Chalcogenide Hybrid Inorganic/organic Polymer (CHIP) materials as improved crosslinking agents for vulcanization

Patent metadata

Field	Value
Publication number	US-11674005-B2
Application number	US-201816622875-A
Country	US
Kind code	B2
Filing date	Jun 14, 2018
Priority date	Jun 15, 2017
Publication date	Jun 13, 2023
Grant date	Jun 13, 2023

Abstract

Methods of vulcanization using a high content sulfur polymer, instead of elemental sulfur, have been developed. These high sulfur content polymers are referred to as Chalcogenide Hybrid Inorganic/Organic Polymers (CHIP) materials and have good polymer compatibility in that they are soluble in a number of polymers. Furthermore, CHIP materials may have weaker bonds than the S—S bonds of elemental sulfur and thus provide for a higher crosslinking efficiency vulcanization.

First claim

What is claimed is:

1. A composition comprising:
a. a latex material; and
b. a vulcanizing agent comprising a chalcogenic hybrid inorganic/organic polymer (CHIP) material, wherein the CHIP material comprises:
i. one or more chalcogenic monomers at a level of at least 45 wt % of the CHIP material, wherein the one or more chalcogenic monomers comprise sulfur and selenium;
ii. a comonomer at a level in the range of about 5-55 wt % of the CHIP material, wherein the comonomer is co-polymerized with the one or more chalcogenic monomers; and
iii. a termonomer at a level in the range of about 5-45 wt % of the CHIP material, wherein the termonomer is co-polymerized with the one or more chalcogenic monomers and the comonomer, wherein the termonomer is different from the comonomer;

wherein the comonomer improves miscibility of the vulcanizing agent, wherein the vulcanizing agent allows for a higher crosslinking efficiency vulcanization than elemental sulfur,
wherein the vulcanizing agent vulcanizes the latex material to provide a crosslinked rubber.

2. The composition of claim 1 , wherein the one or more chalcogenic monomers are at a level of at least 50 wt % of the CHIP material and the comonomer is at a level in the range of about 5-50 wt % of the CHIP material.

3. The composition of claim 1 , wherein the latex material comprises a natural rubber, a polydiene, a polydiene copolymer, polybutadiene, polyisoprene, polychloroprene, a butyl rubber, a silicone rubber latex, an acrylic rubber latex or a combination thereof.

4. The composition of claim 1 , wherein the chalcogenic monomers comprises sulfur monomers derived from elemental sulfur and elemental selenium (Se 8 ).

5. The composition of claim 1 , wherein the comonomer is selected from a group consisting of an amine comonomer, a thiol comonomer, a sulfide comonomer, an alkynylly unsaturated comonomer, an epoxide comonomer, a nitrone comonomer, an aldehyde comonomer, a ketone comonomer, a thiirane comonomer, an ethylenically unsaturated comonomer, a styrenic comonomer, a vinylic comonomer, a methacrylate comonomer, an acrylonitrile comonomer, an allylic monomer, an acrylate monomer, a vinylpyridine monomer, an isobutylene monomer, a maleimide monomer, a norbornene monomer, a monomer having at least one vinyl ether moiety, a monomer having at least one isopropenyl moiety, a monomer having at least one imidazole moiety, and a monomer having at least one heterocyclic moiety.

6. The composition of claim 1 , wherein the comonomer is co-polymerized with the chalcogenic monomers via free radical polymerization, controlled radical polymerization, ring-opening polymerization, ring-opening metathesis polymerization, step-growth polymerization, or chain-growth polymerization.

7. The composition of claim 1 , wherein the composition further comprises one or more additives, wherein the additive comprises an accelerator, a peroxide, a plasticizer, an anti-ozonant, an antioxidant, a retarder, a lubricant, a filler, a colorant or a combination thereof.

8. The composition of claim 1 , wherein the CHIP material comprises one or more reactive functional groups.

9. The composition of claim 8 , wherein the functional groups are capable of activating one or more chalcogen bonds to accelerate vulcanization by accelerating a breaking of one or more chalcogen bonds.

10. The composition of claim 8 , wherein the functional groups are nucleophilic functional groups.

11. The composition of claim 8 , wherein the functional groups are amine, N-heterocyclic, phosphine, or sulphide functional groups.

12. The composition of claim 1 , wherein the comonomer is an activated arene, a vinylic amine, an N-heterocycle, a functional olefin with a polar or a nucleophilic side chain group, a norbornene monomer, a vinylaniline, or a phenylenediamine.

13. The composition of claim 1 , wherein the termonomer is an activated arene, a vinylic amine, an N-heterocycle, a functional olefin with a polar or a nucleophilic side chain group, a norbornene monomer, a vinylaniline, or a phenylenediamine.

14. A method of vulcanizing a latex material to form a crosslinked rubber, said method comprising reacting said latex material with a chalcogenic hybrid inorganic/organic polymer (CHIP) material, wherein the CHIP material comprises:
a. one or more chalcogenic monomers at a level of at least 45 wt % of the CHIP material, wherein the one or more chalcogenic monomers comprise sulfur and selenium; and
b. a comonomer at a level in the range of about 5-55 wt % of the CHIP material, wherein the comonomer is co-polymerized with the one or more chalcogenic monomers;
c. a termonomer at a level in the range of about 5-45 wt % of the CHIP material, wherein the termonomer is co-polymerized with the one or more chalcogenic monomers and the comonomer, wherein the termonomer is different from the comonomer;
wherein the comonomer improves miscibility of the vulcanizing agent, wherein the vulcanizing agent allows for a higher crosslinking efficiency vulcanization than elemental sulfur,
wherein the CHIP material vulcanizes the latex material to provide said crosslinked rubber.

15. The method of claim 14 , wherein reacting the latex material with the CHIP material comprises: mixing said latex material and said CHIP material; and heating the mixed latex material and said CHIP material at a temperature and for a period of time sufficient to effect vulcanization of the latex material.

16. The method of claim 14 , wherein the method is performed at a temperature of less than about 170° C.

17. The method of claim 14 , wherein the method is performed in a time of about 10 to 20 min.

18. A composition comprising:
a. a latex material; and
b. a vulcanizing agent comprising a chalcogenic hybrid inorganic/organic polymer (CHIP) material, wherein the CHIP material comprises one or more chalcogenic monomers at a level of at least 45 wt % of the CHIP material, and a comonomer at a level in the range of about 5-55 wt % of the CHIP material, wherein the comonomer is diisopropenylbenzene or a norbornene monomer;
wherein the comonomer improves miscibility of the vulcanizing agent, wherein the vulcanizing agent allows for a higher crosslinking efficiency vulcanization than elemental sulfur.

19. The composition of claim 18 , wherein the one or more chalcogenic monomers comprise elemental sulfur, a liquid polysulfide, an oligomer containing sulfur, an oligomer containing sulfur and selenium units, or sulfur monomers derived from elemental sulfur and elemental selenium (Se 8 ).

20. The composition of claim 18 , wherein the CHIP material further comprises a termonomer at a level in the range of about 5-45 wt % of the CHIP material, wherein the termonomer is co-polymerized with the one or more chalcogenic monomers and the comonomer, wherein the termonomer is different from comonomer.

Assignees

• Univ Arizona

Inventors

• Pyun Dong-Chul
• Glass Richard S
• Carothers Kyle
• Zhang Yueyan

Classifications

• C08J3/26 Primary

  of latex · CPC title

• C08G75/0209

  derived from monomers containing one aromatic ring · CPC title

• C08F12/28

  Amines · CPC title

• C08F212/08

  Styrene · CPC title

• C08J3/24 Primary

  Crosslinking, e.g. vulcanising, of macromolecules (mechanical aspects B29C35/00; crosslinking agents C08K) · CPC title