Repeating block, oligomer-free, polyphase, thermoformable polyurethanes and method of preparation thereof

Claim 3

The method of claim 1 wherein said diisocyanate is an aliphatic or cycloaliphatic diisocyanate.

Claim 4

The method of claim 1 wherein more than two molecular proportions of said diisocyanate are employed in step (1) and said diisocyanate is of a nature such that if said composition is reacted with a chain extender, the resulting polymer will be essentially free of domain crystallinity.

Claim 5

The method of claim 3 wherein said diisocyanate is a mixture of isomeric, cycloaliphatic diisocyanate species.

Claim 6

The method of claim 4 wherein said mixture consists of isophorone diisocyanate isomers or di(isocyanatocyclohexyl)methane isomers.

Claim 7

The method of claim 1 wherein at least 95 percent of the molecules of said polyether glycol may be represented by the ideal formula: ##STR5## wherein I is the residue of a difunctional initiator, e is zero or 1, Q may be the same or different in each occurrence and is a C 1 -C 10 alkylene or alkylcycloalkylene group and a, b, c and d are integers such that the molecular weight of said glycol is within said range of from about 1000 to about 6000.

Claim 8

The method of claim 6 wherein Q is CH 2 and the ratio of (a+d) to (b+c) is such that the overall ethylene oxide to propylene oxide weight ratio in the glycol is not greater than 20/80.

Claim 9

The method of claim 1 wherein a catalyst is employed.

Claim 10

The method of claim 8 wherein said diisocyanate is a mixture of isophorone diisocyanate isomers or di(isocyanatocyclohexyl)methane isomers.

Claim 11

The method of claim 9 wherein at least 95% of the molecules of said polyether glycol may be represented by the following ideal formula: ##STR6## wherein I is the residue of a difunctional initiator, e is zero or 1, Q is CH 2 and a, b, c and d are integers such that the molecular weight of the polyglycol is within said range of from about 1000 to about 6000.

Claim 12

The method of claim 1 additionally comprising converting said prepolymer composition to a final polymer composition comprising a repeating block, oligomer-free, polyphase, thermoformable, segmented polyurethane which has a weight average molecular weight of about 100,000 or more and consists essentially of alternating hard and soft segments, said conversion being by (i) adding to the prepolymer composition such additional amount of a diisocyanate as may be required to provide a total of up to about 10 molecular proportions of free and converted diisocyanate per molecular proportion of said polyether glycol, with the proviso that the free diisocyanate present when the following step (ii) is initiated is of a nature such that the final polymer will be essentially free of domain crystallinity, (ii) mixing with the prepolymer composition, separately or in admixture with any diisocyanate added in (i), a chain extender which is a short chain, non-flexibilizing compound having from 2 to 4 isocyanate-reactive functional groups, the amount of said chain extender being such that the isocyanate index for the resulting mixture is from about 1.025 to about 1.035, and (iii) adding a catalyst and allowing said isocyanateterminated prepolymer, the free diisocyanate and said chain extender to react, thereby forming said final polymer, said soft segments being contributed to said final polymer by said prepolymer and said hard segments being formed by the interaction of the chain extender with isocyanate terminations of the prepolymer and with free diisocyanate molecules.

Claim 13

The method of claim 11 wherein said diisocyanate present when said step (ii) is initiated consists of one or more aliphatic or cycloaliphatic diisocyanates.

Claim 14

The method of claim 12 wherein said diisocyanate is a mixture of isophorone isomers or di(isocyanatocyclohexyl)methane isomers.

Claim 15

The method of claim 11 wherein said polyether glycol consists essentially of molecules which may be represented by the following ideal formula: ##STR7## wherein I is the residue of a difunctional initiator, e is zero or 1, Q may be the same or different in each occurrence and is a C 1 -10 alkylene or alkylcycloalkylene group, and a, b, c and d are integers such that the molecular weight of said polyglycol is within said range of from about 1000 to about 6000.

Claim 16

The method of claim 14 wherein Q is CH 2 and the ratio of (a+d) to (b+c) is such that the overall ethylene oxide to propylene oxide weight ratio in the polyglycol is not greater than 20/80.

Claim 17

The method of claim 11 wherein a catalyst is employed in preparing said prepolymer composition.

Claim 18

The method of claim 11 wherein said chain extender is 1,4-butane diol or ethylene glycol.

Claim 19

The method of claim 15 wherein a catalyst is employed in preparing said prepolymer composition, the free diisocyanate present when step (ii) is initiated consists of one or more aliphatic or cycloaliphatic diisocyanates and the chain extender is 1,4-butane diol or ethylene glycol.

Claim 20

The method of claim 11 in which the polyglycol to diisocyanate to chain extender mole ratio is within the range of from 1/3/2 to 1/15/14.

Claim 21

The method of claim 18 wherein the polyglycol to diisocyanate to chain extender mole ratio is within the range of from 1/4/3 to 1/6/5.

Claim 22

The method of claim 20 in which said ratio is 1/about 5/about 4.

Claim 23

The method of claim 21 in which the free diisocyanate present when step (ii) is initiated is a mixture of isophorone isomers or di(isocyanatocyclohexyl)methane isomers.

Claim 24

The method of claim 11 in which said polyglycol is an ethylene oxide capped polypropylene glycol having a molecular weight of from about 1900 to about 2100 and an overall ethylene oxide to propylene oxide weight ratio of about 12/88.

Claim 25

The method of claim 20 in which said polyglycol is an ethylene oxide capped polypropylene glycol having a molecular weight of from about 1900 to about 2100 and an overall ethylene oxide to propylene oxide weight ratio of about 12/88.

Claim 26

The method of claim 22 in which said polyglycol is an ethylene oxide capped polypropylene glycol having a molecular weight of from about 1900 to about 2100 and an overall ethylene oxide to propylene oxide weight ratio of about 12/88.

Claim 27

A urethane prepolymer, optionally in admixture with non-polymeric molecules of one or more non-aromatic diisocyanates, said prepolymer consisting essentially of generally linear molecules terminated at each end by an isocyanate group and consisting of n branched, polyether glycol residues joined, through intervening carbamate groups, with (n+1) non-aromatic diisocyanate residues, n ranging from 1 to about 4 and having an average value of about 1.5 to about 1.7 and said glycol being methylol terminated, having a weight average molecular weight of from about 1000 to about 6000 and consisting essentially of chains of --O--CRR'--CH 2 --units in which each of R and R' is H, methyl or ethyI, independently, except that in at least a preponderance of said units one or the other of R and R' is not H.

Claim 28

A urethane prepolymer, optionally in admixture with non-polymeric molecules of one or more non-aromatic diisocyanates, said prepolymer consisting essentially of generally linear molecules terminated at each end by an isocyanate group and consisting of n branched, polyether glycol residues joined, through intervening carbamate groups, with (n+1) non-aromatic diisocyanate residues, n ranging from 1 to about 4 and having an average value of about 1.5 to about 1.7 and said glycol being methylol terminated, having a weight average molecular weight of from about 1000 to about 6000 and consisting essentially of chains of --O--CRR'--CH 2 --units in which each of R and R' is H, methyl or ethyI, independently, except that in at least a preponderance of said units one or the other of R and R' is not H.

Claim 29

A prepolymer as in claim 26 wherein at least 95% of the molecules of said polyglycol may be represented by the following ideal formula: ##STR8## wherein I is the residue of a difunctional initiator, e is zero or 1, Q may be the same or different in each occurrence and is a C 1 -C 10 alkylene or alkylcycloalkylene group, and a, b, c and d are integers such that the molecular weight of said glycol is within said range of from about 1000 to about 6000.

Claim 30

A prepolymer as in claim 26 in which said diisocyanate residues are derived from one or more aliphatic or cycloaliphatic diisocyanates.

Claim 31

A prepolymer as in claim 27 in which said diisocyanate residues are derived from one or more aliphatic or cycloaliphatic diisocyanates.

Claim 32

A prepolymer of claim 26 in admixture with one or more non-polymeric, non-aromatic diisocyanate.

Claim 33

A prepolymer of claim 27 in admixture with one or more non-polymeric, non-aromatic diisocyanate.

Claim 34

A prepolymer of claim 28 in admixture with a non-polymeric, non-aromatic diisocyanate which consists of one or more aliphatic or cycloaliphatic diisocyanates.

Claim 35

A prepolymer of claim 29 in admixture with one or more aliphatic or cycloaliphatic diisocyanates which are the same as those from which said residues are derived.

Claim 36

A prepolymer of claim 29 in which Q is --CH 2 -- and the values of a, b, c and d are such that said polyglycol has a molecular weight of from about 1900 to about 2100 and the weight ratio of --O--CH 2 --CH 2 to --O--CHCH 3 --CH 2 -- units therein is not greater than about 20/80.

Claim 37

A prepolymer of claim 33 in which Q is --CH 2 and said values of a, b, c and d are such that said polyglycol has a molecular weight of from about 1900 to about 2100 and the weight ratio of --O--CH 2 --CH 2 -- to --O--CHCH 3 --CH 2 -- units therein is about 12/88.

Claim 38

A repeating block, oligomer-free, polyphase, thermoformable, segmented polyurethane which is free of domain crystallinity, has a weight average molecular weight of from about 100,000 to about 200,000 and consists essentially of alternating soft and hard segments; said soft segments being deriveable from the reaction of: (1) generally linear molecules terminated at each end by an isocyanate group and consisting of (a) n residues of one or more methylolterminated polyether glycols having molecular weights of from about 1000 to about 6000 and consisting essentially of chains of --O--CRR'--CH 2 -- units in which each of R and R' is H, methyl or ethyl independently, except that in at least a preponderance of said units one or the other of R and R' is not H, and (b) (n+1) residues of one or more non-aromatic diisocyanates, joined to said polyether glycol residues by intervening carbamate groups, n ranging from 1 to about 4 and having an average value of from about 1.5 to about 1.7, and said hard segments being deriveable from the reaction of a chain extender with the isocyanate end groups in said molecules and with one or more non-aromatic, non-polymeric diisocyanates of a nature such that the resulting carbamate groups will be unable to associate with each other in such manner as to result in domain crystallinity in the resulting polymer, the mole ratio of the polyglycol to diisocyanate to chain extender being within the range of from about 1/3/2 to about 1/15/14 and the overall isocyanate index being within the range of from about 1.025 to about 1.035.

Claim 39

A repeating block, oligomer-free, polyphase, thermoformable, segmented polyurethane which is free of domain crystallinity, has a weight average molecular weight of from about 100,000 to about 200,000 and consists essentially of alternating soft and hard segments; said soft segments being deriveable from the reaction of: (1) generally linear molecules terminated at each end by an isocyanate group and consisting of (a) n residues of one or more methylolterminated polyether glycols having molecular weights of from about 1000 to about 6000 and consisting essentially of chains of --O--CRR'--CH 2 -- units in which each of R and R' is H, methyl or ethyl independently, except that in at least a preponderance of said units one or the other of R and R' is not H, and (b) (n+1) residues of one or more non-aromatic diisocyanates, joined to said polyether glycol residues by intervening carbamate groups, n ranging from 1 to about 4 and having an average value of from about 1.5 to about 1.7, and said hard segments being deriveable from the reaction of a chain extender with the isocyanate end groups in said molecules and with one or more non-aromatic, non-polymeric diisocyanates of a nature such that the resulting carbamate groups will be unable to associate with each other in such manner as to result in domain crystallinity in the resulting polymer, the mole ratio of the polyglycol to diisocyanate to chain extender being within the range of from about 1/3/2 to about 1/15/14 and the overall isocyanate index being within the range of from about 1.025 to about 1.035.

Claim 40

A polymer of claim 36 wherein said polyglycol residues are deriveable from a polyether glycol consisting essentially of molecules of the formula: ##STR9## wherein I is the residue of a difunctional initiator, e is zero or 1, Q may be the same or different in each occurrence and is a C 1 -C 10 alkylene or alkylcycloalkylene group, and a, b, c and d are integers such that the molecular weight of said glycol is within said range of from about 1000 to about 6000.

Claim 41

A polymer of claim 36 wherein said hard segments are deriveable from the reaction of a chain extender with the isocyanate end groups in said molecules and with a mixture of isomers of one or more aliphatic or cycloaliphatic diisocyanates.

Claim 42

A polymer of claim 37 in which said hard segments are deriveable from the reaction of a chain extender with the isocyanate end groups in said molecules and with a mixture of isomers of one or more aliphatic or cycloaliphatic diisocyanates.

Claim 43

A polymer of claim 36 wherein the chain extender is ethylene glycol or 1,4-butane diol.

Claim 44

A polymer of claim 37 wherein the chain extender is ethylene glycol or 1,4-butane diol.

Claim 45

A polymer of claim 38 wherein the chain extender is ethylene glycol or 1,4-butane diol.

Claim 46

A polymer of claim 39 wherein the chain extender is ethylene glycol or 1,4-butane diol.

Claim 47

A polymer of claim 36 in which said mole ratio is within the range of from about 1/4/3 to about 1/6/5.

Claim 48

A polymer of claim 41 wherein said mole ratio is about 1/5/4.

Claim 49

A polymer of claim 42 wherein said mole ratio is about 1/5/4.

Claim 50

A polymer of claim 43 wherein said mole ratio is about 1/5/4.

Claim 51

A polymer of claim 37 wherein Q is CH 2 and a, b, c and d are such that said polyglycol has a molecular weight of from about 1900 to about 2100 and the weight ratio of --O--CH 2 --CH 2 -- to --O--CHCH 3 --CH 2 -- units therein is not greater than about 20/80.

Claim 52

A polymer of claim 48 in which said weight ratio is about 12/88.

Claim 53

A polymer of claim 47 wherein Q is CH 2 and a, b, c and d are such that said polyglycol has a molecular weight within the range of from about 1900 to about 2100 and the weight ratio of --O--CH 2 --CH 2 -- to --O--CHCH 3 --CH 2 -- units therein is about 12/88.

Claim 54

A polymer of claim 36 having an average molecular weight of from about 130,000 to 180,000.

Claim 55

A polymer of claim 38 having an average molecular weight of from about 130,000 to about 180,000.

Claim 56

A polymer of claim 40 having an average molecular weight of from about 130,000 to about 180,000.

Claim 57

A polymer of claim 42 having an average molecular weight of from about 130,000 to about 180,000.

Claim 58

A polymer of claim 44 having an average molecular weight of from about 130,000 to about 180,000.

Claim 59

A polymer of claim 46 having an average molecular weight of from about 130,000 to about 180,000.

Claim 60

A polymer of claim 47 having an average molecular weight of from about 130,000 to about 180,000.

Claim 61

A polymer of claim 48 having an average molecular weight of from about 130,000 to about 180,000.

Claim 62

A polymer of claim 49 having an average molecular weight of from about 145,000 to about 155,000.

Claim 63

A polymer of claim 50 having an average molecular weight of from about 145,000 to about 155,000.