diethyltoluene diamine.

Claim 33

The urethane/urea polymer of claim 18 or 19 formed by reacting approximately stoichiometric amounts of the isocyanate moieties of said organic polyisocyanates with the active hydrogen moieties of said polyahls.

Claim 34

The urethane/urea polymer of claim 29 where the equivalent ratio of isocyanate moieties:toal active hydrogen moieties is between 0.95:1.00 and 1.05:1.00.

Claim 35

The urethane/urea polymer of claim 18 or 19 in the form of an elastomer, a film, or a foam.