POLYURETHANES, POLYURETHANEUREAS AND POLYUREAS AND USE THEREOF

• US 20060293487A1
• Filed: 07/10/2006
• Published: 12/28/2006
• Est. Priority Date: 01/08/2004
• Status: Abandoned Application

• Current Assignee: Stichting Dutch Polymer Institute
• Original Assignee: Stichting Dutch Polymer Institute
• Inventors: van der Schuur, Jan M., GAYMANS, Reinoud Jaap, Noordover, Bart A.J.
• Application Number:
  US11/456,451
• Publication Number:
  US 20060293487A1
• Time in Patent Office: Days
• US Class Current: 528/44
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/3221 hydroxylated esters of carboxylic acids other than higher fatty acids
• CPC Class Codes: C08G 18/341 Dicarboxylic acids, esters of polycarboxylic acids containing two carboxylic acid groups
• CPC Class Codes: C08G 18/3825 containing amide groups C08G18/3821 takes precedence
• CPC Class Codes: C08G 18/4854 Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group

Abstract

The present invention is to a chain of polyurethane, polyurethaneurea and/or polyurea segmented copolymer wherein the polyurethane, polyurethaneurea and/or polyurea segments contain a chain extender having an amide segment, an ester segment, or a combination of amide and ester segments.

Claims

1. A chain extended polyurethane, polyurethaneurea and/or polyurea segmented copolymer comprising a polyol soft segment linked via a urethane or urea linkage to a hard segment having an amide segment, an ester segment or a combination of amide and ester segments as represented by Formula I

—

R—

B—

(R′

—

B)_n—

R—

 

 

(I)

wherein each B represents an —

N(H)C(O)—

, —

C(O)N(H)—

, —

C(O)—

O—

or —

O—

C(O)-moiety;

each R and R′

is a member selected from the group consisting of alkylene moieties, alicyclic moieties, arylene moieties, alkaryl moieties, arylalkyl moieties and heterocyclic moieties, and

n has a value of 0 to 6.

2. The copolymer of claim 1 wherein at least 50 percent of the —

R—

B—

(R′

—

B)_n—

R-segments are uniform in length as measured by NMR.

3. The copolymer of claim 1, wherein the segment —

R—

B—

(R′

—

B)_n—

R is a member selected from the group consisting of

—

R—

C(O)N(H)—

R′

—

N(H)C(O)—

R—

—

R—

N(H)C(O)—

R′

—

C(O)N(H)—

R—

—

R—

N(H)C(O)—

R′

—

N(H)C(O)—

R—

wherein each R and R′

is a member selected from the group consisting of alkylene moieties, alicyclic moieties, arylene moieties and heterocyclic moieties.

4. The copolymer of claim 1, wherein the segment —

R—

B—

(R′

—

B)_n—

R is a member selected from the group consisting of

—

R—

C(O)O—

R′

—

OC(O)—

R—

—

R—

OC(O)—

R′

—

C(O)O—

R—

—

R—

OC(O)—

R′

—

OC(O)—

R—

wherein each R and R′

is a member selected from the group consisting of alkylene moieties, alicyclic moieties, arylene moieties and heterocyclic moeities.

5. The copolymer of claim 3, wherein each R and R′

is a member selected from the group consisting of C1-C20 alkylene moieties, C4-C20 alicyclic moieties and C6-C20 arylene moieties.

6. The copolymer according to claim 5, wherein each R and R′

is a member selected from the group consisting of adipic acid residues, terephthalic acid residues, isophthalic acid residues and naphthalic acid residues.

7. The copolymer of claim 5, wherein each R and R′

is a member selected from the group consisting of C2-C8 alkylene moieties, C6-C12 arylene moieties and C6-C12 alicyclic moieties.

8. The copolymer of claim 1, wherein the urethane or urea group is based on isomers of toluene diamine, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, or 1,5-napthalene diisocyanate or mixtures thereof.

9. The copolymer of claim 1, wherein the polyol segment in the soft segment has a molecular weight in the range of 200-10,000 g/mol.

10. The polyol of claim 9, wherein polydispersity of the polyol is less than 1.2.

11. The polyol of claim 10, wherein the polyol has an unsaturation level of less than 0.015 meq unsaturation per gram of polyol.

12. The copolymer of claim 1, wherein the polyol segment is made of a hydroxyl or amine functionalized aliphatic, aromatic, or partially aromatic polymeric segment, wherein the polymeric segment includes a polyolefin, polyether, polyester, polycarbonate, polysiloxane, polysilane, or polyacrylate or copolymers thereof.

13. The copolymer according to claim 12, wherein the polyol segment includes a poly(tetramethylene oxide), poly(propylene oxide), polyethylene oxide), poly(tetramethylene adipate), polycarbonate, poly(ethylene/butylene), poly(dimethylsiloxane), polycarbonate or polyolefin and or copolymers thereof.

14. The copolymer of claim 1, wherein the glass transition temperature of the polymer is less than −

30°

C.

15. The copolymer of claim 1, wherein the melting temperature is at least 50°

C.

16. The copolymer of claim 15, wherein the melting temperature of the polymer is at least 130°

C.

17. The copolymer of claim 15, wherein the copolymer has an onset of crystallization of 50°

C. or less below its peak melting temperature as measured in a differential scanning calorimeter at a scan rate of 20°

C. per minute upon cooling from a melt of said polymer.

18. The copolymer of claim 15, wherein at least one of R is a C4 to C20 alicyclic or C6 to C20 arylene moiety with the proviso that such a moiety is not an amine-benzoic moiety.

19. An elastomer, fiber or extruded foam made from a copolymer of claim 1.

28. The chain extended polyurethane, polyurethaneurea and/or polyurea segmented copolymer according to claim 1, wherein n has a value of from 1 to 3.

29. The copolymer of claim 1, wherein at least 70 percent of the —

R—

B—

(R′

—

B)_n—

R—

segments are uniform in length as measured by NMR.

30. The copolymer of claim 1, wherein the polyol segment in the soft segment has a molecular weight in the range of 300 to 7,000 g/mol.

31. The copolymer of claim 1, wherein the polyol segment in the soft segment has a molecular weight in the range of 400 to 5,000 g/mol.

32. The copolymer of claim 15, wherein the copolymer has an onset of crystallization of 50°

C. or less below its peak melting temperature as measured in a differential scanning calorimeter at a scan rate of 40°

C. per minute upon cooling from a melt of said polymer.

33. The copolymer of claim 15, wherein the copolymer has an onset of crystallization of 50°

C. or less below its peak melting temperature as measured in a differential scanning calorimeter at a scan rate of 30°

C. per minute upon cooling from a melt of said polymer.

20. A method for producing a chain extended polyurethane, polyurethaneurea and/or polyurea segmented copolymer comprising reacting in a one-shot process a polyol, a polyisocyanate, and a chain-extender of the formula

X—

R—

B—

(R′

—

B)<sub>n—

R—

X</sub> 

 

(II)

wherein each B represents an —

N(H)C(O)—

, —

C(O)N(H)—

, —

C(O)—

O—

or —

O—

C(O)-moiety;

each R and R′

is a member selected from the group consisting of alkylene moieties, alicyclic moieties, arylene moieties, alkaryl moieties, arylalkyl moieties or heterocyclic moieties;

n has a value of 0 to 6;

X is an isocyanate reactive group; and

the equivalent ratio of NCO groups on the isocyanate to active hydrogen groups on the polyol plus the chain extender is between 1;

0.7 and 1;

1;

3, and the molar ratio of the chain extender to polyol is between 0.15;

1 and 75;

1.

22. The method of claim 20, wherein n is 1, R includes an even number of atoms and includes fewer atoms than the R′

, and X is an amine group.

24. The method of claim 22, wherein R and R′

are each a member selected from for group consisting of di-methylene, 5 tetra-methylene, hexa-methylene, octa-methylene, dodeca-methylene, p-benze, 1,4-cyclohexyl, p-xylylene, and 1,5-naphthalene.

25. The method of claim 20, wherein n is 1, R includes an uneven number of atoms and includes fewer atoms than the R′

, and X is a hydroxyl moiety.

27. The method of claim 24, wherein R and R′

are each members selected from the group consisting of tri-methylene, penta-methylene, hepta-methylene, m-benzene, 1,3-cyclohexyl, and m-xylylene moiety.

34. The method according to claim 20, wherein the polyisocyanate is a diisocyanate.

35. The method according to claim 20, wherein n has a value of 0 to 3;

36. The method according to claim 20, wherein the isocyanate reactive group is a hydroxyl, primary amine or secondary amine.

37. The method according to claim 20, wherein the equivalent ratio of NCO groups on the isocyanate to active hydrogen groups on the polyol plus the chain extender is between 1:

0.9 and 0.9;

1.

21. A method for producing a chain extended polyurethane, polyuethaneurea and/or polyurea segmented copolymer comprising reacting an isocyanate-terminated prepolymer with a chain extender of the formula

X—

R—

B—

(R′

—

B)_n—

R—

X 

 

(II)

wherein each B represents an —

N(H)C(O)—

, —

C(O)N(H)—

, —

C(O)—

O—

or —

O—

C(O)-moiety;

each R and R′

is independently chosen from the group consisting of alkylene moieties, alicyclic moieties, arylene moieties, alkaryl or arylalkyl moieties or heterocyclic 20 moieties;

n has a value of 0 to 6;

X is an isocyanate reactive group; and

the isocyanate terminated prepolymer is the reaction product of a polyisocyanate and a polyol, where the equivalent ratio of NCO groups on the isocyanate to active hydrogen groups on the polyol plus the chain extender is between 1;

0.7 and 1;

1;

3, and the molar ratio of the chain extender to polyol is between 0.15;

1 and 75;

1.

23. The method of claim 21, wherein n is 1, R includes an even number of atoms and includes fewer atoms than the R′

, and X is an amine group.

26. The method of claim 21, wherein n is 1, R includes an uneven number of atoms and includes fewer atoms than R′

, and X is a hydroxyl moiety.

38. The method according to claim 21, wherein n has a value of 0 to 3.

39. The method according to claim 21, wherein the isocyanate reactive group is a hydroxyl, primary amine or secondary amine.

40. The method according to claim 21, wherein the equivalent ratio of NCO groups on the isocyanate to active hydrogen groups on the polyol plus the chain extender is between 1:

0.9 and 0.9;

1.