Scorch retarding crosslinking compositions comprising a hydroquinone, a sulfur accelerator, a coagent and a free radical initiator

• US 5,876,624 A
• Filed: 06/07/1995
• Issued: 03/02/1999
• Est. Priority Date: 03/22/1991
• Status: Expired due to Term

• Current Assignee: Arkema Incorporated (Arkema)
• Original Assignee: Elf Atochem North America, Inc. (Totalenergies Se)
• Inventors: Novits, Michael Fred, Kmiec, Chester Joseph, Hibbard, Edward Phillip
• Primary Examiner(s): HENDERSON JR, CHRISTOPHER A
• Application Number:
  US08/475,126
• Time in Patent Office: 1,364 Days
• Field of Search: 252/182.17, 252/182.14, 252/182.13, 252/182.18, 252/183.12, 526/261, 526/277, 526/321, 526/322, 526/323, 526/328, 526/335
• US Class Current: 252/182.17
• CPC Class Codes: C08K 5/0025 Crosslinking or vulcanising agents; including accelerators
• CPC Class Codes: C08K 5/13 Phenols; Phenolates
• CPC Class Codes: C08K 5/14 Peroxides
• CPC Class Codes: C08K 5/36 Sulfur-, selenium-, or tellurium-containing compounds C08K5/0091 takes precedence
• CPC Class Codes: C08K 5/39 Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
• CPC Class Codes: C08L 23/04 Homopolymers or copolymers of ethene
• CPC Class Codes: C08L 23/16 Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers

Abstract

A crosslinkable composition of a polymeric thermoplastic and/or elastomeric material which is susceptible to scorching when processed at elevated temperatures, prior to crosslinking, in the presence of a free radical initiator, is protected against such scorching by the incorporation therein of a mixture of at least one hydroquinone compound and a sulfur accelerator. This mixture may also contain at least one monomeric allylic, methacrylic, acrylic or diene type coagent. The mixture exhibits a synergistic effect resulting in improved scorch protection for peroxide cured systems when compared with the protection afforded by the components singly.

Claims

1. An improved composition for inclusion during and for retarding scorch during the compounding of thermoplastic polymers, curable with organic peroxides, elastomeric polymers, curable with organic peroxides, and mixtures of thermoplastic and elastomeric polymers, curable with organic peroxides, in the presence of free radical curing agents selected from the group organic peroxides to produce compounded polymers and for subsequent free radical cure of said compounded polymers by decomposition of the free radical curing agent in said compounded polymer which improved composition is prepared by mixing as the essential ingredients:

a) sulfur accelerator selected from the group dithiocarbamates, thiurams, thiazoles, sulfenamides, thioureas, and xanthates;

b) hydroquinone in a weight ratio of 1;

50 to 500;

1 to sulfur accelerator;

c) free radical initiator selected from the group consisting of organic peroxides in a weight ratio of 2;

1 to 100;

0.5 to the total amount of sulfur accelerator and hydroquinone; and

d) coagent selected from the group consisting of polyfunctional vinyl monomers, polyfunctional allyl monomers, mixtures of monofunctional vinyl monomers with polyfunctional vinyl monomers, mixtures of monofunctional vinyl monomers with polyfunctional allyl monomers, mixtures of monofunctional allyl monomers with polyfunctional vinyl monomers and mixtures of monofunctional allyl monomers with polyfunctional allyl monomers in a weight ratio of 100;

1 to 1;

100 by weight based on total weight of hydroquinone and sulfur accelerator.

2. A composition as defined in claim 1 wherein the organic peroxide is selected from the group consisting of dialkyl peroxides, diperoxyketals and mixtures thereof.

3. A composition as defined in claim 2 wherein the dialkyl peroxides are selected from dicumylperoxide;

alpha, alpha-bis (t-butyl peroxy) diisopropylbenzene;

t-butyl cumyl peroxide;

2,5-dimethyl-2,5-di(t-butylperoxy)-hexane;

2,5-dimethyl-2,5-di(t-butylperoxy)-hexyne-3;

2,5-dimethyl-2,5-di(t-amylperoxy)-hexyne-3;

di-t-amylperoxide;

1,3,5-tri (t-butylperoxy)-isopropyl!-benzene;

1,3-dimethyl-3-(t-butylperoxy)butanol; and

mixtures thereof.

4. A composition as defined in claim 2 wherein the diperoxyketal initiators are selected from the group consisting of:

1,1-di(t-butylperoxy) cyclohexane;

n-butyl-4,4-di(t-amylperoxy) valerate;

ethyl-3,3-di(t-butylperoxy)-butyrate;

2,2-di(t-amylperoxy)-propane;

3,6,6,9,9-pentamethyl-3-ethoxy carbonylmethyl-1,2,4,5-tetraoxacyclonane;

n-butyl-4,4-bis(t-butylperoxy)-valerate;

ethyl-3,3-di(t-amylperoxy)-butyrate and mixtures thereof.

5. A composition as defined in claim 1 wherein the sulfur accelerator is selected from compounds represented by the structure:

##STR4## wherein X is an ion derived from a metal selected from the group consisting of nickel, cobalt, iron, chromium, tin, zinc, copper, lead, bismuth, cadmium, selenium and tellurium, n may vary from 1 to 6 and is equal to the formal valence of the metal ion, and R₁ and R₂ are independently alkyl of 1 to 7 carbon atoms.

6. A composition as defined in claim 1 wherein the sulfur accelerator is selected from compounds represented by the formula ##STR5## wherein R₃ is an alkyl group of 1 to 7 carbon atoms and n may have a positive value from greater than zero up to about 6.

7. A composition as defined in claim 1 wherein the hydroquinone is hydroquinone monomethyl ether, the sulfur accelerator is zinc diamyldithiocarbamate, and the free radical initiator is dicumyl peroxide.

8. A composition as defined in claim 1 wherein the hydroquinone is mono-t-butylhydroquinone, the sulfur accelerator is tetrabutylthiuram disulfide and the free radical initiator is dicumyl peroxide.

9. A composition as defined in claim 1 wherein the hydroquinone is mono-t-butylhydroquinone, the sulfur accelerator is tetrabutylthiuram disulfide and the free radical initiator is 2,5-dimethyl-2,5-di(t-butylperoxy) hexane.

10. A composition as defined in claim 1 wherein the hydroquinone is hydroquinone monomethyl ether, the sulfur accelerator is zinc diamyldithiocarbamate, the free radical initiator is 1,1-bis-(t-butylperoxy)-3,3,5-trimethyl-cyclohexane.

11. A composition as defined in claim 1 wherein the hydroquinone is hydroquinone monomethyl ether, the sulfur accelerator is zinc dibutyldithiocarbamate and the free radical initiator is a mixture of dicumyl peroxide and 1,1-di (t-butylperoxy) isopropyl!-benzene.

12. A composition as defined in claim 1 wherein the coagent is triallylcyanurate.

13. A composition as defined in claim 1 wherein the coagent is triallyltrimellitate.

14. A composition as defined in claim 13 wherein the hydroquinone is hydroquinone monomethylether, the sulfur accelerator is zinc diamyldithio carbamate and the free radical initiator is a mixture of dicumylperoxide and n-butyl-4,4-bis(t-butylperoxy) valerate.

15. A composition as defined in claim 12 wherein the hydroquinone is mono-t-butyl hydroquinone, the sulfur accelerator is zinc diamyldithio carbamate, and the free radical initiator is a mixture of dicumyl peroxide and ethyl-3,3-di-(t-butylperoxy) butyrate.

16. A composition as defined in claim 12 wherein the hydroquinone is hydroquinone monomethyl ether, the sulfur accelerator is tetramethylthiuram monosulfide and the free radical initiator is 2,5 dimethyl-2,5-di(t-butylperoxy)-hexyne-3.

17. A composition as defined in claim 12 wherein the hydroquinone is hydroquinone monomethyl ether, the sulfur accelerator is tetrabutylthiuram disulfide and the free radical initiator is a mixture of dicumyl peroxide and ethyl 3,3-di-(t-butylperoxy)butyrate.

18. A composition as defined in claim 12 wherein the hydroquinone is hydroquinone monomethyl ether, the sulfur accelerator is tetrabutyl-thiuram disulfide and the free radical initiator is dicumyl peroxide.

19. A composition as defined in claim 1 wherein the essential ingredients are mixed substantially contemporaneously.

20. A composition as defined in claim 1 wherein any three of the essential ingredients are mixed substantially contemporaneously to prepare a first submixture and the fourth essential ingredient is then added to the first submixture.

21. A composition as defined in claim 1 wherein any two of the essential ingredients are combined to form a first submixture;

the remaining two essential ingredients are combined to form a second submixture; and

the first and second submixtures are then combined.

22. A composition as defined in claim 1 wherein any two of the essential ingredients are combined to form a first submixture;

one of the remaining essential ingredients is combined with the first submixture to prepare a second submixture; and

the remaining uncombined essential ingredient is combined with the second submixture.