Sulfolanyl-bearing organosilicone polymers

• US 4,049,674 A
• Filed: 06/30/1975
• Issued: 09/20/1977
• Est. Priority Date: 06/30/1975
• Status: Expired due to Term

• Current Assignee: OSI Specialties, Inc.
• Original Assignee: Union Carbide Corporation (Dow, Inc.)
• Inventors: Kanner, Bernard, Prokai, Bela
• Primary Examiner(s): Thomas, Jr., James O.
• Assistant Examiner(s): Siegel, A.
• Application Number:
  US05/592,129
• Time in Patent Office: 813 Days
• Field of Search: 260/332.1, 260/448.2 S, 260/448.2 H, 260/448.2 N
• US Class Current: 549/4
• CPC Class Codes: C08G 77/28 sulfur-containing groups
• CPC Class Codes: C08G 77/392 containing sulfur
• CPC Class Codes: C08G 77/46 containing polyether sequences
• CPC Class Codes: C08J 2375/04 Polyurethanes
• CPC Class Codes: C08J 2483/00 Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
• CPC Class Codes: C08J 9/0061 characterized by the use of several polymeric components
• CPC Class Codes: C08L 75/04 Polyurethanes
• CPC Class Codes: C08L 83/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
• CPC Class Codes: C08L 83/12 containing polyether sequences
• CPC Class Codes: Y10S 521/906 Polyurethane cellular product containing unreacted flame-retardant material

Abstract

A particular class of sulfolanyloxyalkyl-substituted organosilicone polymers are provided which comprise chemically combined monofunctional siloxy units (M_o) and difunctional siloxy units (D_o) and, for every two moles of M_o, an average of from about two to about 100 silicon-bonded sulfolanyloxyalkyl groups (Q) and an average of from about 2 to about 30 silicon-bonded E° groups where E° is hydrogen or a polyoxyalkylene block (E). When E° is hydrogen, the polymers are sulfolanyloxyalkyl-substituted polyalkylsiloxane hydrides and, when E° is E, the polymers are sulfolanyloxyalkyl-substituted polyalkylsiloxane-polyoxyalkylene copolymers. The monofunctional siloxy units encompassed by M_o have at least two alkyls bonded to the respective silicon atoms thereof and the difunctional siloxy units encompassed by D_o have at least one alkyl bonded to the respective silicon atoms thereof, the remaining group bonded to silicon of said M_o and D_o units being alkyl, Q or E°. The sulfolanyloxyalkyl-modified polyalkylsiloxane hydrides are especially useful as hydrosilation and condensation agents such as in forming the correspondingly modified polyalkylsiloxane-polyoxyalkylene copolymers of the invention. The copolymers in turn find particular application in the manufacture of cellular urethane products including urethane foam containing a flame-retardant.

Claims

1. A sulfolanyloxyalkyl-substituted organosiloxane having the average composition, ##STR42## wherein:

R is alkyl having from one to ten carbon atoms;

E°

is hydrogen or a polyoxyalkylene block;

Q is a sulfolanyloxyalkyl group having the formula, ##STR43## where R'"'"' is bivalent alkylene of two to eight carbon atoms, and R¹, R², R³ and R⁴ are independently hydrogen or alkyl of one to four carbon atoms;

t, u, v, w, the sum t+u and the sum v+w are independently zero or one, and each of the sums t+w and u+v is independently zero, one or two;

x is zero or a positive number having an average value up to about 200;

y has an average value from about 2 to about 100; and

z has an average value from about 2 to about 30.

2. A composition as defined in claim 1 in which each of R¹, R², R³ and R⁴ of said sulfolanyloxyalkyl group (Q) is hydrogen.

3. A composition as defined in claim 1 in which --R'"'"'--of said sulfolanyloxyalkyl group (Q) has from three to six carbon atoms.

4. A composition as defined in claim 3 in which --R'"'"'--is trimethylene.

5. A composition as defined in claim 3 in which --R'"'"'--is --CH₂ CH(CH₃)CH₂ --.

6. A composition as defined in claim 1 in which Q is 3-(sulfolan-3-yloxy)propyl.

7. A composition as defined in claim 1 in which E°

is hydrogen.

8. A composition as defined in claim 1 in which E°

is a polyoxyalkylene block.

9. A composition as defined in claim 1 in which each of u and v is one.

10. A composition as defined in claim 1 in which each of t and w is one.

11. A composition as defined in claim 1 in which each of t, u, v and w is zero.

12. A composition as defined in claim 1 in which x is zero.

13. A composition as defined in claim 1 in which x is a positive number having an average value up to about 200.

14. A sulfolanyloxyalkyl-substituted polyalkylsiloxane hydride having the average composition, ##STR44## wherein:

R is alkyl of one to four carbon atoms;

c is an integer having a value from two to eight;

x is zero or a positive number having an average value up to about 200;

y has an average value from about 2 to about 100; and

z has an average value from about 2 to about 30.

15. A sulfolanyloxyalkyl-substituted polyalkylsiloxane hydride as defined in claim 14 in which R is methyl.

16. A sulfolanyloxyalkyl-substituted polyalkylsiloxane hydride as defined in claim 14 in which c is an integer from three to four.

17. A sulfolanyloxypropyl-substituted polymethylsiloxane hydride having the average composition, ##STR45## wherein:

Me is methyl;

x is zero or a positive number having an average value up to about 200;

y has an average value from about 2 to about 100; and

z has an average value from about 2 to about 30.

18. A sulfolanyloxypropyl-substituted polymethylsiloxane hydride as defined in claim 17 in which x is a positive number having an average value up to about 200.

19. A sulfolanyloxypropyl-substituted polymethylsiloxane hydride as defined in claim 17 in which x is zero.

20. A sulfolanyloxypropyl-substituted polymethylsiloxane hydride as defined in claim 17 in which x has an average value no more than about 20 and y has an average value from about 2 to about 20.

21. A sulfolanyloxypropyl-substituted polymethylsiloxane hydride as defined in claim 17 in which x has an average value no more than about 10, y has an average value from about 2 to about 10, and z has an average value from about 2 to about 15.

22. A sulfolanyloxypropyl-substituted polymethylsiloxane hydride as defined in claim 17 in which x has an average value of at least about 10 and no more than about 200.

23. A sulfolanyloxypropyl-substituted polymethylsiloxane hydride as defined in claim 17 in which x has an average value from about 20 to about 100, y has an average value from about 2 to about 30, and z has an average value from about 2 to about 10.

24. An organosilicone composition which comprises a polysiloxane-polyoxyalkylene copolymer having the average composition, ##STR46## wherein:

Me is methyl;

R°

°

is a monovalent hydrocarbon group having one to twelve carbon atoms;

x has an average value from about 20 to about 100;

y has an average value from about 2 to about 30;

z has an average value from about 2 to about 10; and

m and n are positive numbers the average values of which are such that the average molecular weight of the chain, --(OC₂ H₄)_n (OC₃ H₆)_m --, is from about 1000 to about 6000 and the average oxyethylene content of said chain is from about 20 to about 65 weight percent.

25. A composition as defined in claim 24 in which R°

°

of said copolymer is alkyl of one to four carbon atoms.

26. A composition as defined in claim 25 in which R°

°

is methyl.

27. An organosilicone composition which comprises a polymethylsiloxane-polyoxyethylene copolymer having the average composition, ##STR47## wherein:

Me is methyl;

R°

°

is a monovalent hydrocarbon group having from one to twelve carbon atoms;

x is zero or a positive number having an average value no more than about 10;

y has an average value from about 2 to about 10;

z has an average value from about 2 to about 15; and

b has an average value from about 4 to about 15.

28. An organosilicone composition as defined in claim 27 in which x of said copolymer is a positive number having an average value of at least about 0.5 and no more than about 10.

29. An organosilicone composition as defined in claim 27 in which x of said copolymer is zero.

30. An organosilicone composition as defined in claim 27 in which R°

°

of said copolymer is alkyl of one to four carbon atoms.

31. An organosilicone composition as defined in claim 30 in which R°

°

is methyl.

32. An organosilicone composition which comprises a polysiloxane-polyoxyalkylene copolymer having the average composition, ##STR48## wherein:

R is alkyl of one to four carbon atoms;

c has a value from two to eight;

R°

comprises a bivalent alkylene radical a carbon atom of which is bonded to silicon;

r is zero or one;

G is R°

°

-, R°

°

C(O)- or R°

°

NHC(O)- where R°

°

- is a

monovalent hydrocarbon group having from 1 to 12 carbon atoms;

b has an average value from about 3 to about 100;

a has a value from two to four provided at least 20 weight percent of --(OC_a H_2a)_b -- is constituted of oxyethylene;

x is zero or a positive number having an average value of up to about 200;

y has an average value from about 2 to about 100; and

z has an average value from about 2 to about 30.

33. An organosilicone composition as defined in claim 32 in which x of said copolymer has an average value of at least about 10 and no more than about 200, and the average polyoxyalkylene content of --(OC_a H_2a)_b -- is constituted of from about 20 to about 75 weight percent of oxyethylene.

34. An organosilicone composition as defined in claim 32 in which x of said copolymer has an average value of no more than about 20, y has an average value from about 2 to about 20, b has an average value from about 3 to about 30, and the polyoxyalkylene content of --(OC_a H_2a)_b -- is constituted on the average of at least 75 weight percent oxyethylene.

35. An organosilicone composition as defined in claim 32 in which the R groups of said copolymer are methyl.

36. An organosilicone composition as defined in claim 32 in which r of said copolymer is zero.

37. An organosilicone composition as defined in claim 32 in which r of said copolymer is one.

38. An organosilicone composition as defined in claim 32 in which G of said copolymer is said monovalent hydrocarbon group, R°

°

-, having from 1 to 12 carbon atoms.

39. A composition as defined in claim 38 in which G is alkyl of one to four carbon atoms.

40. A composition as defined in claim 38 in which G is aryl.

41. A composition as defined in claim 38 in which G is aralkyl.

42. An organosilicone composition as defined in claim 32 in which G is said R°

°

C(O)-- group where R°

°

is said monovalent hydrocarbon group having from 1 to 12 carbon atoms.

43. An organosilicone composition as defined in claim 32 in which G is said R°

°

NHC(O)-- group where R°

°

is said monovalent hydrocarbon group having from 1 to 12 carbon atoms.

44. An organosilicone composition which comprises a polymethylsiloxane-polyoxyalkylene copolymer having the average composition, ##STR49## wherein:

Me is methyl;

G is R°

°

-, R°

°

C(O)- or R°

°

NHC(O)- where R°

°

- is a monovalent hydrocarbon group having from 1 to 12 carbon atoms;

e has a value from 2 to 6;

c has a value from 2 to 6;

x has an average value from about 10 to about 200;

y has an average value from about 2 to about 100;

z has an average value from about 2 to about 30;

a has a value from two to four provided an average of from 20 to about 75 weight percent of --(OC₂ H_2a)_b -- is constituted of oxyethylene units; and

b has an average value such that the average molecular weight of --(OC_a H_2a)_b -- is from about 1000 to about 6000.

45. An organosilicone composition which comprises a polymethylsiloxane-polyoxyalkylene copolymer having the average composition, ##STR50## wherein:

Me is methyl;

G is R°

°

-, R°

°

C(O)- or R°

°

NH(O)- where R°

°

- is a monovalent hydrocarbon group having from 1 to 12 carbon atoms;

e has a value from 2 to 6;

c has a value from 2 to 6;

x is zero or a positive number having an average value no more than about 20;

y has an average value from about 2 to about 20;

z has an average value from about 2 to about 30;

b has an average value from about 3 to about 30; and

a has a value from 2 to 4 provided an average of at least 75 weight percent of the polyoxyalkylene chain, --(OC_a H_2a)_b --, is constituted of oxyethylene units.