Composition with triallyl compounds and process for avoiding scorching of ethylene polymer composition

• US 4,018,852 A
• Filed: 01/29/1976
• Issued: 04/19/1977
• Est. Priority Date: 11/27/1974
• Status: Expired due to Term

• Current Assignee: Union Carbide Corporation (Dow, Inc.)
• Original Assignee: Union Carbide Corporation (Dow, Inc.)
• Inventors: Schober, Donald Lincoln
• Primary Examiner(s): Hamrock, William F.
• Application Number:
  US05/653,378
• Time in Patent Office: 446 Days
• Field of Search: 260/878 R, 260/47 UA, 526/57, 427/117
• US Class Current: 524/87
• CPC Class Codes: C08F 216/12 by an ether radical
• CPC Class Codes: C08F 255/00 Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
• CPC Class Codes: C08F 255/02 on to polymers of olefins having two or three carbon atoms
• CPC Class Codes: C08K 5/14 Peroxides
• CPC Class Codes: C08L 23/04 Homopolymers or copolymers of ethene
• CPC Class Codes: H01B 3/441 from alkenes

Abstract

Vulcanizable ethylene polymer based compositions which are susceptible to scorching when processed at elevated temperatures, prior to vulcanization, in the presence of certain organic peroxide compounds, are protected against such scorching by the incorporation therein of certain organic hydroperoxide compounds and organic compounds containing at least three allyl groups.

Claims

1. A scorch resistant vulcanizable composition comprising, in weight ratio,parts by weight of ethylene polymer,

about 0.1 to 5.0 parts by weight of at least one first peroxide compound which has a decomposition half-life of about 0.5 to 4.5 minutes at 160°

to 200°

C. and has the structure ##STR3## wherein R is a C₂ to C₁₂ divalent hydrocarbon radical,

R'"'"' and R" are the same or different C₁ to C₁₂ monovalent hydrocarbon radicals, and

n is a whole number of 0 or 1,

about 0.1 to 2.0 parts by weight of at least one second peroxide which has a decomposition rate which is at least about 20 to 100 times slower than that of said first peroxide compound,

said second peroxide having the structure ##STR4## and about 0.1 to 5.0 parts by weight of at least one organic compound containing at least three allyl groups.

2. A composition as in claim 1 in which n = 0.

3. A composition as in claim 2 in which R'"'"' = R".

4. A composition as in claim 3 in which R'"'"' and R" are phenyl radicals.

5. A composition as in claim 3 in which R'"'"' and R" are methyl radicals.

6. A composition as in claim 1 in which n = 1.

7. A composition as in claim 6 in which R'"'"' = R".

8. A composition as in claim 7 in which R is an aromatic radical.

9. A composition as in claim 8 in which R is phenylene.

10. A composition as in claim 9 in which R'"'"' and R" are methyl radicals.

11. A composition as in claim 7 in which R is a C₂ to C₄ linear hydrocarbon radical.

12. A composition as in claim 11 in which R'"'"' and R" are methyl radicals.

13. A composition as in claim 1 in which the allyl compound contains three allyl groups.

14. A composition as in claim 13 in which said allyl compound comprises triallyl cyanurate.

15. A composition as in claim 13 in which said allyl compound comprises triallyl phosphate.

16. A composition as in claim 13 in which said allyl compound comprises triallyl phosphite.

17. A composition as in claim 13 in which said allyl compound comprises triallyl ortho formate.

18. A composition as in claim 1 in which the allyl compound contains four allyl groups.

19. A composition as in claim 18 in which the allyl compound comprises tetra allyloxy ethane.

20. A composition as in claim 1 in which said ethylene polymer comprises ethylene homopolymer.

21. A composition as in claim 20 in which said ethylene homopolymer has a density of <

0.94.

22. A composition as in claim 20 in which said ethylene homopolymer has a density of ≧

0.94.

23. A composition as in claim 1 in which said ethylene polymer comprises ethylene copolymer.

24. A composition as in claim 23 in which said ethylene copolymer comprises ethylene-vinyl acetate copolymer.

25. A composition as in claim 23 in which said ethylene copolymer comprises ethylene-ethyl acrylate copolymer.

29. The composition of claim 1 in vulcanized form.

30. Electric wire or cable insulated with the composition of claim 1 in vulcanized form.

31. A composition as in claim 1 in which said first peroxide comprises at least one compound selected from the group consisting of di-α

-cumyl peroxide, di-α

,p-cyml peroxide, di-t-butyl peroxide, α

,α

-bis(t-butyl peroxy di-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butyl peroxy)hexane and 2,5-dimethyl-2,5-di(t-butyl peroxy)hexyne-3.

32. A composition as in claim 31 in which said second peroxide comprises at least one compound selected from the group consisting of cumene hydroperoxide, t-butyl hydroperoxide and 2,5-dimethyl-2,5-di-hydroperoxyhexane.

33. A composition as in claim 32 in which the allyl compound comprises at least one compound selected from the group consisting of triallyl cyanurate, triallyl phosphate, triallyl phosphite, triallyl ortho formate and tetra-allyloxy ethane.

34. A composition as in claim 33 in which said first peroxide comprises dicumyl peroxide.

35. A composition as in claim 34 in which said second peroxide comprises cumene hydroperoxide.

36. A composition as in claim 1 in which said allyl compound comprises triallyl cyanurate.

37. A composition as in claim 33 in which said first peroxide comprises 2,5-dimethyl-2,5-di(tertiary butyl peroxy)hexane.

38. A composition as in claim 37 in which said second peroxide comprises cumene hydroperoxide.

39. A composition as in claim 38 in which said allyl compound comprises triallyl cyanurate.

40. A composition as in claim 33 in which said first peroxide comprises α

,α

-bis(tertiary butyl peroxy di-isopropyl)benzene.

41. A composition as in claim 40 in which said second peroxide comprises cumene hydroperoxide.

42. A composition as in claim 41 in which said allyl compound comprises triallyl cyanurate.

43. A composition as in claim 34 in which said second peroxide comprises t-butyl hydroperoxide.

44. A composition as in claim 43 in which said allyl compound comprises triallyl cyanurate.

45. A composition as in claim 43 in which said allyl compound comprises triallyl phosphate.

46. A composition as in claim 40 in which said second peroxide comprises t-butyl hydroperoxide.

47. A composition as in claim 46 in which said allyl compound comprises triallyl cyanurate.

48. The composition of claim 33 in vulcanized form.

49. Electric wire or cable insulated with the composition of claim 33 in vulcanized form.

50. A composition as in claim 1 in which about one part by weight of said second peroxide is used per 2 to 10 parts by weight of said first peroxide.

51. A composition as in claim 50 in which about one part by weight of the allyl compound is used per 1 to 5 parts by weight of said first peroxide.

52. A composition as in claim 51 which further comprises about 0.01 to 3.0 parts by weight of at least one antioxidant for said ethylene polymer.

53. A composition as in claim 52 in which said antioxidant comprises at least one sterically hindered phenol.

54. A composition as in claim 53 in which said sterically hindered phenol is selected from the group consisting of

1,3,5-trimethyl-2,4,6-tris(3,5-ditertiary butyl-4-hydroxy benzyl)benzene,

1,3,5-tris(3,5-ditertiary butyl-4-hydroxy benzyl)-5-triazine-2,4,6-(1H,3H,5H)trione,

tetrakis-[methylene-3-(3'"'"' ,5-ditertiary butyl-4'"'"'-hydroxy phenyl)-propionate]methane, and

di(2-methyl-4-hydroxy-5-tertiary butyl phenyl) sulfide.

55. A composition as in claim 52 in which said antioxidant comprises polymerized 2,2,4-trimethyl dihydroquinoline.

56. The composition of claim 52 in vulcanized form.

57. Electric wire or cable insulated with the composition of claim 52 in vulcanized form.

26. A process for preventing the scorching of a vulcanizable composition which is susceptible to scorching during the processing thereof at temperatures of about 120°

to 160°

C. prior to the intended vulcanization thereof,

said composition comprising, in weight ratio, 100 parts by weight of ethylene polymer, and about 0.1 to 5.0 parts by weight of at least one first peroxide compound which has a decomposition half-life of about 0.5 to 4.5 minutes at 160°

to 200°

C. and has the structure ##STR5## wherein R is a C₂ to C₁₂ divalent hydrocarbon radical,

R'"'"' and R" are the same or different C₁ to C₁₂ monovalent hydrocarbon radicals, and

n is a whole number of 0 or 1,

which comprises admixing into said composition, prior to said processing, about 0.1 to 5.0 parts by weight of at least one organic compound containing at least three allyl groups, and about 0.1 to 2.0 parts by weight of a second peroxide compound which has a decomposition rate which is at least about 20 to 100 times slower than that of said first peroxide compound,

said second peroxide having the structure ##STR6## and then processing and vulcanizing said composition.

27. A vulcanized composition prepared by the process of claim 26.

28. Electric wire or cable insulated with a vulcanized composition prepared by the process of claim 26.

58. A process as in claim 26 in which about one part by weight of said second peroxide is used per 2 to 10 parts by weight of said first peroxide.

59. A process as in claim 58 in which about one part by weight of the allyl compound is used per 1 to 5 parts by weight of said first peroxide.

60. A process as in claim 59 in which said composition further comprises about 0.01 to 3.0 parts by weight of at least one antioxidant for said ethylene polymer.

61. A process as in claim 60 in which said antioxidant comprises at least one sterically hindered phenol.

62. A process as in claim 61 in which said sterically hindered phenol is selected from the group consisting of

1,3,5-trimethyl-2,4,6-tris(3,5-ditertiary butyl-4-hydroxy benzyl)benzene,

1,3,5-tris(3,5-ditertiary butyl-4-hydroxy benzyl)-5-triazine-2,4,6-(1H,3H,5H)trione,

tetrakis-[methylene-3-(3'"'"' ,5-ditertiary butyl-4'"'"'-hydroxy phenyl)-propionate]methane, and

di(2-methyl-4-hydroxy-5-tertiary butyl phenyl) sulfide.

63. A process as in claim 60 in which said antioxidant comprises polymerized 2,2,4-trimethyl dihydroquinoline.

64. A vulcanized composition made by the process of claim 60.

65. Electric wire or cable insulated with a vulcanized composition prepared by the process of claim 60.