Novel polyether polycarbonate block copolymers and polyurethanes prepared therefrom

Claim 2

A polyether polycarbonate block copolymer comprising (a) the residue of a hydrocarbon or a hydrocarbyloxy hydrocarbon compound containing 3 or more functional groups with active hydrogens; (b) an alkylene polyether, polyamide, aromatic polycarbonate, polyester, aromatic polyether, polyimide, polysulfide, polysulfone or polysaccharide block wherein such a block is bonded to the residue of each active hydrogen-containing functional group; and (c) polyether polycarbonate blocks which comprise ether and carbonate ether units arranged in random order, wherein the polyether polycarbonate blocks are bonded to the blocks defined in (b).

Claim 3

The polyether polycarbonate block copolymer of claim 1 wherein the ether unit is a substituted or unsubstituted alkylene moiety bonded to an oxygen and the carbonate ether unit is a carbonyl group bonded to an ether unit.

Claim 4

The polyether polycarbonate block copolymer of claim 2 wherein the block (b) comprises a polyalkylene ether.

Claim 5

The polyether polycarbonate block copolymer of claim 3 wherein the polyalkylene ether block comprises unsubstituted or substituted ethylene moieties bonded to oxygen atoms.

Claim 6

The polyether polycarbonate block copolymer of claim 4 wherein block (b) further comprises between about 1 and 200 alkylene ether units.

Claim 7

The polyether polycarbonate block copolymer of claim 5 wherein block (c) comprises the residue of one or more alkylene carbonates.

Claim 8

The polyether polycarbonate block copolymer of claim 5 wherein block (c) comprises the residue of between about 1 and 1000 alkylene carbonates.

Claim 9

The polyether polycarbonate block copolymers of claim 1 wherein two or more polyether polycarbonate block copolymers are bridged by carbonyl moieties.

Claim 10

Polyether polycarbonate block copolymers corresponding to the formulas ##STR18## wherein B is ##STR19## with the proviso that X is always bonded to R 1 ; A is an alkylene ether, amide, aromatic carbonate, ester, imide, sulfide, sulfone or saccharide unit; R 1 is separately in each occurrence an n valent hydrocarbon radical or hydrocarbyloxy hydrocarbon radical; 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 of the following: a halo, cyano, nitro, thioalkyl, tert-amino, alkoxy, aryloxy, aralkoxy, carbonyldioxyalkyl, carbonyldioxyaryl, carbonyl dioxyaralkyl, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, alkylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkylsulfinyl, arylsulfinyl, aralkylsulfinyl, alkylsulfonyl, arylsulfonyl, or aralkylsulfonyl group; X is S, O, NH, ##STR20## m is separately in each occurrence an integer of from 1 to 200; n is separately in each occurrence an integer of from 3 to 25; p is separately in each occurrence 0 or 1; q is separately in each occurrence an integer of 1 or greater; r is separately in each occurrence an integer of from 1 to 25; s is separately in each occurrence an integer of from 1 to 20; and t is separately in each occurrence an integer of from 0 to 24.

Claim 11

Polyether polycarbonate block copolymers corresponding to the formulas ##STR18## wherein B is ##STR19## with the proviso that X is always bonded to R 1 ; A is an alkylene ether, amide, aromatic carbonate, ester, imide, sulfide, sulfone or saccharide unit; R 1 is separately in each occurrence an n valent hydrocarbon radical or hydrocarbyloxy hydrocarbon radical; 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 of the following: a halo, cyano, nitro, thioalkyl, tert-amino, alkoxy, aryloxy, aralkoxy, carbonyldioxyalkyl, carbonyldioxyaryl, carbonyl dioxyaralkyl, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, alkylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkylsulfinyl, arylsulfinyl, aralkylsulfinyl, alkylsulfonyl, arylsulfonyl, or aralkylsulfonyl group; X is S, O, NH, ##STR20## m is separately in each occurrence an integer of from 1 to 200; n is separately in each occurrence an integer of from 3 to 25; p is separately in each occurrence 0 or 1; q is separately in each occurrence an integer of 1 or greater; r is separately in each occurrence an integer of from 1 to 25; s is separately in each occurrence an integer of from 1 to 20; and t is separately in each occurrence an integer of from 0 to 24.

Claim 12

The polyether polycarbonate block copolymer of claim 9 wherein R 1 is aliphatic or cycloaliphatic; R 2 is hydrogen, C 1-20 alkyl, C 1-20 haloalkyl, C 1-20 alkenyl, or phenyl; X is S, O, or NH; m is an integer of between 1 to 75 inclusive; n is an integer of 3 to 10 inclusive; q is an integer of 1 to 1000 inclusive; r is an integer of 2 to 10 inclusive; s is an integer of 1 to 10 inclusive; and t is an integer of 0 to 9 inclusive.

Claim 13

The polyether polycarbonate block copolymer of claim 10 wherein R 1 is an n valent alkane or n valent cycloalkane; R 2 is hydrogen, C 1-3 alkyl, C 2-3 alkenyl or phenyl; m is an integer of 3 to 50 inclusive; n is an integer of 3 to 5 inclusive; q is an integer of 1 to 500 inclusive; r is 1 or 2; s is an integer of 1 to 4 inclusive; and t is an integer of 0 to 4 inclusive.

Claim 14

The polyether polycarbonate block copolymer of claim 11 wherein R 1 is a n valent C 1-10 alkane; and R 2 is hydrogen, methyl or ethyl.

Claim 15

The polyether polycarbonate block copolymer of claim 12 wherein A is an alkylene ether unit.

Claim 16

The polyether polycarbonate block copolymer of claim 13 wherein the alkylene ether unit corresponds to the formula --C(R 2 ) 2 --C(R 2 ) 2 --O--.

Claim 17

A polyether polycarbonate block copolymer prepared by the process which comprises contacting (a) a hydrocarbon or hydrocarbyloxy hydrocarbon substituted with between about 3 and 25 reactive hydrogen-containing functional groups wherein an alkylene polyether, polyamide, aromatic polycarbonate, polyester, aromatic polyether, polyimide, polysulfide, polysulfone or a polysaccharide block is bonded to each active hydrogen-containing functional group; with (b) one or more moles of an alkylene carbonate per block attached to a functional group, under conditions such that a polyether polycarbonate block copolymer is prepared.

Claim 18

A polyether polycarbonate block copolymer prepared by the process which comprises contacting (a) a hydrocarbon or hydrocarbyloxy hydrocarbon substituted with between about 3 and 25 reactive hydrogen-containing functional groups wherein an alkylene polyether, polyamide, aromatic polycarbonate, polyester, aromatic polyether, polyimide, polysulfide, polysulfone or a polysaccharide block is bonded to each active hydrogen-containing functional group; with (b) one or more moles of an alkylene carbonate per block attached to a functional group, under conditions such that a polyether polycarbonate block copolymer is prepared.

Claim 19

The polyether polycarbonate block copolymer of claim 15 wherein the contacting occurs in the presence of a catalytic amount of an ester exchange catalyst at a temperature of between about 125° and 200° C.

Claim 20

The polyether polycarbonate block copolymer of claim 16 which involves contacting between about 1 and 1000 moles of alkylene carbonate with each block bonded to an active hydrogen containing functional group.

Claim 21

A process for the preparation of a polyether polycarbonate block copolymer which comprises contacting (a) hydrocarbon substituted with between about 3 and 25 reactive hydrogen-containing functional groups wherein each reactive hydrogen-containing functional group is further bonded to an alkylene polyether, polyamide, aromatic polycarbonate, polyester, aromatic polyether, polyimide, polysulfide, polysulfone or a polysaccharide block with (b) one or more moles of an alkylene carbonate per block attached to a reactive functional group, at a temperature of between 125° C. and 200° C. under conditions such that a polyether polycarbonate block copolymer is prepared.

Claim 22

A process for the preparation of a polyether polycarbonate block copolymer which comprises contacting (a) hydrocarbon substituted with between about 3 and 25 reactive hydrogen-containing functional groups wherein each reactive hydrogen-containing functional group is further bonded to an alkylene polyether, polyamide, aromatic polycarbonate, polyester, aromatic polyether, polyimide, polysulfide, polysulfone or a polysaccharide block with (b) one or more moles of an alkylene carbonate per block attached to a reactive functional group, at a temperature of between 125° C. and 200° C. under conditions such that a polyether polycarbonate block copolymer is prepared.

Claim 23

The process of claim 18 wherein the contacting occurs in the presence of a catalytic amount of an ester exchange catalyst.

Claim 24

The process of claim 19 wherein between about 1 and 1000 inclusive moles of alkylene carbonate per block bonded to a reactive functional group is contacted.

Claim 25

The process of claim 20 wherein between about 1 and 500 moles or alkylene carbonate per block connected to a reactive functional group is contacted.

Claim 26

The process of claim 21 wherein the temperature is between about 150° C. to 180° C.

Claim 27

The process of claim 21 wherein the amount of the ester exchange catalyst is between about 0.01 to 5 percent by weight.

Claim 28

The process of claim 23 wherein the amount of the ester exchange catalyst is between about 0.1 and 1.0 weight percent.

Claim 29

The process of claim 24 wherein the catalyst is an alkali metal carbonate, an alkali metal metaborate or an alkali metal stannate.

Claim 30

A polyether polycarbonate block copolymer comprising: (a) the residue of a hydrocarbon or a hydrocarbyloxy hydrocarbon compound containing 3 or more functional groups with active hydrogens; (b) an alkylene polyether block wherein such block is bonded to the residue of each active hydrogen-containing functional group; and (c) polyether polycarbonate blocks which comprise ether and carbonate ether units arranged in random order, wherein the polyether polycarbonate blocks are bonded to the blocks defined in (b) and the ether unit is a substituted or unsubstituted alkylene moiety bonded to an oxygen and the carbonate ether unit is a carbonyl group bonded to an ether unit.

Claim 31

A polyether polycarbonate block copolymer comprising: (a) the residue of a hydrocarbon or a hydrocarbyloxy hydrocarbon compound containing 3 or more functional groups with active hydrogens; (b) an alkylene polyether block wherein such block is bonded to the residue of each active hydrogen-containing functional group; and (c) polyether polycarbonate blocks which comprise ether and carbonate ether units arranged in random order, wherein the polyether polycarbonate blocks are bonded to the blocks defined in (b) and the ether unit is a substituted or unsubstituted alkylene moiety bonded to an oxygen and the carbonate ether unit is a carbonyl group bonded to an ether unit.

Claim 32

The polyether polycarbonate block copolymer of claim 26 wherein the polyalkylene ether block comprises unsubstituted or substituted ethylene moieties bonded to oxygen atoms.

Claim 33

The polyether polycarbonate block copolymer of claim 27 wherein block (b) further comprises between about 1 and 200 alkylene ether units.

Claim 34

The polyether polycarbonate block copolymer of claim 28 wherein block (c) comprises the residue of one or more alkylene carbonates.

Claim 35

The polyether polycarbonate block copolymer of claim 28 wherein block (c) comprises the residue of between 1 and 1000 alkylene carbonates.

Claim 36

The polyether polycarbonate block copolymers of claim 26 wherein two or more polyether polycarbonate block copolymers are bridged by carbonyl moieties.

Claim 37

Polyether polycarbonate block copolymers corresponding to the formulas ##STR21## wherein B is ##STR22## with the proviso that X is always bonded to R 1 ; A is an alkylene ether unit; R 1 is separately in each occurrence an n valent hydrocarbon radical or hydrocarbyloxy hydrocarbon radical; 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 of the following: a halo, cyano, nitro, thioalkyl, tert-amino, alkoxy, aryloxy, aralkoxy, carbonyldioxyalkyl, carbonyldioxyaryl, carbonyl dioxyaralkyl, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, alkylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkylsulfinyl, arylsulfinyl, aralkylsulfinyl, alkylsulfonyl, arylsulfonyl, or aralkylsulfonyl group; X is S, O, NH, ##STR23## m is separately in each occurrence an integer of from 1 to 200; n is separately in each occurrence an integer of from 3 to 25; p is separately in each occurrence 0 to 1; q is separately in each occurrence an integer of 1 or greater; r is separately in each occurrence an integer of from 1 to 25; s is separately in each occurrence an integer of from 1 to 20; and t is separately in each occurrence an integer of from 0 to 24.

Claim 38

Polyether polycarbonate block copolymers corresponding to the formulas ##STR21## wherein B is ##STR22## with the proviso that X is always bonded to R 1 ; A is an alkylene ether unit; R 1 is separately in each occurrence an n valent hydrocarbon radical or hydrocarbyloxy hydrocarbon radical; 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 of the following: a halo, cyano, nitro, thioalkyl, tert-amino, alkoxy, aryloxy, aralkoxy, carbonyldioxyalkyl, carbonyldioxyaryl, carbonyl dioxyaralkyl, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, alkylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkylsulfinyl, arylsulfinyl, aralkylsulfinyl, alkylsulfonyl, arylsulfonyl, or aralkylsulfonyl group; X is S, O, NH, ##STR23## m is separately in each occurrence an integer of from 1 to 200; n is separately in each occurrence an integer of from 3 to 25; p is separately in each occurrence 0 to 1; q is separately in each occurrence an integer of 1 or greater; r is separately in each occurrence an integer of from 1 to 25; s is separately in each occurrence an integer of from 1 to 20; and t is separately in each occurrence an integer of from 0 to 24.

Claim 39

The polyether polycarbonate block copolymer of claim 32 wherein the alkylene ether unit corresponds to the formula --C(R 2 ) 2 --C(R 2 ) 2 --O --.