Functionalized resin having a polar linker

Patent metadata

Field	Value
Publication number	US-11142594-B2
Application number	US-201916596506-A
Country	US
Kind code	B2
Filing date	Oct 8, 2019
Priority date	Apr 10, 2017
Publication date	Oct 12, 2021
Grant date	Oct 12, 2021

Abstract

Polar silane linkers are provided that attach to resins to form silane-functionalized resins. The functionalized resins can be bound to hydroxyl groups on the surface of silica particles to improve the dispersibility of the silica particles in rubber mixtures. Further disclosed are synthetic routes to provide the silane-functionalized resins, as well as various uses and end products that benefit from the unexpected properties of the silane-functionalized resins. Silane-functionalized resins impart remarkable properties on various rubber compositions, such as tires, belts, hoses, brakes, and the like. Automobile tires incorporating the silane-functionalized resins are shown to possess excellent results in balancing the properties of rolling resistance, tire wear, and wet braking performance.

First claim

What is claimed is:

1. A non-vulcanized composition, comprising:
a polymer, and
a functionalized resin,
wherein the functionalized resin comprises Formula I:
resin-[Z k —X n —R 1 —(CH 2 ) m —Si(R 2 ) p ] q   (I)

wherein Z is an aromatic group or an aliphatic group, optionally comprising a heteroatom;
wherein X is a linker comprising a heteroatom selected from sulfur, oxygen, nitrogen, a carbonyl group, or a combination thereof;
wherein R 1 comprises one or more of an aliphatic C 1 to C 18 , and is one or more of —O—CO—NH—R 3 —(CH 2 ) 2 —, O—CO—R 3 —(CH 2 ) 2 —, —O—CH 2 —R 3 —(CH 2 ) 2 —, (CH 2 ) 2 —, and —CO—NH—R 3 —(CH 2 ) 2 —, and R 3 comprises an aliphatic or aromatic C 1 to C 8 carbon chain, optionally branched, and/or optionally comprises one or more heteroatoms;
wherein each R 2 is the same or different and is independently selected from a C 1 to C 18 alkoxy, aryloxy, alkyl, aryl, or H, or OH, and is optionally branched, and wherein at least one R 2 is C 1 to C H alkoxy, aryloxy, or H, or OH;
wherein q is an integer from of at least 1;
wherein k is 0;
wherein n is an integer from 1 to 10;
wherein m is an integer from 0 to 10; and,
wherein p is 1, 2, or 3.

2. The non-vulcanized composition of claim 1 , wherein:
the functionalized resin is obtained by polymerizing or co-polymerizing one or more of an unsaturated aliphatic monomer, terpenes, rosin acid, unsaturated cycloaromatic monomers, unsaturated cycloaliphatic monomers, unsaturated fatty acids, methacrylates, unsaturated aromatic monomers, vinyl aromatic monomers, and an unsaturated aliphatic/aromatic monomer mixture, wherein the functionalized resin is hydrogenated, partially hydrogenated, or non-hydrogenated,
wherein the polymer is one or more of natural rubber, synthetic polyisoprene, natural polyisoprene, styrene-butadiene copolymer, solution-polymerized styrene-butadiene (SSBR), emulsion-polymerized styrene-butadiene rubber (ESBR), butadiene rubber (BR), halobutyl rubber, bromobutyl rubber, chlorobutyl rubber, nitrile rubber, liquid rubbers, polynorbornene copolymer, isoprene-isobutylene copolymer, ethylene-propylene-diene rubber, chloroprene rubber, acrylate rubber, fluorine rubber, silicone rubber, polysulfide rubber, epichlorohydrin rubber, styrene-isoprene-butadiene terpolymer, hydrated acrylonitrile butadiene rubber, isoprene-butadiene copolymer, butyl rubber, hydrogenated styrene-butadiene rubber, butadiene acrylonitrile rubber, a terpolymer formed from ethylene monomers, propylene monomers, and/or ethylene propylene diene monomer (EPDM), isoprene-based block copolymers, butadiene-based block copolymers, styrenic block copolymers, styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene/butylene-styrene block copolymer (SEBS), styrene-[ethylene-(ethylene/propylene)]-styrene block copolymer (SEEPS), styrene-isoprene-styrene block copolymer (SIS), random styrenic copolymers, hydrogenated styrenic block copolymers, styrene butadiene copolymers, polyisobutylene, ethylene vinyl acetate (EVA) polymers, polyolefins, amorphous polyolefins, semi-crystalline polyolefins, alpha-polyolefins, reactor-ready polyolefins, acrylates, metallocene-catalyzed polyolefin polymers and elastomers, reactor-made thermoplastic polyolefin elastomers, olefin block copolymer, co-polyester block copolymer, polyurethane block copolymer, polyamide block copolymer, thermoplastic polyolefins, thermoplastic vulcanizates, ethylene vinyl acetate copolymer, ethylene n-butyl acrylate copolymer, ethylene methyl acrylate copolymer, neoprene, acrylics, urethane, poly(acrylate), ethylene acrylic acid copolymer, polyether ether ketone, polyamide, atactic polypropylene, polyethylene including atactic polypropylene, ethylene-propylene polymers, propylene-hexene polymers, ethylene-butene polymers, ethylene octene polymers, propylene-butene polymers, propylene-octene polymers, metallocene-catalyzed polypropylene polymers, metallocene-catalyzed polyethylene polymers, ethylene-propylene-butylene terpolymers, copolymers produced from propylene, ethylene, C4-C10 alpha-olefin monomers, polypropylene polymers, maleated polyolefins, polyester copolymers, copolyester polymers, ethylene acrylic acid copolymer, and/or polyvinyl acetate, and/or
wherein the polymer optionally comprises a modification and/or functionalization selected from one or more of hydroxyl-, ethoxy-, epoxy-, siloxane-, amine-, aminesiloxane-, carboxy-, phthalocyanine-, and silane-sulfide-groups, at the polymer chain ends or pendant positions within the polymer.

3. The non-vulcanized composition of claim 1 , wherein q is an integer from 2 to 8, and/or wherein n is an integer from 1 to 4.

4. The functionalized resin of claim 1 , wherein —[Z k —X n —R 1 —(CH 2 ) m —Si(R 2 ) p ] q of Formula I is positioned at one or more ends of the functionalized resin, is distributed randomly throughout the functionalized resin, is present in blocks throughout the functionalized resin, is present in segments of the functionalized resin, is present at least once per functionalized resin, is present at least twice per functionalized resin, and/or is present in the middle of each functionalized resin.

5. The non-vulcanized composition of claim 2 , wherein:
the aromatic monomers and/or vinyl aromatic monomer comprises one or more of styrene, vinyl toluene, alpha-methyl styrene, and diisopropylbenzene, or
the aliphatic monomer comprises one or more of C 5 piperylenes, coumarone, indene, and dicyclopentadiene.

6. The non-vulcanized composition of claim 1 , wherein:
X comprises a phenol, a hydroxyl, an amine, an imidazole, an amide, a polysulfide, a sulfoxide, a sulfone, a sulfonamide, a sulfonium, an ammonium, a carboxylic acid, an ester, a thioester, an ether, a maleimide, a carbamate, cyanate, isocyanate, thiocyanate, a pyridinium, or combinations thereof,
R′ is a C 1 to C 10 carbon chain or a C 1 to C 5 carbon chain,
R 2 is a C 1 to C 10 alkoxy, aryloxy, alkyl, or aryl group, or a C 1 to C 5 alkoxy, aryloxy, alkyl, or aryl group, and is optionally branched, and/or
Z is a 6-membered aromatic group, or a saturated or unsaturated cyclo-aliphatic group.

7. The non-vulcanized composition of claim 1 , wherein:
X is oxygen or carbonyl, and/or
each R 2 is independently selected from a hydroxy, a methoxy, ethoxy, and a propoxy group.

8. The non-vulcanized composition of claim 1 , wherein:
an amount of silane-containing groups grafted onto the functionalized resin is about 0.001 to about 100 mol %, about 0.1 to about 50 mol %, or about 5 to about 50 mol %,
the functionalized resin has a molecular weight of about 200 g/mol to about 200,000 g/mol, about 200 g/mol to about 175,000 g/mol, or about 200 g/mol to about 150,000 g/mol,
the functionalized resin has a polydispersity index (PDI) of about 1 to 10,
the functionalized resin has a glass transition temperature Tg of below about 200° C. or less than about 160° C.,
the amount of silane groups grafted onto the functionalized resin is from about 0.01 to about 30 mol %, and/or
wherein the functionalized resin is present in an amount of from 5 to 400 phr, from 5 to 120 phr, from 5 to 100 phr, from 5 to 40 phr, from 5 to 30 phr, or from 5 to 10 phr.

9. The non-vulcanized composition of claim 1 , wherein:
the functionalized resin has the molecular weight of from about 400 to about 2,000 g/mol, and/or
the polydispersity index (PDI) of the functionalized resin is of about 1 to about 5, or from 1 to 2.

10. The non-vulcanized composition of claim 1 , further comprising at least one of a silica, carbon black, a silane coupling agent, a processing oil, a zinc compound, a wax, a vulcanizing agent, a vulcanizing retardant, a vulcanizing accelerator, and/or an

Assignees

• Continental Reifen Deutschland Gmbh
• Eastman Chem Co

Inventors

• Anderson Emily Baird
• Baker Jr John Dayton
• Carvagno Terri Roxanne
• Chapelet Judicael Jacques
• Cheng Wei Min
• Deng Liu
• De Hullu Jacobus Gillis
• Finger Sebastian
• Hirschlag Hubert
• Lester Christopher Lee
• Li Wentao
• Muvundamina Mutombo Joseph
• Pavlin Mark Stanley
• Peters Fabian
• Recker Carla
• Scilla Christopher Thomas

Classifications

• C08F12/22 Primary

  Oxygen · CPC title

• C08F230/085

  the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes · CPC title

• C08F220/1811

  C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate · CPC title

• C08L7/00 Primary

  Compositions of natural rubber · CPC title

• C08F212/08

  Styrene · CPC title