Polyenes for curable liquid rubber-based compositions

Patent metadata

Field	Value
Publication number	US-11214676-B2
Application number	US-201916376375-A
Country	US
Kind code	B2
Filing date	Apr 5, 2019
Priority date	Apr 5, 2019
Publication date	Jan 4, 2022
Grant date	Jan 4, 2022

Abstract

A curable liquid rubber composition including at least one liquid polyene component and at least one heat activated crosslinking agent. The liquid polyene component may be a single polyene or a blend of polyenes. In one embodiment, the liquid polyene component may contain on a molar basis, at least one monomer that results in at least 45 molar percent of C2-C13 pendant groups. In another embodiment, the liquid polyene component may contain on a molar basis at least one monomer that results in at least 20 molar percent of C2-C5 pendant groups, and at least one monomer that results in at least 7 molar percent of C6-C13 pendant groups. After curing, the liquid rubber composition may have a loss factor greater than 0.51, a maximum loss factor temperature greater than −10° C., and a swelling ratio in toluene from 40% to 170% by weight.

First claim

What is claimed:

1. A heat curable liquid rubber composition comprising:
a. a liquid polyene component, wherein the liquid polyene component is a liquid polyene comprising a polyene backbone or a blend of liquid polyenes each comprising a polyene backbone, wherein the liquid polyene component comprises on a total molar basis, as polymerized units,
i. at least one monomer that results in at least 45 molar percent of C2-C13 pendant groups along the polyene backbone; or
ii. at least one monomer that results in at least 20 molar percent of C2-C5 pendant groups along the backbone of the polyene, and at least one monomer that results in at least 7 molar percent of C6-C13 pendant groups along the backbone of the polyene;

b. between 0% and 1% by weight in total of a solid rubber or a solid thermoplastic; and
c. at least one heat activated crosslinking agent; and
wherein, after curing, the heat curable liquid rubber composition yields a cured rubber composition comprising:
i) a loss factor (tan δ) greater than 0.51 when measured at 50 Hz frequency, 3 μm amplitude, and temperatures of −10° C. to 45° C.;
ii) a maximum loss factor temperature greater than −10° C.; and
iii) a swelling ratio from 40% to 170% by weight, as measured by equilibrium weight gain in toluene at 25° C.

2. The heat curable liquid rubber composition according to claim 1 , wherein the liquid polyene component has a weight average molecular weight greater than 2000 g/mol and a Brookfield S spindle viscosity of 500-700,000 mPa·sec at 25° C.

3. The heat curable liquid rubber polyene composition according to claim 1 , wherein the liquid polyene or at least one liquid polyene in the blend of liquid polyenes is terminated with hydroxyl groups or functional derivatives thereof.

4. The heat curable liquid rubber composition according to claim 1 , wherein after curing the cured rubber composition has a Shore A hardness greater than 55 as measured by ASTM Standard D2240-15.

5. The heat curable liquid rubber composition according to claim 1 , wherein the at least one monomer that results in the C2-C13 pendant group is selected from the group consisting of C4 to C15 dienes, C6 to C15 trienes, C8-C15 tetraenes, vinyl aromatic compounds comprising 15 or fewer carbon atoms, and mixtures thereof.

6. The heat curable liquid rubber composition according to claim 5 , wherein the at least one monomer that results in the C2-C13 pendant group comprises at least one vinyl aromatic compound selected from the group consisting of styrene; alpha-methyl styrene; 2-methylstyrene; 3-methylstyrene; 4-methylstyrene; 4-propyl styrene; 4-t-butylstyrene; 4-cyclohexyl styrene; 2,4-dimethylstyrene; 2,4-diisopropyl styrene; 2,4,6-trimethyl styrene; 1-vinylnaphthalene; 2-vinyl naphthalene; N, N-diethyl-4-aminoethyl styrene; vinyl pyridine; 4-methoxystyrene; monochloro styrene; dichloro styrene; divinyl benzene; and mixtures thereof.

7. The heat curable liquid rubber composition according to claim 5 , wherein the at least one monomer that results in the C2-C13 pendant group comprises at least one of: a) a C4 to C14 diene selected from the group consisting of butadiene, isoprene, 2,3-dimethyl butadiene, 2-phenyl butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, and mixtures thereof; b) a C6 to C15 triene selected from the group consisting of 1,3,7-octatriene, myrcene, and mixtures thereof; or c) farnesene.

8. The heat curable liquid rubber composition according to claim 1 , wherein the at least one monomer that results in the C2-C13 pendant groups is selected from the group consisting of butadiene, isoprene, alpha-methyl styrene, styrene, myrcene, farnesene, and mixtures thereof.

9. The heat curable liquid rubber composition according to claim 1 , wherein the at least one monomer that results in the C2-C5 pendant groups is selected from the group consisting of C4-C7 dienes, C6-C7 trienes, and mixtures thereof.

10. The heat curable liquid rubber composition according to claim 1 , wherein the at least one monomer that results in the C6-C13 pendant groups is selected from the group consisting of C8-C15 dienes, C8-C15 trienes, C8-C15 tetraenes, vinyl aromatic monomers comprising between 8 and 15 carbon atoms, and mixtures thereof.

11. The heat curable liquid rubber composition according to claim 1 , wherein the at least one monomer that results in the C2-C5 pendant groups is selected from the group consisting of butadiene; isoprene; 2,3-dimethyl butadiene; 1,3-pentadiene; 2-methyl-1,3-pentadiene; 1,3-hexadiene; 1,3-cyclohexadiene; and mixtures thereof; and the at least one monomer that results in the C6-C13 pendant groups is selected from the group consisting of 1,3-octadiene; 2-methyl-1,3-octadiene; 1,3,7-octatriene; myrcene; styrene; alpha-methyl styrene; 2-methylstyrene; 3-methylstyrene; 4-methylstyrene; 4-propyl styrene; 4-t-butylstyrene; 4-cyclohexyl styrene; 2,4-dimethylstyrene; 2,4-diisopropyl styrene; 2,4,6-trimethyl styrene; 1-vinylnaphthalene; 2-vinyl naphthalene; N, N-diethyl-4-aminoethyl styrene; vinyl pyridine; 4-methoxystyrene; monochloro styrene; dichloro styrene; divinyl benzene, farnesene; and mixtures thereof.

12. The heat curable liquid rubber composition according to claim 1 , wherein the heat activated crosslinking agent comprises sulfur, and the heat curable liquid rubber composition further comprises at least one accelerator and at least one activator.

13. The heat curable liquid rubber composition according to claim 12 , wherein the at least one accelerator is selected from the group consisting of a sulfenamide, a thiazole, a dithiocarbamate, a thiuram-based compound, and mixtures thereof; and the at least one activator is selected from the group consisting of a metal oxide, a fatty acid metal salt, a fatty acid, and mixtures thereof.

14. The heat curable composition according to claim 13 , wherein: the at least one accelerator is selected from the group consisting of N-cyclohexyl-2-benzothiazolesulfenamide (CBS), N-tert-butyl-2-benzothiazyl sulfenamide (TBBS), and mixtures thereof; and the at least one activator is selected from the group consisting of zinc oxide, calcium oxide, magnesium oxide, zinc stearate, and mixtures thereof.

15. The heat curable liquid rubber composition according to claim 1 , wherein the heat activated crosslinking agent comprises an organic peroxide having a 10-hour half-life from 47° C. to 127° C.

16. The heat curable liquid rubber composition according to claim 15 , wherein the heat curable liquid rubber composition further comprises a metal oxide and a fatty acid and at least one coagent, wherein the at least one coagent is selected from the group consisting of metallic acrylates, metallic methacrylates, and mixtures thereof.

17. The heat curable liquid rubber composition according to claim 1 , wherein the liquid polyene component has a weight average molecular weight greater than 2500 g/mol.

18. The heat curable liquid rubber composition according to claim 1 , comprising between 10 and 80 weight percent of the liquid polyene component.

19. The heat curable liquid rubber composition according to claim 1 , comprising between 15 and 55 weight percent of the liquid polyene component.

20. The heat curable liquid rubber composition according to claim 1 , further comprising at least one filler.

21. The heat curable liquid rubber composition according to claim 20 , wherein the at least one filler is selected from the group consisting of calcium carbonate, silicas, ca

Assignees

• Fina Technology

Inventors

• Defrain Olivier
• Trnka Tomás̆
• Lodefier Philippe

Classifications

• C09J147/00

  Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Adhesives based on derivatives of such polymers (C09J145/00 takes precedence; based on conjugated diene rubbers C09J109/00 - C09J121/00) · CPC title

• C09J109/10

  Latex (C09J109/04, C09J109/08 take precedence) · CPC title

• C09J109/08

  Latex · CPC title

• C08L47/00 Primary

  Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers (C08L45/00 takes precedence; of conjugated diene rubbers C08L9/00 - C08L21/00) · CPC title

• C08L9/10

  Latex (C08L9/04, C08L9/08 take precedence) · CPC title