Low molecular weight liquid injection molding resins having a high vinyl content

• US 5,674,966 A
• Filed: 04/09/1996
• Issued: 10/07/1997
• Est. Priority Date: 06/05/1995
• Status: Expired due to Term

• Current Assignee: General Electric Company
• Original Assignee: General Electric Company
• Inventors: Johnson, Donald S., Ward, Brian J., McDermott, Philip J., Jeram, Edward Matthew
• Primary Examiner(s): Marquis, Melvyn I.
• Application Number:
  US08/631,302
• Time in Patent Office: 546 Days
• Field of Search: 528/15, 528/32, 528/39, 525/477
• US Class Current: 528/32
• CPC Class Codes: B29K 2083/005 LSR, i.e. liquid silicone rubbers, or derivatives thereof
• CPC Class Codes: C08G 77/12 containing silicon bound to hydrogen C08G77/045 takes precedence
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/70 Siloxanes defined by use of the MDTQ nomenclature
• CPC Class Codes: C08G 77/80 Siloxanes having aromatic substituents, e.g. phenyl side groups
• CPC Class Codes: C08L 83/00 Compositions 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; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/04 Polysiloxanes

Abstract

Low molecular weight, high alkenyl content silicone resins of the general formula M_y M^vi_z D_a D^vi_b T_c T^vi_d Q or M_y M^vi_z D_a D^vi_b T_c T^vi_d are disclosed, their use in curable liquid injection molding compositions, a process for varying the cure properties of such compositions and articles of manufacture made thereby and therewith.

Claims

1. A silicone resin selected from the group consisting of silicone resins having the formula:

space="preserve" listing-type="equation">M.sub.y M.sup.vi.sub.z D.sub.a D.sup.vi.sub.b T.sub.c T.sup.vi.sub.d Q and M.sub.y M.sup.vi.sub.z D.sub.a D.sup.vi.sub.b T.sub.c T.sup.vi.sub.d ;

where

Q=SiO_4/2 ;

M=(R²)₃ SiO_1/2 ;

M^vi =R¹ (R²)₂ SiO_1/2 ;

D=R²₂ SiO_2/2 ;

D^vi =R¹ R² SiO_2/2 ;

T=R² SiO_3/2 ; and

T^vi =R¹ SiO_3/2 ;

where each R¹ is independently selected and is a two to twelve carbon atom alkenyl group and where each R² is independently selected and is a one to eight carbon atom alkyl, aryl, or alkylaryl group and where the subscripts a, b, c, d, and y may be zero or a positive number when Q is present and when Q is absent one of the subscripts c or d must be positive and non-zero and where the subscripts y and z satisfy the following relationship;

space="preserve" listing-type="equation">2≦

(y+z)≦

4

subject to the limitation that z and y satisfy one of the two relationships;

space="preserve" listing-type="equation">(z/y)>

1 or z>

y.

2. The resin of claim 1 where all of the sub-scripts are greater than zero.

3. The resin of claim 1 where the subscript d is zero.

4. The resin of claim 1 where the subscript c is zero.

5. The resin of claim 1 where the subscripts d and c are zero.

6. The resin of claim 5 where the subscript b is zero.

7. The resin of claim 5 where the subscript a is zero.

8. The resin of claim 5 where the subscripts a and b are zero.

9. The resin of claim 1 where the subscript a is zero.

10. The resin of claim 1 where the subscript b is zero.

11. The resin of claim 1 where the subscripts a and b are zero.

12. The resin of claim 11 where the subscript c is zero.

13. The resin of claim 11 where the subscript d is zero.

14. The resin of claim 8 where the subscript y is zero.

15. The resin of claim 8 where R¹ is vinyl and R² is methyl.

16. The resin of claim 8 where R¹ is vinyl and R² is methyl.

17. A silicone liquid injection molding composition comprising the resin of claim 1.

18. A silicone liquid injection molding composition comprising the resin of claim 15.

19. A silicone liquid injection molding composition comprising the resin of claim 16.

20. A liquid injection molded article of manufacture comprising the resin of claim 1.

21. A liquid injection molded article of manufacture comprising the resin of claim 15.

22. A liquid injection molded article of manufacture comprising the resin of claim 16.

23. The liquid injection molding composition of claim 17 where the molar ratio of hydride to alkenyl is defined by a molar excess of about 30 percent for the quantity of hydride present relative to the quantity of alkenyl present in the composition.

24. A process for controlling the cured properties of a curable silicone liquid injection molding composition which comprises the resin of claim 1 comprising varying the amount of said resin present in said composition and curing said composition.

25. A silicone resin selected from the group consisting of silicone resins having the formula:

space="preserve" listing-type="equation">M.sub.y M.sup.vi.sub.z D.sub.a D.sup.vi.sub.b T.sub.c T.sup.vi.sub.d Q and M.sub.y M.sup.vi.sub.z D.sub.a D.sup.vi.sub.b T.sub.c T.sup.vi.sub.d ;

where

Q=SiO_4/2 ;

M=(R²)₃ SiO_1/2 ;

M^vi =R¹ (R²)₂ SiO_1/2 ;

D=R²₂ SiO_2/2 ;

D^vi =R¹ R² SiO_2/2 ;

T=R² SiO_3/2 ; and

T^vi =R¹ SiO_3/2 ;

where each R¹ is independently selected and is a two to twelve carbon atom alkenyl group and where each R² is independently selected and is a one to eight carbon atom alkyl, aryl, or alkylaryl group and where the subscripts a, b, c, d, and y may be zero or a positive number when Q is present and when Q is absent one of the subscripts c or d must be positive and non-zero and where the subscripts y and z satisfy the following relationship;

space="preserve" listing-type="equation">≦

(y+z)≦

4

subject to the limitation that z and y satisfy one of the two relationships;

space="preserve" listing-type="equation">(z/y)>

1 or z>

y;

whereby said resin has a molecular weight below about 2,000 g/mole, an alkenyl content of up to about 30 weight percent, and a viscosity of up to about 15,000 centipoise at 25°

C.

26. A mixture of silicone resins comprising the resin of claim 25.

27. A silicone resin selected from the group of silicone resins having the formula:

space="preserve" listing-type="equation">M.sub.y M.sup.vi.sub.z D.sub.a D.sup.vi.sub.b T.sub.c T.sup.vi.sub.d Q and M.sub.y M.sup.vi.sub.z D.sub.a D.sup.vi.sub.b T.sub.c T.sup.vi.sub.d ;

where

Q=SiO_4/2 ;

M=(R²)₃ SiO_1/2 ;

M^vi =R¹ (R²)₂ SiO_1/2 ;

D=R²₂ SiO_2/2 ;

D^vi =R¹ R² SiO_2/2 ;

T=R² SiO_3/2 ; and

T^vi =R¹ SiO_3/2 ;

where each R¹ is independently selected and is a two to twelve carbon atom alkenyl group and where each R² is independently selected and is a one to eight carbon atom alkyl, aryl, or alkylaryl group and where the subscripts a, b, c, d and y may be zero or a positive number, one of the subscripts c or d must be positive and non-zero, and the subscripts y and z satisfy the following relationship;

space="preserve" listing-type="equation">≦

(y+z)≦

4

subject to the limitation that z and y satisfy one of the two relationships;

space="preserve" listing-type="equation">(z/y)>

1 or z>

y.

28. The resin of claim 27 whereby y and z satisfy the relationship 2≦

(y+z)≦

4.

29. The resin of claim 28 where all of the sub-scripts are greater than zero.

30. The resin of claim 27 where the subscript d is zero.

31. The resin of claim 27 where the subscript c is zero.

32. The resin of claim 27 where the subscripts c and d are positive and non-zero.

33. The resin of claim 32 where the subscript b is zero.

34. The resin of claim 32 where the subscript a is zero.

35. The resin of claim 32 where the subscripts a and b are zero.

36. The resin of claim 27 where the subscript a is zero.

37. The resin of claim 27 wherein the subscript b is zero.

38. The resin of claim 27 where the subscripts a and b are zero.

39. The resin of claim 38 where the subscript c is zero.

40. The resin of claim 38 where the subscript d is zero.

41. The resin of claim 35 where the subscript y is zero.

42. The resin of claim 35 where R¹ is vinyl and R² is methyl.

43. The resin of claim 35 where R¹ is vinyl and R² is methyl.

44. A silicone liquid injection molding composition comprising the resin of claim 29.

45. A silicone liquid injection molding composition comprising the resin of claim 42.

46. A silicone liquid injection molding resin composition comprising the resin of claim 43.

47. A liquid injection molded article of manufacture comprising the resin of claim 27.

48. A liquid injection molded article of manufacture comprising the resin of claim 42.

49. A liquid injection molded article of manufacture comprising the resin of claim 43.

50. The liquid injection molding composition of claim 44 where the molar ratio of hydride to alkenyl is defined by a molar excess of about 30 percent for the quantity of hydride present relative to the quantity of alkenyl present in the composition.

51. A process for controlling the cured properties of a curable silicone liquid injection molding composition which comprises the resin of claim 27 comprising varying the amount of said resin present in said composition and curing said composition.

52. A silicone resin selected from the group consisting of silicone resins having the formula:

space="preserve" listing-type="equation">M.sub.y M.sup.vi.sub.z D.sub.a D.sup.vi.sub.b T.sub.c T.sup.vi.sub.d Q and M.sub.y M.sup.vi.sub.z D.sub.a D.sup.vi.sub.b T.sub.c T.sup.vi.sub.d ;

where

Q=SiO_4/2 ;

M=(R²)₃ SiO_1/2 ;

M^vi =R¹ (R²)₂ SiO_1/2 ;

D=R²₂ SiO_2/2 ;

D^vi =R¹ R² SiO_2/2 ;

T=R² SiO_3/2 ; and

T^vi =R¹ SiO_3/2 ;

where each R¹ is independently selected and is a two to twelve carbon atom alkenyl group and where each R² is independently selected and is a one to eight carbon atom alkyl, aryl, or alkylaryl group and where the subscripts a, b, c, d and y may be zero or a positive number, one of the subscripts c or d must be positive and non-zero, and the subscripts y and z satisfy the following relationship;

space="preserve" listing-type="equation">1≦

(y+z)≦

4

subject to the limitation that z and y satisfy one of the two relationships;

space="preserve" listing-type="equation">(z/y)>

1 or z>

y;

whereby said resin has a molecular weight below about 2,000 g/mole, an alkenyl content of up to about 30 weight percent, and a viscosity of up to about 15,000 centipoise at 25°

C.

53. A mixture of silicone resins comprising the resin of claim 52.