Functionalized resin having a polar linker
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.
1. A process to produce a silane functionalized resin having 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 and/or aromatic C 1 to C 18 group and/or a linkage group comprising a heteroatom;
wherein each R 2 is the same or different and is independently selected from a C 1 to C 18 alkoxy, aryloxy, alkyl, aryl, H, or OH, and is optionally branched, and wherein at least one R 2 is C 1 to C 18 alkoxy, aryloxy, H, or OH;
wherein q is an integer of at least 1;
wherein k is an integer of 0 or 1;
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;
the process comprising:
providing a phenol modified resin having Formula (II):
resin-Z k —OH (II), and
reacting the phenol modified resin of Formula (II) with a cyclic acid anhydride of Formula (IV) or a terminal halogen-substituted straight-chain carboxylic acid of Formula (V), optically in the presence of a catalyst:
wherein R 3 is independently selected from the group consisting of substituted and unsubstituted, saturated, unsaturated, and polyunsaturated C 1 -C 8 alkyl, substituted and unsubstituted C 6 -C 20 carbocyclic aryl, and substituted and unsubstituted C 4 -C 20 heterocycle;
wherein the heteroatoms are selected from the group consisting of sulfur, nitrogen, and oxygen;
wherein Y is a halogen atom; and
wherein s is an integer from 1 to 6,
to yield an acid-modified resin of Formula (III):
resin-Z k —X n —OH (III), and
reacting said acid-modified resin of Formula (III) with a silane coupling agent optionally in the presence of an activation agent and optionally in the presence of a catalyst to produce the functionalized resin of Formula (I).
2. The process according to claim 1 , wherein the cyclic acid anhydride of Formula (IV) is selected from the group consisting of: malonic anhydride, succinic anhydride, methylsuccinic anhydride, glutaric anhydride, adipic anhydride, pimelic anhydride, phthalic anhydride, trimellitic anhydride, and maleic anhydride.
3. The process according to claim 1 , wherein the process is performed in no solvent or in an inert solvent.
4. The process according to claim 3 , wherein the process is performed in an inert solvent selected from one or more of the group consisting of: a cyclic ether solvent, an acyclic ether solvent, a ketone solvent, aromatic hydrocarbons, aliphatic saturated hydrocarbons, aliphatic unsaturated hydrocarbons, alicyclic saturated hydrocarbons, alicyclic unsaturated hydrocarbons, halogenated hydrocarbons, and polar aprotic solvents.
5. The process according to claim 1 , further comprising reacting the acid-modified resin of Formula (III) with a silane coupling agent having Formula (VI)
W—(CH 2 ) m —Si(R 2 ) p (VI)
wherein m, R 2 , and p as defined above;
wherein W is independently selected from the group consisting of: amine, diamine, thiol, isocyanate, epoxide, alkene, and halogen,
to yield the silane functionalized resin.
6. The process according to claim 1 , wherein the temperature at which the process is performed is in a range of about 0° C. to about 300° C.
7. The process according to claim 1 , wherein the temperature at which the process is performed is in a range of about 100° C. to about 250° C.
8. The process according to claim 1 , wherein the temperature at which the process is performed is in a range of about 150° C. to about 250° C.
9. The process according to claim 1 , wherein reacting is performed in the presence of a catalyst, and wherein the catalyst is selected from one or more of the group consisting of: quaternary ammonium salts, quaternary phosphonium salts, iodide salts, triphenylphosphine, 4-dimethylaminopyridine, alkaline, Lewis acids, and Bronsted acids.