阅读说明：本技术 具有极性连接基的官能化树脂 (Functionalized resins with polar linking groups ) 是由 E.B.安德森 J.D.贝克 T.R.卡瓦诺 J.J.沙普莱特 郑伟民 邓榴 J.G.德 于 2018-04-09 设计创作，主要内容包括：提供连接到树脂以形成硅烷官能化树脂的极性硅烷连接基。可以将所述官能化树脂结合到二氧化硅粒子表面上的羟基,以改善所述二氧化硅粒子在橡胶混合物中的可分散性。进一步公开了提供所述硅烷官能化树脂的合成路线,以及得益于所述硅烷官能化树脂的出乎意料的性质的各种用途和最终产物。硅烷官能化树脂为诸如轮胎、带、软管、制动器等的各种橡胶组合物赋予卓越的性质。显示掺入了所述硅烷官能化树脂的汽车轮胎在平衡滚动阻力、轮胎撕裂和湿制动性能的性质方面具有优异的结果。(Polar silane linking groups are provided that are linked to the resin to form a silane-functionalized resin. The functionalized resin may be bound to hydroxyl groups on the surface of the silica particles to improve dispersibility of the silica particles in the rubber compound. 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 excellent properties to various rubber compositions such as tires, belts, hoses, brakes, and the like. The vehicle tires incorporating the silane-functionalized resins are shown to have excellent results in balancing the properties of rolling resistance, tire tear, and wet braking performance.)

1. A non-vulcanized composition comprising:

a polymer, and

a functionalized resin, a light-sensitive resin,

wherein the functionalized resin comprises formula I:

wherein Z is an aromatic or aliphatic group optionally containing heteroatoms;

wherein X is a linker comprising a heteroatom selected from sulfur, oxygen, nitrogen, carbonyl, or combinations thereof;

wherein R is¹Comprising aliphatic C₁To C₁₈And/or a heteroatom-containing linking group;

wherein R is²Each of which is the same or different and is independently selected from C₁To C₁₈Alkoxy, aryloxy, alkyl, aryl, or H, or OH, and optionally branched, and wherein at least one R²Is C₁To C₁₈Alkoxy, aryloxy, or 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 is

Wherein p is 1,2 or 3.

2. The non-vulcanized composition of claim 1 wherein:

the functionalized resin is obtained by polymerization or copolymerization of one or more of unsaturated aliphatic monomers, terpenes, rosin acids, unsaturated aromatic cyclic monomers, unsaturated alicyclic monomers, unsaturated fatty acids, methacrylates, unsaturated aromatic monomers, vinyl aromatic monomers, and unsaturated aliphatic/aromatic monomer mixtures,

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), halogenated butyl rubber, brominated butyl rubber, chlorinated butyl rubber, nitrile rubber, liquid rubber, polynorbornene copolymer, isoprene-isobutylene copolymer, ethylene-propylene-diene rubber, chloroprene rubber, acrylate rubber, fluoro 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, terpolymers formed from ethylene monomer, propylene monomer and/or Ethylene Propylene Diene Monomer (EPDM), isoprene-based block copolymers, butadiene-based block copolymers, styrenic block copolymers, styrene-butadiene-styrene block copolymers (SBS), styrene-ethylene/butylene-styrene block copolymers (SEBS), styrene- [ ethylene- (ethylene/propylene) ], styrene-ethylene-butadiene-styrene block copolymers (styrene-ethylene-styrene block copolymers (SEBS), styrene-ethylene-propylene-styrene block copolymers (SEBS), styrene-ethylene-propylene-ethylene-styrene copolymers (styrene copolymers, styrene-ethylene-propylene-ethylene-propylene copolymer copolymers (SEBS), styrene copolymers, styrene-ethylene-propylene-ethylene-propylene copolymers, styrene-ethylene-

Wherein the polymer optionally comprises a modification and/or functionalization at the polymer chain end or at a lateral position within the polymer, selected from one or more of hydroxyl-, ethoxy-, epoxy-, siloxane-, amine-, aminosiloxane-, carboxyl-, phthalocyanine-and silane-sulfide-groups.

3. The non-vulcanized composition according to 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 ] of formula I_k-X_n-R¹-(CH₂)_m-Si(R²)_p]_qAt one or more ends of the functionalized resin, randomly distributed throughout the functionalized resin, present in blocks throughout the functionalized resin, present in segments of the functionalized resin, present at least once in each functionalized resin, present at least twice in each functionalized resin, and/or present in the middle of each functionalized resin.

5. The non-vulcanized composition of claim 2 wherein:

the aromatic monomer and/or vinyl aromatic monomer comprises one or more of styrene, vinyl toluene, α -methyl styrene and diisopropylbenzene, or

The aliphatic monomer comprises C₅One or more of piperylene, coumarone, indene and dicyclopentadiene.

6. The non-vulcanized composition of claim 1 wherein:

x comprises phenol, hydroxyl, amine, imidazole, amide, polysulfide, sulfoxide, sulfone, sulfonamide, sulfonium, ammonium, carboxylic acid, ester, thioester, ether, maleimide, carbamate, cyanate, isocyanate, thiocyanate, pyridinium, or combinations thereof,

R¹is C₁To C₁₀Carbon chain or C₁To C₅The carbon chain is a carbon chain,

R²is C₁To C₁₀Alkoxy, aryloxy, alkyl or aryl, or C₁To C₅Alkoxy, aryloxy, alkyl or aryl, and optionally branched, and/or

Z is a 6-membered aromatic group or a saturated or unsaturated cycloaliphatic group.

7. The non-vulcanized composition of claim 1 wherein:

x is oxygen or carbonyl, and/or

R²Each independently selected from the group consisting of hydroxy, methoxy, ethoxy, and propoxy.

8. The non-vulcanized composition of claim 1 wherein:

the amount of silane-containing groups grafted to the functionalized resin is from about 0.001 to about 100 mole percent, from about 0.1 to about 50 mole percent, or from about 5 to about 50 mole percent,

the functionalized resin has a molecular weight of from about 200 g/mol to about 200,000 g/mol, from about 200 g/mol to about 175,000g/mol, or from 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 less than about 200 ℃ or less than about 160 ℃,

the amount of silane groups grafted to the functionalized resin is from about 0.01 to about 30 mole percent, and/or

Wherein the functionalized resin is present in an amount of 5 to 400phr, 5 to 120 phr, 5 to 100phr, 5 to 40 phr, 5 to 30phr, or 5 to 10 phr.

9. The non-vulcanized composition of claim 1 wherein:

the functionalized resin has a molecular weight of about 400 to about 2,000 g/mol, and/or

The functionalized resin has a polydispersity index (PDI) of about 1 to about 5, or 1 to 2.

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

11. The non-vulcanized composition of claim 10 wherein:

the functionalized resin is hydrolyzed by at least one-R²The radicals are then bonded to the silica particles through Si-O-Si moieties,

the functionalized resin molecule is hydrolyzed by at least one-R²The group is then bound to a second functionalized resin molecule through a Si-O-Si moiety, or

The functionalized resin is covalently attached to the surface of the silica filler material through a reactive group bonded to a polar linking group.

12. The non-vulcanized composition of claim 1 wherein

R¹is-O-CO-NH-R¹-(CH₂)₂-、O-CO-R³-(CH₂)₂-、-O-CH₂-R³-(CH₂)₂-、-CO-R³-(CH₂)₂-and-CO-NH-R³-(CH₂)₂One or more of the above-mentioned, and

R³is aliphatic or aromatic C₁To C₈The carbon chain, optionally branched, and/or optionally containing one or more heteroatoms.

13. The non-vulcanized composition according to claim 1, wherein the polymer is one or more of natural polyisoprene, synthetic polyisoprene, solution polymerized styrene-butadiene (SSBR), and/or Butadiene Rubber (BR).

14. An article comprising the non-vulcanized composition of claim 1, wherein the article is an adhesive, a laminate, a tape, a heat seal coating, a heat seal cap, a disposable hygiene article, an adhesive, a joint compound, an Insulating Glass (IG) unit, a bridge deck, a waterproofing film, a waterproofing compound, a gasketing material, a cable impregnation/filling compound, a low shrinkage sheet molding compound, a mass molding compound, an overmolding compound, a polyester composite, a glass fiber reinforced plastic, a coupling agent for wood-plastic composites, a polyvinyl chloride extrusion compound, a polyacrylic blend compound, a precision dewaxed casting, a cast wax composition, a candle, a window, a film, a gasket, a seal, an O-ring, an automotive molded part, an automotive extrusion, a sealant, an apparel article, a low shrinkage additive for Sheet Molding Compounds (SMC) and mass molding compounds (DMC), Woven fabric sizing, nonwoven fabric sizing, rubber additives/processing aids, shoe soles, treads, tire sidewalls, tire innerliners, tire squeegees, wheel body profiles, tire belt plies, tire shoulders, tire belt profiles, carcass plies, bead wires, tire cord profiles, tire trumpet profiles, tire bandages, innertubes, hoses, belts, strips, tubes, brakes or engine components, and

wherein the adhesive is a packaging adhesive, a food contact grade adhesive, an indirect food contact packaging adhesive, a product assembly adhesive, a woodworking adhesive, a flooring adhesive, an automotive assembly adhesive, a construction adhesive, a Pressure Sensitive Adhesive (PSA), a PSA tape, a PSA label, a PSA protective film, a laminating adhesive, a flexible packaging adhesive, a heat seal adhesive, an industrial adhesive, a sanitary nonwoven construction adhesive, a sanitary core integrity adhesive, or a sanitary elastic attachment adhesive.

Technical Field

Silane-functionalized resins containing polar silane linkages as functional groups are disclosed. The functionalized resin may be bonded to hydroxyl groups on the surface of the silica particles to improve the dispersibility of the silica particles in the rubber mixture, which changes the viscoelastic and performance properties of the cured rubber compound. Additionally, synthetic routes to prepare polar or amphiphilic silane linkers and to link the linkers to resins are disclosed, as well as synthetic routes to copolymerize silane-functional monomers. Various uses and end products that impart superior properties due to the unexpected properties of these functionalized resins are also disclosed.

Background

The rubber compounds often contain filler materials to improve the specifications of the tire composition, such as high wear resistance, low rolling resistance or wet grip. However, these technical requirements often conflict with each other, since for example the composition is changed to reduce the rolling resistance of the tire and thus the wet grip can be reduced.

Silica is a filler material widely used in rubber mixtures. In particular, silica is generally contained in rubber mixtures for vehicle tires. However, due to the presence of polar hydroxyl groups, the surface of the silica particles is hydrophilic, while the rubber material in the tire is generally more hydrophobic, which may make it difficult to disperse the silica particles in the rubber mixture during tire manufacture.

Current resin technology for tires uses high glass transition resins to modify the rubber glass transition temperature Tg and viscoelasticity, thereby improving the wet grip and rolling resistance performance balance. Wet grip performance must be balanced with other tire properties including rolling resistance and wear affected by resin incorporation.

Recently, resins have been increasingly used in rubber compounds for vehicle tire applications, particularly in rubber compounds for tire treads. U.S. patent application publication No. 2016/0222197 discloses tire treads containing resin in an amount of more than 50 phr. Good compatibility between rubber and resin is a prerequisite to achieve high resin loading in the polymer matrix.

Commercially available resins are not functionalized to achieve specific attachment to the surface of the filler material. Thus, commercially available resins are distributed throughout the polymer matrix and do not target the interface of silica and rubber.

International patent application publication No. WO 2015/153055 discloses dicyclopentadiene (DCPD) -based polymers functionalized with functional groups of the formula P-S-X, wherein S is an aliphatic or aromatic spacer, P is the polymer backbone, and X is a silane. However, DCPD-based resins exhibit reduced solubility in at least some rubber compounds used in tires.

In addition, it is known from U.S. patent application publication No. 2013/0296475 to provide thermoplastic polymers with terminal functional groups. In some of these embodiments, resins having a relatively high Mn (number average molecular weight) of 2,500 to 10,000 g/mol are used. However, as the molecular weight of the hydrocarbon resin gradually increases, the compatibility with the polymer matrix may decrease.

Thus, functionalized resins are disclosed for use as processing aids or for preventing the damping or energy dissipation effects provided by unbound resins in vehicle tires. In particular, the damping properties of the rubber mixtures can be modified in a site-specific manner. The functionalized resins disclosed herein are attached to the surface of a filler material, preferably silica, through a reactive group, preferably a reactive silane group, bonded to a polar linking group. Surprisingly, the functionalized resin can efficiently modify the polymer-filler interface, thereby improving the viscoelastic properties of the rubber compound. Conflicting technical requirements of the tire composition, such as improved wet grip and lower rolling resistance, can be effectively solved at higher levels.

SUMMARY

Provided herein are resin compositions functionalized with silanes. It has been found that functionalizing resins with silanes as disclosed herein imparts superior unexpected properties such that products such as rubber products, adhesives, tires, belts, gaskets, hoses, and the like, have superior properties compared to similar products without the disclosed functionalized resins. Also disclosed are methods of obtaining, making, synthesizing, or producing such resins, as well as various products incorporating the disclosed functionalized resins.

The composition comprising the functionalized resin comprises a polymer and one (or more) functionalized resins having the general structure of formula I, wherein "resin" represents the backbone of the resin:

wherein Z is an aromatic or aliphatic group optionally containing heteroatoms;

wherein X is a linker comprising a heteroatom selected from sulfur, oxygen, nitrogen, carbonyl, or combinations thereof;

wherein R is¹Comprising aliphatic and/or aromatic C₁To C₁₈And/or a heteroatom-containing linking group;

wherein R is²Each of which is the same or different and is independently selected from C₁To C₁₈Alkoxy, aryloxy, alkyl, aryl, or H, or OH, and optionally branched, and wherein at least one R²Is C₁To C₁₈Alkoxy, aryloxy, or 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 is

Wherein p is 1,2 or 3.

In particular, non-vulcanized embodiments of the disclosed compositions are described herein in which the functionalized resin is obtained by polymerization or copolymerization of one or more of unsaturated aliphatic monomers, terpenes, rosin acids, unsaturated aromatic cyclic monomers, unsaturated cycloaliphatic monomers, unsaturated fatty acids, methacrylates, unsaturated aromatic monomers, vinyl aromatic monomers, and unsaturated aliphatic/aromatic monomer mixtures₅One or more of piperylene, coumarone, indene and dicyclopentadiene.

In such non-vulcanized compositions containing functionalized resins, 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), halogenated butyl rubber, brominated butyl rubber, chlorinated butyl rubber, nitrile rubber, liquid rubber, polynorbornene copolymer, isoprene-isobutylene copolymer, ethylene-propylene-diene rubber, chloroprene rubber, acrylate rubber, fluoro rubber, silicone rubber, polysulfide rubber, epichlorohydrin rubber, styrene-isoprene-SSbutadiene terpolymer, hydrated acrylonitrile butadiene rubber, isoprene-butadiene copolymer, butyl rubber, hydrogenated styrene-butadiene rubber, butadiene acrylonitrile rubber, terpolymers formed from ethylene monomer, propylene monomer and/or Ethylene Propylene Diene Monomer (EPDM), isoprene-based block copolymers, butadiene-based block copolymers, styrene-butadiene-styrene block copolymers (SBS), styrene-ethylene/butylene-styrene block copolymers (EPDM), polypropylene-styrene-ethylene-styrene block copolymers (SBS), styrene-ethylene/styrene block copolymers (EPDM), polypropylene-ethylene-propylene-styrene block copolymers (styrene-styrene copolymer), polypropylene-ethylene-propylene-styrene block copolymers (SEBS), polypropylene-ethylene-styrene copolymer, styrene-ethylene-propylene-butadiene copolymer, styrene-styrene copolymer, styrene-ethylene-propylene copolymer, styrene-ethylene-styrene copolymer, styrene-ethylene-styrene copolymer, styrene.

In other embodiments of the non-vulcanized composition, the polymer optionally comprises a modification and/or functionalization selected from the group consisting of hydroxyl-, ethoxy-, epoxy-, siloxane-, amine-, aminosiloxane-, carboxyl-, phthalocyanine-and silane-sulfide-groups at the polymer chain end or at a lateral position within the polymer.

In other embodiments of the non-vulcanized composition comprising a functionalized resin according to formula I, q is an integer from 2 to 8, and/or n is an integer from 1 to 4. In such embodiments, the moiety- [ Z ] of formula I_k-X_n-R¹-(CH₂)_m-Si(R²)_p]_qLocated at one or more ends of the functionalized resin, randomly distributed throughout the functionalized resin, present as blocks throughout the functionalized resin, present in segments of the functionalized resin, present at least once in each functionalized resin, present at least twice in each functionalized resin, and/or present in the middle of each functionalized resin.

In other embodiments of the non-vulcanized composition comprising a functionalized resin according to formula I, X is phenol, hydroxyl, amine, imidazole, amide, polysulfide, sulfoxide, sulfone, sulfonamide, sulfonium, ammonium, carboxylic acid, ester, thioester, ether, maleimide, carbamate, cyanate, isocyanate, thiocyanate, pyridinium, or a combination thereof. In further embodiments, R¹Is C₁To C₁₀Carbon chain or C₁To C₅A carbon chain. In another such embodiment, R²Is C₁To C₁₀Alkoxy, aryloxy, alkyl or aryl, or C₁To C₅Alkoxy, aryloxy, alkyl or aryl, and optionally branched. In another alternative embodiment, Z is a 6-membered aromatic radicalA group or a saturated or unsaturated alicyclic group. Alternatively, X is oxygen or carbonyl. Additionally, in another embodiment, R²Each independently selected from the group consisting of hydroxy, methoxy, ethoxy, and propoxy.

In other embodiments of the non-vulcanized composition comprising the functionalized resin according to formula I, the amount of silane-containing groups grafted onto the functionalized resin is from about 0.001 to about 100 mole%, from about 0.1 to about 50 mole%, or from about 5 to about 50 mole%. In another such embodiment, the functionalized resin has a molecular weight of from about 200 g/mol to about 200,000 g/mol, from about 200 g/mol to about 175,000g/mol, or from about 200 g/mol to about 150,000 g/mol. In another such embodiment, the functionalized resin has a polydispersity index (PDI) of about 1 to 10. In another alternative embodiment of the non-vulcanized composition, the functionalized resin has a glass transition temperature Tg of less than about 200 ℃ or less than about 160 ℃. In another such embodiment, the amount of silane groups grafted to the functionalized resin is from about 0.01 to about 30 mole percent. Alternatively, in another embodiment, the functionalized resin is present in the non-vulcanized composition in an amount of 5 to 400phr, 5 to 120 phr, 5 to 100phr, 5 to 40 phr, 5 to 30phr, or 5 to 10 phr. Other embodiments contemplated herein include non-vulcanized compositions wherein the functionalized resin has a molecular weight of from about 400 to about 2,000 g/mol. In other such embodiments, the functionalized resin has a polydispersity index (PDI) of about 1 to about 5, or 1 to 2.

Other embodiments of the disclosed non-vulcanized compositions comprise at least one of silica, carbon black, silane coupling agents, processing oils, zinc compounds, waxes, vulcanizing agents, vulcanization retarders, vulcanization accelerators, and/or antioxidants. In such embodiments, the functionalized resin is, for example, hydrolyzed with at least one-R²The radicals are then bonded to the silica particles through the Si-O-Si moiety. Alternatively, in such embodiments, the functionalized resin molecule is hydrolyzed by at least one-R²The groups are then bonded to the second functionalized resin molecule through the Si-O-Si moiety. In another such embodiment, the functionalized resin is functionalized by incorporation into the polymer by way of a polar groupThe reactive group of the linker is covalently attached to the surface of the silica filler material.

In other embodiments of the non-vulcanized composition comprising a functionalized resin according to formula I, R¹is-O-CO-NH-R¹-(CH₂)₂-、O-CO-R³-(CH₂)₂-、-O-CH₂-R³-(CH₂)₂-、-CO-R³-(CH₂)₂-and-CO-NH-R³-(CH₂)₂-and R³Is aliphatic or aromatic C₁To C₈The carbon chain, optionally branched, and/or optionally containing one or more heteroatoms.

Also disclosed herein are end products made from or comprising the non-vulcanized composition. Such end products include, but are not limited to, for example, adhesives, laminates, tapes, heat seal coatings, heat-seal caps, disposable hygiene articles, adhesives, caulks, Insulating Glass (IG) units, bridge decks, waterproofing membranes, waterproofing compounds, padding materials, cable impregnation/filling compounds, low shrinkage sheet molding compounds, mass molding compounds, overmolding compounds, polyester composites, glass fiber reinforced plastics, coupling agents for wood-plastic composites, polyvinyl chloride extrusion compounds, polyacrylic blends, dewaxed precision castings, investment casting wax compositions, candles, windows, films, gaskets, seals, O-rings, automotive molded parts, automotive extrusions, sealants, apparel articles, low shrinkage additives for Sheet Molding Compounds (SMCs) and mass molding compounds (DMCs), Woven fabric sizing, nonwoven fabric sizing, rubber additives/processing aids, shoe soles, treads, tire sidewalls, tire innerliners, tire squeegees, wheel body profiles, tire belt plies, tire shoulders, tire belt profiles, carcass plies, bead wires, tire cord profiles, tire trumpet profiles, tire bandages, innertubes, hoses, belts, strips, tubes, brakes, or engine components. In such embodiments, the adhesive is a packaging adhesive, a food contact grade adhesive, an indirect food contact packaging adhesive, a product assembly adhesive, a woodworking adhesive, a flooring adhesive, an automotive assembly adhesive, a construction adhesive, a Pressure Sensitive Adhesive (PSA), a PSA tape, a PSA label, a PSA protective film, a laminating adhesive, a flexible packaging adhesive, a heat seal adhesive, an industrial adhesive, a sanitary nonwoven construction adhesive, a sanitary core integrity adhesive, or a sanitary elastic attachment adhesive.

Brief Description of Drawings

The present invention will now be described with reference to the accompanying drawings. The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate certain embodiments and together with the written description, serve to explain certain principles of the constructions and methods disclosed herein.

Fig. 1A through 1M show aspects of the synthetic route and architecture of silane-functionalized resins. FIG. 1A shows the synthesis of a pendant silane-containing resin by acetoxystyrene functionalization. FIG. 1B shows the synthesis of end-capped silane-containing resins by phenol functionalization. FIG. 1C shows the synthesis of a pendant silane-containing resin by phenol functionalization with anhydride silane. FIG. 1D shows the synthesis of a pendant silane-containing resin by grafting succinic anhydride onto the resin. FIG. 1E shows the synthesis of a pendant silane-containing resin by free radical copolymerization. Figure 1F shows various architectural embodiments surrounding the variable group Z. FIG. 1G shows the synthesis of end-capped silane-containing resins by phenol functionalization with succinic anhydride. FIG. 1H shows the synthesis of end-capped silane-containing resins by phenol functionalization with chlorosilane. FIG. 1I shows the synthesis of a pendant silane-containing resin by copolymerization of isobornyl methacrylate and 3- (trimethoxysilyl) propyl methacrylate. FIG. 1J shows the synthesis of a blocked silane-containing resin by phenol functionalization with a glycidoxysilane. FIG. 1K shows the synthesis of end-capped silane-containing resins by acid functionalization with glycidoxysilanes. FIG. 1L shows the synthesis of a blocked silane-containing resin by phenol functionalization with a glycidoxysilane. FIG. 1M shows the synthesis of end-capped silane-containing resins by phenol functionalization with phthalic anhydride and glycidoxysilane.

Figure 2A schematically shows a prior art resin simply inserted into a polymer matrix. FIG. 2B schematically shows an officerFunctionalized resin and silicon dioxide particle SiO₂The surface of (a).

FIG. 3 shows a representative Fourier transform Infrared Spectroscopy (FT-IR) spectrum of a functionalized resin synthesis product of step 1A (synthesis of a pendant phenol-functionalized resin by deprotection of acetoxystyrene), as described in example 1.1.

Figure 4 shows a representative Thermal Gravimetric Analysis (TGA) trace of the functionalized resin synthesis product of step 1A (synthesis of a pendant phenol-functionalized resin by deprotection of acetoxystyrene), as described in example 1.1.

Figure 5 shows a representative Differential Scanning Calorimetry (DSC) trace of the functionalized resin synthesis product of step 1A (synthesis of a pendant phenol-functionalized resin by deprotection of acetoxystyrene), as described in example 1.1.

FIG. 6 shows a representative FT-IR spectrum of a functionalized resin synthesis product of step 1B (synthesis of a pendant carboxylic acid-functionalized resin by phenol functionalization), as described in example 1.1.

Figure 7 shows a representative TGA trace of the functionalized resin synthesis product of step 1B (synthesis of a pendant carboxylic acid-functionalized resin from phenol functionalization) as described in example 1.1.

Figure 8 shows a representative DSC trace of the functionalized resin synthesis product of step 1B (synthesis of a pendant carboxylic acid-functionalized resin from phenol functionalization), as described in example 1.1.

FIG. 9 shows a representative FT-IR spectrum of the functionalized resin synthesis product of step 1C (synthesis of a pendant silane-functionalized resin functionalized with carboxylic acid groups), as described in example 1.1.

Figure 10 shows a representative TGA trace of the functionalized resin synthesis product of step 1C (synthesis of a pendant silane-functionalized resin functionalized by carboxylic acid group functionalization), as described in example 1.1.

Figure 11 shows a representative DSC trace of the functionalized resin synthesis product of step 1C (synthesis of a pendant silane-functionalized resin functionalized with carboxylic acid groups), as described in example 1.1.

Figure 12 shows a representative Gel Permeation Chromatography (GPC) trace of the functionalized resin synthesis product of step 1C (synthesis of a pendant silane-functionalized resin functionalized by carboxylic acid group functionalization), as described in example 1.1.

Figure 13 shows a representative FT-IR spectrum of the functionalized resin synthesis product of step 2A (synthesis of end-capped carboxylic acid-functionalized resin from phenol functionalization) as described in example 1.2.

Figure 14 shows a representative TGA trace of the functionalized resin synthesis product of step 2A (synthesis of end-capped carboxylic acid-functionalized resin from phenolic group functionalization) as described in example 1.2.

Figure 15 shows a representative DSC trace of the functionalized resin synthesis product of step 2A (synthesis of end-capped carboxylic acid-functionalized resin from phenol group functionalization) as described in example 1.2.

Fig. 16 shows a representative FT-IR spectrum of the functionalized resin synthesis product of step 2B (synthesis of a blocked silane-functionalized resin functionalized with carboxylic acid groups), as described in example 1.2.

Figure 17 shows a representative TGA trace of the functionalized resin synthesis product of step 2B (synthesis of a terminated silane-functionalized resin functionalized with carboxylic acid groups), as described in example 1.2.

Figure 18 shows a representative DSC trace of the functionalized resin synthesis product of step 2B (synthesis of a terminated silane-functionalized resin functionalized with carboxylic acid groups), as described in example 1.2.

Figure 19 shows representative GPC traces of the functionalized resin synthesis product of step 2B (synthesis of a blocked silane-functionalized resin functionalized with carboxylic acid groups), as described in example 1.2.

FIG. 20 shows a representative functionalized resin synthesis product of step 2B (synthesis of a blocked silane-functionalized resin functionalized with carboxylic acid groups)¹³C Nuclear Magnetic Resonance (NMR) trace as described in example 1.2.

FIG. 21 shows a representative functionalized resin synthesis product of step 2B (synthesis of a blocked silane-functionalized resin functionalized with carboxylic acid groups)²⁹Si NMR trace as described in example 1.2.

FIG. 22 shows a representative FT-IR spectrum of the functionalized resin synthesis product of step 3B (synthesis of a pendant silane-functionalized resin by deprotection of acetoxystyrene), as described in example 1.3.

Figure 23 shows a representative TGA trace of the functionalized resin synthesis product of step 3B (synthesis of a pendant silane-functionalized resin by deprotection of acetoxystyrene), as described in example 1.3.

Figure 24 shows a representative DSC trace of the functionalized resin synthesis product of step 3B (synthesis of a pendant silane-functionalized resin by deprotection of acetoxystyrene), as described in example 1.3.

Figure 25 shows a representative FT-IR spectrum of the functionalized resin synthesis product of step 4A (synthesis of a pendant carboxylic acid-functionalized resin from phenol modification with anhydride silane), as described in example 1.4.

Figure 26 shows a representative TGA trace of the functionalized resin synthesis product of step 4A (synthesis of a pendant carboxylic acid-functionalized resin from phenol modification with anhydride silane), as described in example 1.4.

Figure 27 shows a representative DSC trace of the functionalized resin synthesis product of step 4A (synthesis of a pendant carboxylic acid-functionalized resin from phenol modification with anhydride silane), as described in example 1.4.

Figure 28 shows representative GPC traces of the functionalized resin synthesis product of step 4A (synthesis of a pendant carboxylic acid-functionalized resin from phenol modification with anhydride silane) as described in example 1.4.

FIG. 29 shows a representative FT-IR spectrum of the functionalized resin synthesis product of step 4B (synthesis of a pendant silane-functionalized resin derived from grafting succinic anhydride onto Kristalex ™ 3085), as described in example 1.4.

FIG. 30 shows a representative TGA trace of the functionalized resin synthesis product of step 4B (synthesis of a pendant silane-functionalized resin derived from grafting succinic anhydride onto Kristalex ™ 3085), as described in example 1.4.

FIG. 31 shows a representative DSC trace of the functionalized resin synthesis product of step 4B (synthesis of a pendant silane-functionalized resin derived from grafting succinic anhydride onto Kristalex ™ 3085), as described in example 1.4.

FIG. 32 shows representative GPC traces of the functionalized resin synthesis product of step 4B (synthesis of a pendant silane-functionalized resin derived from grafting succinic anhydride onto Kristalex ™ 3085), as described in example 1.4.

FIG. 33 shows representative functionalized resin synthesis products of step 4B (Synthesis of a pendant silane-functionalized resin derived from grafting succinic anhydride onto Kristalex ™ 3085)¹H NMR traces, as described in example 1.4.

FIG. 34 shows a representative of the functionalized resin synthesis products of step 4B (Synthesis of a pendant silane-functionalized resin derived from grafting succinic anhydride onto Kristalex ™ 3085(Eastman chemical, Ltd., Kingsport, TN, US))¹³C NMR traces as described in example 1.4.

FIG. 35 shows representative functionalized resin synthesis products of step 4B (Synthesis of a pendant silane-functionalized resin derived from grafting succinic anhydride onto Kristalex ™ 3085)²⁹Si NMR trace as described in example 1.4.

Figure 36 shows representative GPC traces of the functionalized resin synthesis product of step 5A (synthesis of a pendant silane-functionalized resin from free radical copolymerization with methyl propionate silane), as described in example 1.5.

FIG. 37 shows a representation of the functionalized resin synthesis product of step 5A (synthesis of a pendant silane-functionalized resin from free radical copolymerization with methyl propionate silane)¹H NMR trace as described in example 1.5.

Figure 38 shows a representative FT-IR spectrum of a functionalized resin synthesis product obtained by phenol functionalization with succinic anhydride as described in example 1.6.

Figure 39 shows a representative TGA trace of a functionalized resin synthesis product obtained by phenol functionalization with succinic anhydride as described in example 1.6.

Figure 40 shows a representative DSC trace of a functionalized resin synthesis product obtained by phenol functionalization with succinic anhydride as described in example 1.6.

Figure 41 shows a representative GPC trace of a functionalized resin synthesis product obtained by phenol functionalization with succinic anhydride as described in example 1.6.

FIG. 42 shows a representation of end-capped silane-containing resins produced by phenol functionalization with chloro-silanes as described in example 1.7²⁹Si NMR trace.

FIG. 43 shows a representation of pendant silane-containing resins synthesized by copolymerization of isobornyl methacrylate and 3- (trimethoxysilyl) propyl methacrylate as described in example 1.8¹H-NMR trace.

FIG. 44 shows a representative DSC trace of a pendant silane-containing resin synthesized by copolymerization of isobornyl methacrylate and 3- (trimethoxysilyl) propyl methacrylate as described in example 1.8.

FIG. 45 shows a representative of pendant silane-containing resins synthesized by copolymerization of isobornyl methacrylate and 3- (trimethoxysilyl) propyl methacrylate as described in example 1.8²⁹Si-NMR trace.

FIG. 46 shows a representative IR trace of a pendant silane containing resin synthesized by copolymerization of isobornyl methacrylate and 3- (trimethoxysilyl) propyl methacrylate as described in example 1.8.

Figure 47 shows a representative TGA trace obtained for the end-capped silane-containing resin end-product obtained by phenol functionalization with glycidoxysilanes as described in example 1.9.

Figure 48 shows a representative DSC trace obtained for the end-capped silane-containing resin end-product obtained by phenol functionalization with glycidoxysilanes as described in example 1.9.

FIG. 49 shows a representative of the end-capped silane-containing resin end-products obtained by phenol functionalization with glycidoxysilanes as described in example 1.9¹H-NMR trace.

Figure 50 shows representative GPC traces obtained for the end-capped silane-containing resin end-product obtained by phenol functionalization with glycidoxysilanes as described in example 1.9.

Figure 51 shows representative GPC traces obtained for the capped silane-containing resins obtained by acid functionalization with glycidoxysilanes as described in example 1.10.

FIG. 52 shows a representation of the blocked silane-containing resin obtained by acid functionalization with glycidoxysilanes as described in example 1.10¹H-NMR trace.

Figure 53 shows a representative TGA trace obtained for the capped silane-containing resin obtained by acid functionalization with a glycidoxysilane as described in example 1.10.

Figure 54 shows a representative DSC trace of the capped silane-containing resin obtained by phenol functionalization with glycidoxysilanes as described in example 1.11.

Figure 55 shows representative GPC traces of the capped silane-containing resins obtained by phenol functionalization with glycidoxysilanes as described in example 1.11.

FIG. 56 shows a representative of blocked silane-containing resins obtained by phenol functionalization with glycidoxysilanes as described in example 1.11¹H-NMR trace.

Figure 57 shows a representative TGA trace of a capped silane-containing resin obtained by phenol functionalization with a glycidoxysilane as described in example 1.11.

FIG. 58 shows a representative of capped silane-containing resins obtained by phenol functionalization with phthalic anhydride and glycidoxysilane as described in example 1.12¹H-NMR trace. Figure 59 shows representative GPC traces of the capped silane-containing resins obtained by phenol functionalization with phthalic anhydride and glycidoxysilane as described in example 1.12.

Figure 60 shows a plot of the resiliency vs shore a hardness for each sample tested in example 3.

Detailed description of the invention

It should be understood that the following detailed description is provided to give the reader a more complete understanding of certain embodiments, features and details of the invention, and should not be construed to limit the scope of the invention.

Definition of

Certain terms used throughout the present disclosure are defined below so that the present invention may be more easily understood. Additional definitions are set forth throughout the disclosure.

Every term not explicitly defined in this application is to be understood as having a meaning commonly accepted by those skilled in the art. A term's definition should be taken from a standard dictionary if its construction makes it meaningless or substantially meaningless in context.

The use of numerical values in the various ranges specified herein is considered approximate, as if the minimum and maximum values within the ranges were both preceded by the word "about," unless expressly specified otherwise. As used herein, the term "about" is intended to include deviations of the stated value by 1%, 2%, 3%, 4%, or no more than 5% of the stated value. In this manner, minor variations above and below the stated ranges can be used to achieve substantially the same results as values within the ranges. Further, the disclosure of these ranges is intended as a continuous range including every value between the minimum and maximum values.

Unless otherwise indicated, percent solids or weight percent (wt%) is specified with reference to the total weight of the particular formulation, emulsion, or solution.

Unless otherwise specified, the terms "polymer" and "resin" refer to the same species and include homopolymers having the same repeat units along the backbone as well as copolymers having two or more different repeat units along the backbone. Such polymers or resins include, but are not limited to, materials prepared by condensation, cationic, anionic, ziegler-natta, reversible addition-fragmentation chain transfer (RAFT), or free radical polymerization.

The term "comprising" (and grammatical variations thereof) as used herein is used in an inclusive sense of "having" or "including" and not in an exclusive sense of "consisting only of.

The terms "a" and "an" and "the" as used herein are understood to cover one or more of the referenced components, i.e., the plural as well as the singular.

The "phr" means parts per hundred parts of rubber by weight and is used in this specification to mean the amount conventionally specified in the rubber industry for blend formulations. The dosage in parts by weight of the individual substances in this context is always based on 100 parts by weight of the total rubber present in the blend. In the context of the present disclosure, the above-mentioned resins are not considered to be rubbers.

"thermoplastic polymer" refers to a polymer that has no sites for covalent crosslinking between individual polymer macromolecules, and that becomes liquid, pliable, or moldable above a particular temperature, and then returns to a solid state upon cooling. In many cases, the thermoplastic polymer may also be dissolved in a suitable organic solvent medium.

Unless otherwise indicated, the term "mole%" when used in reference to a repeat unit in a polymer refers to the nominal (theoretical) amount of repeat unit based on the molecular weight of the ethylenically unsaturated polymerizable monomer used during polymerization, or the actual amount of repeat unit in the resulting polymer as determined using suitable analytical techniques and equipment.

The term "vulcanization" as used herein means subjecting a chemical composition such as a polymer (e.g., an elastomeric and/or thermoplastic polymer composition) to a chemical process including the addition of sulfur or other similar curing agents, activators and/or accelerators at elevated temperature (see, e.g., WO 2007/033720, WO 2008/083242 and PCT/EP 2004/052743.) curing agents and accelerators are used to form crosslinks or chemical bridges between individual polymer chains. curing agents sulfur vulcanizing agents and vulcanization accelerators suitable sulfur vulcanizing agents include, for example, elemental sulfur (free sulfur) or sulfur-donating vulcanizing agents which make sulfur available at temperatures of about 140 ℃ to about 190 ℃ for vulcanization.suitable examples of sulfur-donating vulcanizing agents include aminodisulfides, polymeric polysulfides and thioolefin adducts. in some embodiments, the polymer composition described herein which can be vulcanized may also contain one or more vulcanization accelerators which control the time and/or temperature required for vulcanization and affect the properties of the vulcanized rubber and which include, as well, in one or more detail, more of the following embodiments, a primary and secondary vulcanization accelerators including, for example, thiothiuram-thiolane, or thiolane, after reaction, these embodiments include, a mixture of bis-thiolane, bis-thiolane, bis-thiolane, bis-thiolane, bis-thiolane, bis-thiolane, bis-thiolane, or bis-bis.

"weight average molecular weight (M)_w) "determined using Gel Permeation Chromatography (GPC). The values reported herein are reported as polystyrene equivalents.

The term "Mn" as used herein refers to the number average molecular weight in g/mol, i.e., the statistical average molecular weight of all polymer chains in a sample, or the total weight of all molecules in a polymer sample divided by the total number of molecules present.

The term "Mz" as used herein refers to the z-average molecular weight in g/mol and is generally determined by sedimentation equilibrium (ultracentrifugation) and light scattering. Here, Mz was determined by Gel Permeation Chromatography (GPC) according to the method described below. Mz is the thermodynamic equilibrium position of a polymer, where the polymer molecules are distributed according to their molecular size. In some cases, this value is used as an indicator of high molecular weight tail in the thermoplastic resin.

"glass transition temperature (Tg)" is the second-order transition, and is the temperature range over which an amorphous material reversibly changes from a hard, rigid, or "glassy" solid state to a more flexible, compliant, or "rubbery" viscous state, and is measured in degrees celsius or fahrenheit. Tg is different from the melting temperature. Tg can be determined using Differential Scanning Calorimetry (DSC) as disclosed in example 2 below.

The terms "end-capped" and "end-capped" are used interchangeably herein to refer to the end or terminus of a polymer having a silane group located at the terminus or terminus of the polymer. The silane molecules of formula I may be located at the end points or ends of the resinous polymer, resulting in a capped or end-capped resinous polymer.

The term "pendant" is used herein to indicate that the silane molecule of formula I can be grafted or attached or copolymerized into a non-terminal position of the polymer, i.e., a position on the polymer backbone, rather than an endpoint, to create a multi-derivatized polymer resin. The silane-functional moiety of formula I is attached to the side positions of the polymer, while the terminal or end-capping silane moieties are attached to the final chain units at either end of the polymer (resin), when the polymer chain units to which the silane-functional moiety is attached occupy an internal position remote from either end of the polymer backbone. Types of polymers suitable for silane functionalization according to the process include, but are not limited to, pure monomer thermoplastic resins (PMR), C5 thermoplastic resins, C5/C9 thermoplastic resins, C9 thermoplastic resins, terpene thermoplastic resins, indene-coumarone (IC) thermoplastic resins, dicyclopentadiene (DCPD) thermoplastic resins, hydrogenated or partially hydrogenated Pure Monomer (PMR) thermoplastic resins, hydrogenated or partially hydrogenated C5 thermoplastic resins, hydrogenated or partially hydrogenated C5/C9 thermoplastic resins, hydrogenated or partially hydrogenated C9 thermoplastic resins, hydrogenated or partially hydrogenated dicyclopentadiene (DCPD) thermoplastic resins, terpene thermoplastic resins, modified indene-coumarone (IC) thermoplastic resins.

Silane functionalization of resins

Resins functionalized to include silane molecules including various addenda are disclosed. The functionalized resins disclosed herein have different structures and can be manufactured or synthesized using a variety of methodologies, methods, and strategies. For example, several possible synthetic routes to the functionalized resins disclosed herein are schematically shown in fig. 1A to 1M. That is, fig. 1A through 1M provide schematic depictions of several exemplary embodiments of synthetic strategies for deriving the silane-containing resins disclosed herein.

As non-limiting examples thereof, phenolic-containing resins having functional groups or functional monomers from the intra-chain position copolymerized with acetoxystyrene may be used to provide starting materials for silane functionalization.

As another non-limiting example of a general synthetic strategy that can be used to obtain the disclosed silane-functionalized resins, end-capped resins having phenolic end groups can be used in these same synthetic reactions, thereby producing resins having one or more end-functionalized groups. As another exemplary embodiment, the phenolic groups may be reacted in a williamson ether synthesis route followed by a mixed anhydride reaction to produce a silane-containing resin as in fig. 1C. The reaction of phenolic-based resins with anhydride-containing silanes was also very successful. Other synthetic strategies produce a pendant functionalized resin that can produce the desired degree of functionalization at an internal position.

The functionalized resin may be in the form of a block copolymer, and alternatively, the silane moieties of the functionalized resin may occur randomly throughout the polymer, more or less uniformly distributed throughout the resin backbone. That is, non-limiting examples of functionalized resins disclosed herein include resins formed by the block copolymer process, as well as functionalization of resins that have been formed, resulting in resins having random monomers functionalized throughout the resin backbone. Additionally, as depicted in scheme 5, the functionalized resins disclosed herein can be synthesized starting from resin monomers that react directly with silane moieties in one step to form the functionalized resin. The functionalized resins can also be synthesized by starting with fully formed resins such as those disclosed in schemes 1-4, examples 1 and 2 below.

The silane-functionalized resins disclosed herein have the general chemical structure of formula I below, where "resin" represents the backbone of the resin, as shown, for example, in fig. 1A-1E and fig. 1G-1M:

wherein Z is an aromatic or aliphatic group optionally containing heteroatoms;

wherein X is a linker comprising a heteroatom selected from sulfur, oxygen, nitrogen, carbonyl, or combinations thereof;

wherein R is¹Comprising aliphatic and/or aromatic C₁To C₁₈And/or a heteroatom-containing linking group;

wherein R is²Each of which is the same or different and is independently selected from C₁To C₁₈Alkoxy, aryloxy, alkyl, aryl, or H, or OH, and optionally branched, andwherein at least one R²Is C₁To C₁₈Alkoxy, aryloxy, or 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 is

Wherein p is 1,2 or 3.

Typically, the heteroatom group R¹And a silane group Si (R)²)_pThe carbon chain linker in between is methylene, but shorter or longer carbon chain linkers may also be used. Urethane linkages are formed by reacting a phenol or hydroxyl containing resin with a silyl isocyanate (triethoxysilylpropyl isocyanate) to produce a functionalized resin having the formula: resin-OCONH- (CH)₂)₃-Si(OCH₂CH₃)₃. The phenol or hydroxyl based resin reacts with an anhydride silane, such as 3- (triethoxysilyl) propyl succinic anhydride, causing the formation of an ester linkage, forming a compound having the formula: resin-O-CO-CH (CH)₂COOH)((CH₂)₃-Si(OCH₂CH₃)₃) The functionalized resin of (1). Ester bonds with the resin may also be obtained by esterification or transesterification. Silanes such as Cl- (CH) which can be functionalized directly with alkyl halides by the ether linkage to the backbone with oxygen₂)₃Si(O CH₂CH₃)₃Derivatization by Williamson ether synthesis of resin-OH to form resin-O- (CH)₂)₃-Si(OCH₂CH₃)₃. In the case of other reagents such as sodium chloroacetate, post-modification after Williamson ether synthesis is required to obtain silane-functionalized resins, for example, by resin-O-CH₂Reaction of COOH with ethyl chloroformate and 3- (aminopropyl) triethoxysilane to form resin-O-CH₂CO-NH-(CH₂)₃-Si(OCH₂CH₃)₃. Any rosin acid-resin copolymer or any resin-COOH can be functionalized with ethyl chloroformate and 3- (aminopropyl) triethoxysilane to form resin-CO-NH- (CH)₂)₃-Si(OCH₂CH₃)₃For example, succinic anhydride may be grafted onto styrene or α -methylstyrene by using a Lewis acid catalyst to form the resin-CO- (CH)₂)₂-COOH to obtain a resin-COOH. Further functionalization to produce resin-CO- (CH)₂)₂-CO-NH-(CH₂)₃-Si(OCH₂CH₃)₃. Maleic anhydride can be grafted onto a resin containing unsaturated groups by ring-opening maleic anhydride with triethoxysilylpropylamine to obtain the resin-CO-NH- (CH)₂)₃-Si(OCH₂CH₃)₃。

The copolymer may include any number of other comonomers, but most likely includes a resin of styrene or α -methylstyrene, or mixtures thereof.

In a typical embodiment, Z is an aromatic group, more typically a 6-membered aromatic group. In another typical embodiment, Z is a saturated or unsaturated cycloaliphatic radical. Additionally, the variable Z may comprise one or more heteroatoms, as disclosed in the scheme provided in fig. 1F. The heteroatom may be one or more of oxygen, sulfur and/or nitrogen.

In another specific embodiment, the heteroatom-containing linking group X includes a phenol, hydroxyl, amine, imidazole, amide, carboxylic acid, isocyanate, carbamate, urea, ketone, anhydride, ester, ether, thioether, sulfoxide, sulfone, sulfonamide, sulfonium, ammonium, maleimide, or pyridinium linking group that is para, meta, or ortho-linked to covalently link a silane group and/or a carbonate_nR¹-(CH₂)_mComprises oneOr a plurality of groups including carbamate, ester, ether, ketone, amide, and propyl.

In general, R²Each of which is the same or different and is independently selected from C₁To C₁₈Alkoxy, aryloxy, alkyl, aryl, or H, or OH, and optionally branched, and wherein at least one R²Is C₁To C₁₈Alkoxy, aryloxy, or H, or OH.

The silane-containing groups grafted onto the resins disclosed herein may be located at the ends of the polymer resin units, i.e., capped, or randomly distributed along the polymer backbone, i.e., pendant positions within the polymer resin, or any combination thereof, i.e., capped and pendant. In embodiments of the end-capped functionalized resin, the amount of silane-containing groups grafted to the functionalized resin is from 0.001 to 100 mole%, more typically from 0.1 to 50 mole%, and most typically from 0.1 to 30 mole%, from 0.1 to 25 mole%, from 0.1 to 20 mole%, from 0.1 to 15 mole%, from 0.1 to 10 mole%, or from 0.1 to 9 mole%. In one embodiment, the amount of silane group(s) containing grafted to the resin is from 0.01 to 30 mole%.

In another embodiment, the silane-containing groups of formula I are located in one or more pendant positions within the polymer. In such embodiments, the amount of silane-containing groups grafted to the resin is from about 0.0001 to about 100 mole%, from about 0.1 to about 30 mole%, from about 0.1 to about 50 mole%, or from about 0.1 to about 100 mole%.

In another non-limiting embodiment, more than one silane functional group, i.e., -R¹-(CH₂)_m-Si(R²)_pAttached to the same linking group X or R¹The above. The silane groups on the same linking group may be the same or different. In addition, the functionalized resins disclosed herein encompass R's containing branch points¹And X moieties, which may also contain one or more silane functionalization (see, e.g., example 1.3, infra)Scheme 3)。

In particular, the molecular weight (Mw) of the resin may be 200 to 200,000 g/mol, more typically 200 to 175,000g/mol, more typically 200 to 150,000 g/mol, 200 to 125,000g/mol, 200 to 100,000 g/mol, 200 to 75,000g/mol, and most typically 200 to 50,000 g/mol. In another exemplary embodiment, the molecular weight of the resin is from 400 g/mol to 200,000 g/mol, more typically from 400 to 175,000g/mol, more typically from 400 to 150,000 g/mol, from 400 to 125,000g/mol, from 400 to 100,000 g/mol, from 400 to 75,000g/mol, and most typically from 400 to 50,000 g/mol. In yet another exemplary embodiment, the molecular weight of the resin is from 400 to 25,000 g/mol.

In another embodiment, the resin may have any polydispersity index (PDI) of 1 to 10, 1 to 9, 1 to 8, 1 to 7,1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 to 2. In another typical embodiment, the resin may have any molecular weight or PDI, but must have a Tg low enough to be compounded with rubber formulations at 150 to 160 ℃, and must be compounded with various rubbers or mixtures of rubbers with other additives at that temperature.

In one embodiment, the glass transition temperature Tg of the resin is less than 200 ℃. In another embodiment, the Tg is less than 190 ℃, 180 ℃, 170 ℃, 160 ℃, 150 ℃,140 ℃, 130 ℃, 120 ℃, 110 ℃, 100 ℃, 90 ℃, 80 ℃, 70 ℃, 60 ℃,50 ℃, 40 ℃, 30 ℃, 20 ℃, 10 ℃,0 ℃, -5 ℃, -10 ℃, -15 ℃, -20 ℃, -25 ℃ or-30 ℃. More particularly, in one embodiment, the Tg is not less than-10 ℃. In another embodiment, the Tg is not higher than 70 ℃.

In another embodiment, the resin comprises one or more terminal functional groups- [ Z ]_k-X_n-R¹-(CH₂)_m-Si(R²)_p]_q. Furthermore, one or more (q) moieties Z, which are typically pendant to the resin backbone in a random, segmented or block structure_k-X_n-R¹-(CH₂)_m-Si(R²)_pThe resin is functionalized. In another embodiment, the side chain is end-capped. In another embodiment, the side chain is a mixture of a capped side chain and a pendant side chain.

In particular, at least one-R²After hydrolysis of the groups, the functionalized resin bonds to the silica particles through Si-O-Si bonds. Also, the same applies toIn particular, at least one-R²After hydrolysis of the group, the functionalized resin molecule is attached to the second functionalized resin molecule by a Si-O-Si bond. In addition, bridged side chains can be formed in which the Si group passes through one, two or three R²The group is covalently bound to itself.

In one exemplary embodiment, R¹is-O-CO-NH-R³-(CH₂)₂-、O-CO-R³-(CH₂)₂-、-O-CH₂-R³-(CH₂)₂-、-CO-R³-(CH₂)₂-and-CO-NH-R³-(CH₂)₂Or mixtures thereof, and R³Is aliphatic or aromatic C₁To C₈The carbon chain, optionally branched, and/or optionally containing one or more heteroatoms. Preferably, R³Is aliphatic or aromatic C₁To C₈A carbon chain.

In formula I, n may be an integer from 1 to 10, 1 to 9, 1 to 7,1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 to 2. Additionally, the variable m may be any integer from 0 to 10, 1 to 10, 2 to 10, 3 to 10, 4 to 10, 5 to 10, 6 to 10, 7 to 10, 8 to 10, or 9 to 10. The variables n and m may also be separated by any range of integers therebetween, such as 1 to 2,2 to 3,3 to 4, 4 to 5, 5 to 6, 6 to 7, 7 to 8, 8 to 9, or 9 to 10, or any other range therein. In particular, m may be 0 to 3, 1 to 3 or 2 to 3.

Formula I encompasses several preferred embodiments. For example, several non-limiting embodiments of the functionalized resin include the following structures:

resin- [ Z ]_k-CH₂-Si(R²)_p]_q，

Resin- [ Z ]_k-O-CO-R-(CH₂)₂-CH₂-Si(R²)_p]_q，

Resin- [ Z ]_k-O-CH₂-R-(CH₂)₂-CH₂-Si(R²)_p]_q，

Resin- [ Z ]_k-CO-(CH₂)₂-CH₂-Si(R²)_p]_q，

Resin- [ Z ]_k-CO-NH-R-(CH₂)₂-CH₂-Si(R²)_p]_q，

Wherein Z is an aromatic or aliphatic-containing group and the silane linkage number "q" can be any integer of at least 1, but is typically 1 to 20, 1 to 19, 1 to 18, 1 to 17, 1 to 16, 1 to 15, 1 to 14, 1 to 13, 1 to 12, 1 to 11, 1 to 10, 1 to 9, 1 to 8, 1 to 7,1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 to 2, and wherein the silane functional groups are attached at the end or pendant to the resin chain, or mixtures thereof. In these embodiments, k may be an integer of 0 or 1.

Other non-limiting embodiments of the functionalized resin may include, for example, the following structures:

resin- [ Z ]_k-O-CH₂CO-NH-(CH₂)₃-Si(OCH₂CH₃)₃]_q，

Resin- [ Z ]_k-O-CO-CH(CH₂COOH)-(CH₂)₃-Si(OCH₂CH₃)₃]_q，

Resin- [ Z ]_k-CO-NH-(CH₂)₃-Si(OCH₂CH₃)₃]_q，

Resin- [ Z ]_k-CO-(CH₂)₂-CO-NH-(CH₂)₃-Si(OCH₂CH₃)₃]_q，

Resin- [ Z ]_k-O-CO-NH-(CH₂)₃-Si(OCH₂CH₃)₃]_q，

Resin- [ Z ]_k-O-(CH₂)₃-Si(OCH₂CH₃)₃]_q。

Wherein Z is a group containing an aliphatic or aromatic group, such as a styrene or benzene ring structure, or alternatively contains a long C₁To C₁₈An aliphatic chain, and wherein the number of silane linkages "q" can be any number, but is typically 1 to 20, 1 to 19, 1 to 18, 1 to 17,1 to 16, 1 to 15, 1 to 14, 1 to 13, 1 to 12, 1 to 11, 1 to 10, 1 to 9, 1 to 8, 1 to 7,1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 to 2, are linked at the end or lateral position of the resin chain, or a mixture thereof. In these embodiments, k may be an integer of 0 or 1.

Additional preferred, non-limiting exemplary embodiments of the disclosed silane-functionalized resins have the following general structure:

resin- [ Z ]_k-X_n-R¹-(CH₂)_m-Si(R²)_p]_q，

resin-Z_k-SO₂NH-(CH₂)₂-CH₂-Si(OCH₂CH₃)₃，

resin-Z_k-SONH -(CH₂)₂-CH₂-Si(OCH₂CH₃)₃，

resin-Z_k-S-(CH₂)₂-CH₂-Si(OCH₂CH₃)₃，

resin-Z_k-SO-(CH₂)₂-CH₂-Si(OCH₂CH₃)₃，

resin-Z_k-SO2-(CH₂)₂-CH₂-Si(OCH₂CH₃)₃，

Resin- (Z)_k(COO-R-(CH₂)₂-Si(OCH₂CH₃)₃))_q-a resin,

resin- [ Z ]_k(COO(CH₂)₂OCOC(COCH₃)N(CH₂)₃Si(OCH₃)₃)]_q-a resin,

resin-Z_k-SO₂NH-(CH₂)₂-CH₂-Si(OCH₂CH₃)₃，

resin-Z_k-Ph-O-Si(OCH₂CH₃)₃。

Other exemplary silane structures can be obtained and provided herewithHis silane-functionalized resin, which is prepared from a mixture of Si (OH)_nBy hydrolysis or substitution of Si (R)²)_pIs produced by sol-gel chemistry of (a) wherein for silane R²One or more of the groups, n is an integer from 1 to 3. After hydrolysis, any two Si (OH) s may occur_nCondensation of the groups to form Si-O-Si structures links the resin to the resin, the resin to other commercially available silanes, the resin to functionalized rubber grades, or the resin to fillers. Can select-Si (R)²)_pR of (A) to²Groups, e.g., as heteroatom-containing or carbon chain linkers with another similar resin, linkers with another type of silane-functionalized resin, linkers with another small molecule silane or silane polysulfides, e.g., bis [3- (triethoxysilyl) propyl ] can be used]Tetrasulfide (e.g., Si69, Evonik Industries AG, Essen, Germany) or bis [3- (triethoxysilyl) propyl ] ketone]Disulfides (e.g., Si266, Evonik industries AG, Essen, Germany), linkages to filler particles or linkages to functionalized rubber grades. These non-limiting exemplary structures include Si-O-Si bonds. Any known combination of condensation resin and resin is possible, i.e. interchain bond formation between two different silane-containing groups, and/or intrachain bond formation within the same silane-containing group, resin to other silanes, resin to functionalized rubber grades, or resin to filler structures, thereby condensing Si (oh) with Si-O-Si to link the two Si-containing groups. In another embodiment, the functionalized resin may contain an aromatic group (Ar) as the Z-group, e.g., to produce a structural resin-Ar-O-R¹-(CH₂)_m-Si(R²)_pOr resin-Ar-CO-R¹-(CH₂)_m-Si(R²)_p。

In another non-limiting embodiment, X is an oxygen atom and the phenolic group is from a resin synthesis with phenol as a chain terminator, or using an acetoxystyrene comonomer to derive a hydroxystyrene containing resin the carbonyl (C = O) group attachment may be from a group grafted onto styrene or α -methylstyrene, for example using succinic anhydride or another anhydride and a Lewis acid catalyst such as aluminum chloride.

Compositions comprising silane-functionalized resins

More specifically, in one embodiment, various thermoplastic polymers and elastomers, such as ethylene-vinyl acetate (EVA) or poly (ethylene-vinyl) acetate (PEVA) compounds, various polyolefins and α -polyolefins, reactor-ready polyolefins, thermoplastic polyolefins, elastomers such as styrene-butadiene rubber (SBR), Butadiene Rubber (BR), and natural rubber, polyesters, styrene block copolymers, acrylics, and acrylates can be blended with the disclosed functionalized resins.

In one embodiment, the functionalized resin is blended with an alkoxysilane low molecular weight polymer that can be used as an additive, which will be used in the same manner as typical low molecular weight polymers are used. The presence of the functionalized resins disclosed herein in compositions with alkoxysilane low molecular weight polymers enhances processability (higher melt flow rate, lower viscosity) and promotes adhesion. The alkoxysilane low molecular weight polymer is further reacted after processing to produce a crosslinked polymer that increases the heat and chemical resistance of the final article incorporating such blended resins. If the polymer to be modified has alkoxysilane functional groups, the low molecular weight polymer can be grafted onto the polymer to be modified, in addition to being crosslinked with itself. In addition, the ability to react further is beneficial in filling systems (particles, fibers, etc.) where the alkoxysilane is chemically bonded to surface groups on various fillers.

In another embodiment, styrene-ethylene/butylene-styrene block copolymers (e.g., Kraton G1650, Kraton Polymers U.S., LLC, Houston, TX, US) were blended/processed with about 20 weight percent alkoxysilane-functionalized polystyrene at a temperature below that which activates hydrolysis and crosslinking of the alkoxysilanes. The blend may optionally include other additives such as thermoplastic polymers, oils, and fillers. After processing into an article (film, fiber, profile, gasket, PSA tape, molded handle, sealant, etc.), the article is exposed to a temperature sufficient to initiate hydrolysis and subsequent reaction of the alkoxysilane. For thermoplastic elastomer applications such as films, fiber profiles, gaskets, and the like, high temperature compression set and chemical resistance are improved. For tape applications, chemical crosslinking can be triggered in the same manner while increasing shear resistance, shear bond failure temperature, and chemical resistance.

In another embodiment, disposable hygiene articles are disclosed that comprise an adhesive comprising the disclosed silane-functionalized resins that exhibit improved adhesive and cohesive strength through improved values in peel adhesion testing of laminate structures, improved peel adhesion after aging at body temperature, reduced creep of elastic strands over time, and improved core stability in the final hygiene article, as compared to such articles without the disclosed silane-functionalized resins. The articles have improved chemical resistance and barrier properties, particularly with respect to exposure to fluids such as body fluids.

The Polymer composition also optionally comprises a polyolefin comprising two or more amorphous or crystalline homopolymers or copolymers of different monomers derived from α -monoolefins having from 2 to about 12 carbon atoms or from 2 to about 8 carbon atoms non-limiting examples of suitable olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-i-isopropene, 3-methyl-i-isopentene, 4-methyl-i-isopentene, 5-methyl-i-isohexene, and combinations thereof further suitable polyolefins include, but are not limited to, low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene (isotactic and syndiotactic), ethylene/propylene copolymers, polybutene, and olefin block copolymers further comprise a major weight portion of one or more olefin monomers and a minor amount of one or more non-olefin monomers, such as vinyl monomers including vinyl acetate, or diene monomers, EPDM, etc. typically, the polyolefin copolymers comprise less than about 30 weight% non-olefin monomers, less than 20 weight% or less than about 10 weight% non-olefin monomers, and copolymers available from molecu, including molecu, r.

Migration and volatilization of the low molecular weight components of currently commercially available thermoplastic resins used to modify elastomeric compounds, such as adhesives, thermoplastic elastomer (TPE) compounds, molding compounds, adhesives, and the like, can release unpleasant odors, volatiles, fog, product defects, reduce the cohesive strength of the product, reduce adhesion, and degrade performance over time.

TPE compositions incorporating the silane-functionalized or modified resins described herein are formed, in some embodiments, into a variety of articles well known to those of ordinary skill in the art. For example, TPE compositions are reprocessed, such as by pressing, compression molding, injection molding, calendering, thermoforming, blow molding, or extrusion into finished articles and embodiments thereof. When the TPE composition is reprocessed, the composition is typically heated to a temperature of at least the softening or melting point of the thermoplastic component of the TPE composition to facilitate further formation into the desired articles of various shapes and sizes. The end user of the TPE composition would benefit from the processing advantages described throughout this disclosure.

Any polymer known in the art can be mixed with the silane-functionalized resins described herein to produce compositions useful in various end products, such as adhesives, described herein. For example, in one embodiment, TPEs include, but are not limited to, block copolymer thermoplastic/elastomer blends and alloys, such as styrene block copolymers (TPE-S), metallocene-catalyzed polyolefin polymers and elastomers, and reactor-made thermoplastic polyolefin elastomers. Block copolymers include, but are not limited to, styrene block copolymers, olefin block copolymers, copolyester block copolymers, polyurethane block copolymers, and polyamide block copolymers. Thermoplastic/elastomer blends and alloys include, but are not limited to, thermoplastic polyolefins and thermoplastic vulcanizates. In some embodiments, the two-phase TPEs are combined with the disclosed modified thermoplastic resins in these end-use applications described herein. TPE-S copolymers include, but are not limited to, styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene/butylene-styrene block copolymer (SEBS), styrene-ethylene/propylene-styrene block copolymer (SEEPS), and styrene-isoprene-styrene block copolymer (SIS).

That is, in some embodiments, the disclosed modified silane resins are used to modify the properties of thermoplastic elastomer (TPE) compositions. Accordingly, embodiments include TPE compositions comprising at least one thermoplastic elastomer and at least one modified silane resin. Early versions of TPEs were thermoset rubbers, which could also be used in such compositions. TPEs are known to be used extensively in various industries to modify the properties of rigid thermoplastics to achieve improved impact strength. This is quite common for sheet goods and general purpose molded TPEs. Thus, the addition of the modified silane resins described herein to these compositions imparts further superior properties to these compositions and their standard end uses.

TPE compositions comprising the disclosed silane-functionalized resins incorporate any TPE known in the art. In one embodiment, the TPE includes at least one or a combination of block copolymers, thermoplastic/elastomer blends and alloys thereof, metallocene catalyzed polyolefin polymers and elastomers, and reactor made thermoplastic polyolefin elastomers. Block copolymers include, but are not limited to, styrene block copolymers, copolyester block copolymers, polyurethane block copolymers, and polyamide block copolymers. Thermoplastic/elastomer blends and alloys useful in such compositions include, but are not limited to, thermoplastic polyolefins and thermoplastic vulcanizates.

Various known TPE types, such as block copolymers and thermoplastic/elastomer blends and alloys, are known as two-phase systems. In such systems, the rigid thermoplastic phase is mechanically or chemically linked to the soft elastomer phase, resulting in a TPE with two-phase bonding properties.

Styrene block copolymers (TPE-S) are based on two-phase block copolymers with hard and soft segments. Exemplary styrene block copolymers include, but are not limited to, styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene/butylene-styrene block copolymer (SEBS), styrene-ethylene/propylene-styrene block copolymer (SEEPS), styrene-isoprene-styrene block copolymer (SIS). It is known that styrene-butadiene-styrene is commonly incorporated into compositions for footwear, adhesives, asphalt modification, and lower gauge seals and grips where chemical and aging resistance is not a concern for the end use. Monoprene, Tekron and Elexar products from Teknor Apex Company (Pawtucket, RI, US) are examples of fully formulated TPE-S compounds as hydrogenated styrene block copolymers. Styrene- [ ethylene- (ethylene/propylene) ] -styrene (SEEPS) block copolymers are commercially available from Kuraray co. Styrene-ethylene/butylene-styrene (SEBS) block copolymers are commercially available from kraton performance Polymers.

Table 1 provides the performance enhancements expected from incorporating silane-functionalized resins in various applications where such attributes may be advantageous. The capital "X" in table 1 represents attributes that may be possible by incorporating the silane-functionalized resins disclosed herein into the indicated compositions, and which are desirable in every application.

TABLE 1

Polymer modification applications performed on thermoplastic elastomers using the silane-functionalized resins include, but are not limited to, roofing applications (especially asphaltene modifiers in modified asphalt roofing), waterproofing membranes/compounds, underlayments, cable impregnation/filling compounds, caulks and sealants, polymer compounds/blends, membranes (e.g., cling film, TPE films, etc.), molded goods, rubber additives/processing aids, carpet backing (e.g., high performance precoats, thermoplastic compounds, etc.), wires and cables, power and hand tools, pens, air bag covers, grips and handles, seals and laminated articles such as paper lamination, water activation, hot melt adhesion, scrim reinforced tapes, and the like. When the silane-functionalized resins described herein are incorporated into such end-use applications, in some instances the silane-functionalized resin is the only resin in the composition. In other embodiments, the silane-functionalized resin is combined with other resins, elastomers/polymers, and/or additives. In such end-use embodiments, the above-described compositions comprise at least 1,2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60 and/or no more than 99, 95, 90, 85, 80, 75, 70, or 65 weight percent of at least one silane-functionalized resin.

Thus, other embodiments include Adhesives for Packaging, product assembly, woodworking, automotive assembly, and other applications consisting of ethylene vinyl acetate, ethylene butyl acrylate, semi-crystalline single site catalyzed (metallocene) polyolefins, amorphous α -olefins such as Ziegler-Natta catalyzed polymers, acrylic and styrene block copolymers, these products may exhibit improved adhesive and cohesive strength as determined by Peel Adhesion Failure Temperature (PAFT) testing, fiber tear testing, peel testing for adhered structures, Shear Adhesion Failure Temperature (SAFT) testing, IoPP (insulation of Packaging Profections) test T-3006Heat Stress Resistance of Hot Melt Adhesives and shear holding power.

In contrast to compositions that do not include the disclosed functionalized resins, particularly after heat aging, as measured by the test methods described above: compositions comprising the disclosed functionalized resins can act as a barrier to plasticizer migration as evidenced by changes in adhesion characteristics over time, as evidenced by any of PAFT, SAFT, peel, fiber tear, and shear retention at and above room temperature. Similarly, the compositions adhere well to difficult surfaces or substrates having migrating components (e.g., slip agents or plasticizers) as evidenced by the adhesion tests listed above, as compared to adhesives that do not contain the disclosed functionalized resins.

Investment casting wax compositions comprising the disclosed functionalized resins have excellent rheology to consistently produce parts, as evidenced by the rheology of the composition (stress-strain curve). The outstanding properties in terms of dimensional stability of the wax casting composition and stability of the casting composition during manufacture of the moulding are demonstrated by improved tolerances of the cast product.

In another embodiment, a composition comprising a functionalized resin comprises a heat seal coating and an adhesive that exhibit excellent heat resistance according to the peel adhesion test using ASTM F88 at temperatures near and above the sealing temperature.

In another embodiment, disclosed are sealant compositions comprising the disclosed functionalized resins that exhibit reduced sealing window fogging after aging as compared to the performance of sealants that do not comprise the disclosed functionalized resins.

Superior structural stability of sealants and gaskets and other rubber-based materials comprising the disclosed functionalized resins is demonstrated by dimensional stability measurements after compression or elongation as compared to sealants and gaskets and other rubber-based materials that do not comprise the disclosed functionalized resins.

The vibration and sound damping improvements of sealants, gaskets, structural adhesives, cement glues, asphalt and bituminous adhesives, thermoplastic elastomer (TPE) compounds and pressure sensitive adhesives can be measured by ASTM E756.

Also provided are compositions comprising the disclosed functionalized resins, such as adhesives containing asphalt, asphaltenes, or similar materials. Such compositions have a lower viscosity than compositions that do not comprise the disclosed functionalized resins, allowing for easier processing while exhibiting excellent adhesion to aggregate components, fillers, and substrates such as stone or cement as evidenced by tensile testing of adhered stone or cement samples. Such adhesives are useful in the production of bridge decking, flooring, road construction and roofing.

In another embodiment, pressure sensitive adhesives (PSAs, tapes, labels, graphic protective films, window films) comprising the disclosed functionalized resins are provided.

One problem associated with Pressure Sensitive Adhesives (PSAs) based on tackified elastomeric blends is the diffusion and migration of tackifiers and other substances from the adhesive composition or component of the article to the facestock or substrate. As a result, the facestock or substrate may become soiled over time and the structure may lose some of its adhesion. Such migration or bleeding of some or all of the components of the adhesive, compounded film, or other thermoplastic resin-containing composition may also leave a residue on the bonding surface, for example, when removed with a protective film, or may cause undesirable surface contamination, skin irritation, and the like. More critical for adhesive applications, compounds comprising thermoplastic resins, or multilayer films, migration or "bleed out" of chemical components to bonding interfaces such as adhesive-substrate or film-adhesive-nonwoven can result in immediate or delayed reduction or elimination of bond strength, damage to the bond or laminate, and/or reduction in adhesion with aging.

In some embodiments, the above-described composition comprising a silane-functionalized thermoplastic resin further comprises at least one polymer and from about 0 to about 75 weight percent of an unmodified thermoplastic tackifying resin. In another embodiment, the adhesive composition comprises at least one thermoplastic elastomer and at least one thermoplastic resin in addition to the silane-functionalized resin. The thermoplastic elastomer may be, for example, one or more of hydrogenated and/or non-hydrogenated styrene block copolymers, including but not limited to styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene/butylene-styrene block copolymer (SEBS), styrene- [ ethylene- (ethylene/propylene) ] -styrene block copolymer (SEEPS), and/or styrene-isoprene-styrene block copolymer (SIS). In another embodiment, the adhesive composition described herein has a viscosity of from about 50 to about 10,000 cP at 177 ℃, and a softening point of from about 60 ℃ to about 180 ℃, and is a suitable adhesive.

In composition embodiments described herein, the adhesive composition may comprise at least 1,2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60 and/or no more than 99, 95, 90, 85, 80, 75, 70, or 65 weight percent of at least one modified thermoplastic resin.

Exemplary polymeric components of the disclosed compositions include, but are not limited to, ethylene vinyl acetate copolymers, ethylene n-butyl acrylate copolymers, ethylene methyl acrylate copolymers, polyesters, neoprene, acrylics, urethanes, poly (acrylates), ethylene acrylic acid copolymers, polyetheretherketones, polyamides, styrene block copolymers, random styrene copolymers, hydrogenated styrene block copolymers, styrene butadiene copolymers, natural rubber, polyisoprene, polyisobutylene, random polypropylene, polyethylene including random 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-butene terpolymers, copolymers made from propylene, ethylene and various C4-C10 α -olefin monomers, polypropylene polymers, functional polyethylene compounds such as maleated polyolefins, butyl rubber, polyester copolymers, ethylene-propylene-butylene terpolymers, copolymers made from propylene, ethylene and various C4-C10 α -olefin monomers, copolymers such as ethylene-butadiene copolymers, ethylene-propylene-ethylene-butadiene copolymers, and/or ethylene-propylene-acrylate copolymers based on acrylic acid monomers (referred to as acrylic acid/butadiene copolymers).

In various embodiments, the compositions disclosed herein comprise polymers, tackifying resins, and other additives such as, but not limited to, oils, waxes, plasticizers, antioxidants, and fillers, depending on the end use application. In various embodiments, the composition comprises at least about 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50, and/or no more than 500, 450, 400, 350, or 300 parts of polymer, tackifying resin, and/or other additives per 100 parts of modified thermoplastic resin. For example, in one embodiment, the compositions disclosed herein comprise from about 50 to about 300 parts of elastomer per 100 parts of silane-functionalized resin.

As mentioned above, in some embodiments, the composition comprises additives that are particularly suited for specific end-use applications. For example, as mentioned above, if the adhesive is intended for use as a hot melt packaging adhesive, in this embodiment the composition will also contain a wax. In some embodiments, the adhesive composition comprises at least 1,2, 5, 8, or 10 and/or no more than 40, 30, 25, or 20 weight percent of at least one wax. In another embodiment, the compositions described herein comprise from about 1 to about 40, from about 5 to about 30, from about 8 to about 25, or from about 10 to about 20 weight percent of at least one wax. Suitable waxes include, but are not limited to, microcrystalline waxes, paraffin waxes, waxes produced by the fischer-tropsch process, vegetable waxes, functionalized waxes (maleated waxes, fumarated waxes, or waxes having functional groups), and the like. In such embodiments, the wax is present in the composition in an amount of about 10 to about 100 parts wax per 100 parts polymer component.

In embodiments of Pressure Sensitive Adhesive (PSA) compositions, such as adhesives used in tapes, adhesives, and labels, as well as in nonwoven applications of the adhesive compositions, various oils are added to the adhesive composition. In one embodiment, the adhesive composition comprises at least about 1,2, 5, 8, or about 10 and/or no more than about 40, 30, 25, or about 20 weight percent of at least one processing oil. In another embodiment of the pressure sensitive adhesive composition, the adhesive composition comprises from about 2 to about 40, from about 5 to about 30, from about 8 to about 25, or from about 10 to about 20 weight percent of at least one processing oil. Processing oils include, but are not limited to, mineral oils, naphthenic oils, paraffinic oils, aromatic oils, castor oils, rapeseed oils, triglyceride oils, and combinations thereof. Processing oils also include extender oils commonly used in various pressure sensitive adhesive compositions. In another embodiment, the adhesive composition does not comprise a processing oil.

In another embodiment of the composition, one or more plasticizers are added to the adhesive composition, such as, but not limited to, phthalates (e.g., dibutyl phthalate and dioctyl phthalate), benzoates, terephthalates, and chlorinated paraffins. In one embodiment, the adhesive composition comprises at least about 0.5, 1,2, or about 3 and/or no more than about 20, 10, 8, or about 5 weight percent of at least one plasticizer. In another embodiment, the adhesive composition comprises from about 0.5 to about 20, from about 1 to about 10, from about 2 to about 8, or from about 3 to about 5 weight percent of at least one plasticizer. Other exemplary plasticizers include Benzoflex^TMAnd Eastman 168^TM(Eastman Chemical Company,Kingsport, TN, US)。

In other embodiments, the composition incorporating one or more silane-functionalized resins further comprises at least about 0.1, 0.5, 1,2, or about 3 and/or no more than about 20, 10, 8, or about 5 weight percent of at least one antioxidant. Any antioxidant known to one of ordinary skill in the art may be used in the adhesive compositions disclosed herein. Non-limiting examples of suitable antioxidants include aminic antioxidants such as alkyl diphenylamines, phenyl naphthylamines, alkyl or aralkyl substituted phenyl naphthylamines, alkylated p-phenylenediamines, tetramethyl diaminodiphenylamine and the like; and hindered phenol compounds such as 2, 6-di-tert-butyl-4-methylphenol; 1,3, 5-trimethyl-2, 4, 6-tris (3',5' -di-tert-butyl-4 ' -hydroxybenzyl) benzene; tetra [ (methylene (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) ] methane, such as IRGANOX 1010 (BASF Corp., LA, US), octadecyl 3, 5-di-tert-butyl-4-hydroxycinnamate, such as IRGANOX 1076 (BASF Corp., LA, US), and combinations thereof when used, the antioxidant can be in the composition in an amount of greater than about 0 to about 1 weight percent, about 0.05 to about 0.75 weight percent, or about 0.1 to about 0.5 weight percent, based on the total weight of the composition.

In another embodiment of the composition, the composition comprises one or more fillers such as, but not limited to, carbon black, calcium carbonate, clay and other silicates, titanium oxide, and zinc oxide. In another embodiment of the composition, the composition comprises at least about 10, 20, 30, or about 40 and/or no more than about 90, 80, 70, or about 55 weight percent of at least one filler. In another embodiment, the composition comprises from about 1 to about 90, from about 20 to about 80, from about 30 to about 70, or from about 40 to about 55 weight percent of at least one filler. In some embodiments, silica is added as a filler in addition to or in place of silicates present in the clay and fly ash. That is, silica, a combination of silicon (silica) and oxygen (SiO)₂) Manufactured by known methods and commercially available as a white powder in pure or relatively pure form. The silica typically formed by precipitation is a synthetic crystalline amorphous form of silica, derived from quartz sand. In some embodiments, such silicas and silicates are added to the composition as fillers. In addition to organosilanes used as coupling agents, silica is often incorporated into rubber compositions used in the manufacture of articles such as seals, cables, profiles, belts and hoses. When synthetic (pure) silica is used together as filler and an organosilane as coupling agent, a silica-silane system results, which is commonly used or incorporated in industrial rubber articles where high reinforcement is required and the possibility of making white or colored products. In such background and embodiments, silica is incorporated as a filler to improve tear resistance, and in some embodiments, the silica-silane system reduces heat build-up. (see, Uhrland, S., "Silica", Encyclopedia of chemical Technology, Kirk-Othmer, John Wiley&Sons, inc., 2006). In contrast, clay consists of fine-grained clay minerals and is essentially a combination of silica, alumina, and water, to associate with the alkali metal andalkaline earth elements produce hydrated aluminum silicates. Such clays are the raw materials present in clay deposits of different composition and particle size. Clays are commonly used as fillers in sealants and adhesives. For example, sodium bentonite is incorporated as a filler in sealants, which imparts water resistance due to high swelling capacity and the ability to block water movement. The clay incorporated into the binder is in some cases in the form of attapulgite which improves viscosity under shear. In other embodiments, the incorporation of kaolin fillers can affect the viscosity of the composition. Thus, there are various hydrated aluminum silicates present in clays that differ from silica in that they are synthetic and, in some embodiments, also incorporated as fillers in the compositions. (see, supra, Murray, H.H., "Clays, Uses" and "Clays, Survey").

Tackifying resins added to the composition in the embodiments include, but are not limited to, cycloaliphatic hydrocarbon resins, C5 hydrocarbon resins, C5/C9 hydrocarbon resins, aromatic modified C5 resins, C9 hydrocarbon resins, pure monomer resins, such as copolymers of styrene with α -methylstyrene, vinyltoluene, p-methylstyrene, indene and methylindene, DCPD resins, dicyclopentadiene based/containing resins, cyclopentadiene based/containing resins, terpene phenolic resins, terpene styrene resins, rosin esters, esters of modified rosins, liquid resins of fully or partially hydrogenated rosin, fully or partially hydrogenated rosin esters, fully or partially hydrogenated modified rosin resins, fully or partially hydrogenated rosin alcohols, fully or partially hydrogenated C5 resins, fully or partially hydrogenated C5/C9 resins, fully or partially hydrogenated d resins, fully or partially hydrogenated DCPD resins, fully or partially hydrogenated modified rosin resins, fully or partially hydrogenated dicyclopentadiene based resins, fully or partially hydrogenated styrene based copolymers, fully hydrogenated C5/C9 resins, fully or fully hydrogenated styrene based on hydrogenated styrene.

In some embodiments, the compositions described herein comprise other conventional plastic additives in an amount sufficient to obtain the desired processing or performance characteristics of the adhesive. The amount should not waste additives nor impair the processing or performance of the adhesive. Those skilled in the art of thermoplastic compounding will be able to select from many different types of Additives for inclusion in the compounds described herein without undue experimentation, with reference to articles such as Plastics Additives Database (2004) by Plastics Design Library (www.elsevier.com). Non-limiting examples of optional additives include adhesion promoters; biocides (antibacterial, fungicidal and mildewcides), antifogging agents; an antistatic agent; binders, foaming agents and foaming agents; a dispersant; fillers and extenders; fire retardant and smoke suppressant; an impact modifier; an initiator; a lubricant; mica; pigments, colorants, and dyes; oils and plasticizers; a processing aid; a release agent; silanes, titanates and zirconates; slip and anti-tack agents; stabilizers (e.g., Irganox 1010 and Irganox 1076, BASF Corporation, LA, US); a stearate; an ultraviolet light absorber; a viscosity modifier; a wax; and combinations thereof. Antioxidants are particularly useful with these compounds to provide additional durability.

In one embodiment, such compositions are made by blending a silane-functionalized resin with an elastomer (at least one polymer) to form an adhesive. That is, in one embodiment, the adhesive compositions described herein are prepared by combining the silane-functionalized resin, elastomer, and additives using conventional techniques and equipment. As one non-limiting exemplary embodiment, the components of the compositions described herein are blended in a mixer such as a Sigma blade mixer, a plasticator, a Brabender mixer, a twin screw extruder, and/or an in-can blending tank (pint tank). In another embodiment, the composition is formed into a desired form, such as a tape or sheet, by suitable techniques including, for example, extrusion, compression molding, calendering, or roll coating techniques (gravure, reverse roll, etc.). In some embodiments, the compositions described herein are applied using curtain coating, slot die coating, or sprayed through different nozzle configurations at different speeds using typical application equipment.

In another embodiment, the compositions described herein are applied to a substrate by melting the composition and then using conventional hot melt adhesive application equipment recognized in the art to coat the substrate with the composition. Substrates include, for example, textiles, fabrics, paper, glass, plastics, and metallic materials. Typically, about 0.1 to about 100 g/m²The adhesive composition of (a) is applied to a substrate.

In some embodiments, the silane-functionalized resins described herein are incorporated into various types of compositions including, but not limited to, hot melt or solvent-based pressure sensitive adhesives, such as tapes, labels, adhesives, HVAC, and the like; hot melt nonwoven adhesives, such as those used in the construction industry, elastic attachment, or stretch; and hot melt packaging adhesives. Additionally, in another embodiment, the silane-functionalized resins described herein are incorporated into different polymer systems as explained above to provide physical and chemical properties that are excellent in processability, stability, thermal properties, barrier properties, viscoelasticity, vibration damping, rheology, volatility, fogging profile, and/or adhesion and mechanical properties of such polymer systems. In addition, the silane-functionalized resins described herein enhance various physical and chemical properties in thermoplastic elastomer applications, such as roofing applications (construction), adhesives, sealant applications, cable impregnation/filling applications, and tire elastomer applications, for example, tread compositions, sidewalls, innerliners, innertubes, and various other pneumatic tire components.

Although the foregoing discussion has been primarily directed to adhesive applications incorporating the silane-functionalized resins described herein, these principles can generally be extended and applied to other polymer compositions containing the silane-functionalized resins for use in a variety of end products. For example, polymer modification applications incorporating the silane-functionalized resins described herein include, but are not limited to, roofing applications (such as asphaltene modifiers in modified asphalt roofing), waterproofing membranes/compounds, underlayments, cable impregnation/filling compounds, caulks and sealants, structural adhesives, polymer compounds/blends, films (e.g., cling films, TPE films, biaxially oriented polypropylene (BOPP) films, and the like), molded articles, rubber additives/processing aids, carpet backing (e.g., high performance precoats, thermoplastic compounds, and the like), wire and cable, power and hand tools, pen grips, air bag covers, grips and handles, seals and laminates, such as paper lamination, water activation, hot melt adhesion, reinforced scrim tape, and the like. When incorporated into these various end-use applications, in some embodiments, the silane-functionalized resin is the only resin in the composition. In other embodiments, the silane-functionalized resin is combined with other resins, elastomers/polymers, and/or additives. In such combined resin applications, the aforementioned compositions comprise at least about 1,2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or about 60 and/or no more than about 99, 95, 90, 85, 80, 75, 70, or about 65 weight percent of at least one silane-functionalized resin.

Thus, in various embodiments, one or more of the silane-functionalized resins described herein are incorporated into a hot melt adhesive composition. Thus, according to one or more embodiments, the adhesive comprises at least about 1, 5, 10, 20, 30, 40, 50, or 60 and/or no more than about 95, 90, 80, 70, or 60 weight percent (wt%) silane-functionalized resin or mixtures thereof. Further, in other embodiments, the binder comprises in the range of about 1 to 95, 5 to 90, 10 to 80, 20 to 70, 30 to 60, or 40 to 60 weight percent of the modified thermoplastic resin described herein, or mixtures thereof. In certain additional embodiments, the adhesive consists entirely of one or more of the silane-functionalized resins described herein. In addition, depending on the desired end use, in certain embodiments, these hot melt adhesives also include various additives, such as polymers, tackifiers, processing oils, waxes, antioxidants, plasticizers, pigments, and/or fillers.

In various embodiments, the adhesive comprises at least about 5, 10, 20, 30, or 40 and/or no more than about 95, 90, 80, 70, or 55 weight percent of at least one thermoplastic tackifying resin that is different from the silane-functionalized resins described herein. Further, in other embodiments, the adhesive comprises in the range of about 10 to 90, 20 to 80, 30 to 70, or 40 to 55 weight percent of at least one resin other than the silane-functionalized resin described herein. Contemplated thermoplastic tackifying resins include neat monomer thermoplastic resins (PMR), C5 thermoplastic resins, C5/C9 thermoplastic resins, C9 thermoplastic resins, terpene thermoplastic resins, indene-coumarone (IC) thermoplastic resins, dicyclopentadiene (DCPD) thermoplastic resins, hydrogenated or partially hydrogenated neat monomer (PMR) thermoplastic resins, hydrogenated or partially hydrogenated C5 thermoplastic resins, hydrogenated or partially hydrogenated C5/C9 thermoplastic resins, hydrogenated or partially hydrogenated C9 thermoplastic resins, hydrogenated or partially hydrogenated dicyclopentadiene (DCPD) thermoplastic resins, terpene thermoplastic resins, modified indene-coumarone (IC) thermoplastic resins, or mixtures thereof.

In various embodiments, the adhesive comprises at least about 10, 20, 30, 40, 50, or 60 and/or no more than about 90, 80, 70, or 60 weight percent of at least one tackifier in addition, in such embodiments, the adhesive comprises at least one tackifier in the range of about 10 to 90, 20 to 80, 30 to 70, or about 40 to 60 weight percent suitable tackifiers contemplated herein include, for example, cycloaliphatic hydrocarbon resins, C5 hydrocarbon resins, C5/C9 hydrocarbon resins, aromatic modified C5 resins, C9 hydrocarbon resins, pure monomer resins such as copolymers of styrene with α -methylstyrene, vinyltoluene, p-methylstyrene, indene, methylindene, C5 resins and C9 resins, terpene phenolic resins, terpene resins, rosin esters, modified rosin esters, fully or partially hydrogenated liquid resins, fully or partially hydrogenated rosin esters, fully or partially hydrogenated modified rosin resins, fully or partially hydrogenated thermoplastic resins, fully or partially hydrogenated rosin alcohols, fully or partially hydrogenated rosin resins, thermoplastic resins such as hydrogenated rosin esters, fully or partially hydrogenated rosin esters, thermoplastic resins of hydrogenated soybean, hydrogenated rosin (IC) 5, hydrogenated rosin esters, hydrogenated soybean, hydrogenated thermoplastic resins, hydrogenated soybean, soybeanHydrogenated C9 resin; fully or partially hydrogenated pure monomer resins; fully or partially hydrogenated C5/cycloaliphatic resin; fully or partially hydrogenated C5/cycloaliphatic/styrene/C9 resin; fully or partially hydrogenated cycloaliphatic resins; and combinations thereof. Exemplary commercial hydrocarbon resins include Regalite^TMHydrocarbon resins (eastman chemical co., Kingsport, TN, US).

In various embodiments, the adhesive comprises at least about 1,2, 5, 8, or 10 and/or no more than about 40, 30, 25, or 20 weight percent of at least one processing oil. Further, in such embodiments, the binder comprises at least one processing oil in the range of about 2 to 40, 5 to 30, 8 to 25, or about 10 to 20 weight percent. Suitable processing oils are those known in the art and include, for example, mineral oil, naphthenic oil, paraffinic oil, aromatic oil, castor oil, rapeseed oil, triglyceride oil, or combinations thereof. As will be understood by those skilled in the art, the processing oil may also include extender oils commonly used in adhesives. The use of oil in adhesives is desirable in some cases if the adhesive is to be used as a Pressure Sensitive Adhesive (PSA) to produce tapes or labels, or as an adhesive to bond nonwoven articles. In certain further embodiments, the adhesive does not comprise a processing oil.

In various embodiments, the adhesive comprises at least about 1,2, 5, 8, or 10 and/or no more than about 40, 30, 25, or 20 weight percent of at least one wax. Further, in such embodiments, the adhesive comprises at least one wax in the range of about 1 to 40, 5 to 30, 8 to 25, or 10 to 20 weight percent. Suitable waxes may include those known in the art, for example, microcrystalline waxes, paraffin waxes, waxes produced by the fischer-tropsch process, functionalized waxes (maleated waxes, fumarated waxes, or waxes having functional groups, etc.), and vegetable waxes. If the adhesive is to be used as a hot melt packaging adhesive, it may be desirable in some cases to use a wax in the adhesive. In certain embodiments, the adhesive does not comprise a wax.

In various embodiments, the adhesive comprises at least about 0.1, 0.5, 1,2, or 3 and/or no more than about 20, 10, 8, or 5 weight percent of at least one antioxidant. Further, in such embodiments, the adhesive comprises at least one antioxidant in the range of about 0.1 to 20, 1 to 10, 2 to 8, or 3 to 5 weight percent. In other embodiments, the adhesive does not comprise an antioxidant.

In various embodiments, the adhesive comprises at least about 0.5, 1,2, or 3 and/or no more than about 20, 10, 8, or 5 weight percent of at least one plasticizer. Further, in such embodiments, the adhesive comprises at least one plasticizer in the range of about 0.5 to 20, 1 to 10, 2 to 8, or 3 to 5 weight percent. Suitable plasticizers are those known in the art and include, for example, dibutyl phthalate, dioctyl phthalate, chlorinated paraffins, and phthalate-free plasticizers. Commercial plasticizers include, for example, Benzoflex and Eastman 168 ™ plasticizers (Eastman Chemical Co., Kingsport, TN, US).

In various additional embodiments, the adhesive comprises at least about 10, 20, 30, or 40 and/or no more than about 90, 80, 70, or 55 weight percent of at least one filler. Further, in such embodiments, the adhesive comprises at least one filler in the range of about 1 to 90, 20 to 80, 30 to 70, or 40 to 55 weight percent. Suitable fillers are those known in the art and include, for example, carbon black, clays and other silicates, calcium carbonate, titanium oxide, zinc oxide, or combinations thereof.

Rubber composition comprising silane-functional resin

Also disclosed are various rubber compositions useful, for example, in automotive parts, such as, but not limited to, tires and tire parts, automotive belts, hoses, brakes, and the like, as well as non-automotive and/or mechanical devices, including industrial rubber articles, such as belts, as in conveyor belts, such as, for example, strips, brakes, and hoses or pipes, and the like, and articles of apparel, such as, but not limited to, shoes, boots, slippers, and the like, that incorporate the disclosed functionalized resins. The disclosed silane-functionalized resins can be used as processing aids during mixing of rubber formulations by associating with the silica surface. The functionalization of the silica surface can be compared to other commercially available silanes used for rubber compounding (fig. 2A), except that the embodiments involve one or more covalent bonds through polar group-containing bonds(s)Silane functionality attached to the polymer or resin structure (fig. 2B). In fig. 2A, the element 110 corresponds to a polymer, and the element 100B corresponds to a resin. This is a theoretical description of the normal arrangement present in such compositions using non-functionalized resins. In fig. 2B, again, element 110 corresponding to a polymer is shown, as well as element 100B corresponding to a resin, and element 100A corresponding to a linker, as contemplated herein. That is, in FIG. 2B, elements 100A and 100B together are in a schematic diagram equivalent to formula I, where the "resin" in formula I corresponds to portion 100B and the remainder of the equation of formula I, i.e., - [ Z ]_k-X_n-R¹-(CH₂)_m-Si(R²)_p]_qCorresponding to element 100A in fig. 2B.

Thus, rubber compositions are disclosed that comprise an elastomer, a filler, and the silica-functionalized resins disclosed herein. The elastomer may be one or more of natural rubber, polyisoprene, styrene-butadiene rubber, polybutadiene, halobutyl rubber and nitrile rubber, or a functionalized rubber grade, or rubber blends thereof. In another particular embodiment, the halobutyl rubber is bromobutyl rubber, chlorobutyl rubber, functionalized rubber grade, or mixtures thereof. When used in a tire, the main rubber component includes various polymers such as, but not limited to, polyisoprene (synthetic or natural), styrene-butadiene copolymers or butadiene polymers, and the like. Such rubbery polymers may contain various modifications and/or functionalizations at the end of the chain or laterally along the polymer chain. These modifications may comprise various standard moieties such as, but not limited to, hydroxyl-and/or ethoxy-and/or epoxy-and/or siloxane-and/or amine-and/or aminosiloxane-and/or carboxyl-and/or phthalocyanine-and/or silane-sulfide groups, and/or combinations thereof. Other modifications known to those skilled in the art, such as metal atoms, can also be included in the rubber polymers used to make the disclosed tires and other rubber-containing components disclosed herein.

The rubber mixtures according to the present disclosure also comprise from 5 to 80 phr, preferably from 5 to 49 phr, particularly preferably from 5 to 30phr and more particularly preferably from 5 to 20 phr, of at least one further diene rubber.

In this case, the at least one other rubber is one or more of the following rubbers: natural polyisoprene and/or synthetic polyisoprene and/or butadiene rubber and/or solution polymerized styrene-butadiene rubber and/or emulsion polymerized styrene-butadiene rubber and/or liquid rubber with a molecular weight Mw of more than 20,000 g/mol and/or halobutyl rubber and/or polynorbornene and/or isoprene-isobutylene copolymer and/or ethylene-propylene-diene rubber and/or nitrile rubber and/or chloroprene rubber and/or acrylate rubber and/or fluoro rubber and/or silicone rubber and/or polysulfide rubber and/or epichlorohydrin rubber and/or styrene-isoprene-butadiene terpolymer and/or hydrated acrylonitrile butadiene rubber and/or isoprene-butadiene copolymer and/or hydrated styrene- Butadiene rubber.

In particular, nitrile rubber, hydrated acrylonitrile butadiene rubber, chloroprene rubber, butyl rubber, halobutyl rubber or ethylene-propylene-diene rubber are used for producing industrial rubber articles such as strips, belts and hoses.

In another embodiment, the other diene rubber is one or more of synthetic polyisoprene and natural polyisoprene and polybutadiene. Preferably, the other diene rubber is at least natural polyisoprene. This allows particularly advantageous processability (extrudability, miscibility, etc.) of the rubber mixtures to be achieved.

According to a further embodiment of the invention, the rubber mixture contains from 10 to 70 phr of a conventional solution-polymerized styrene-butadiene rubber having a glass transition temperature of from-40 to +10 ℃ (high Tg SSBR) and from 10 to 70 phr of a styrene-butadiene rubber having a Tg of from-120 to-75 ℃, preferably from-110 to-75 ℃, particularly preferably from-110 to-80 ℃ and most particularly preferably from-87 to-80 ℃, wherein in this embodiment the rubber preferably has a styrene content of from 1 to 12% by weight, particularly preferably from 9 to 11% by weight and most particularly preferably from 10 to 11% by weight.

The rubber mixture may also contain at least one other diene rubber, in particular natural and/or synthetic polyisoprene.

When used in tire mixtures, the resins described above may be used as the base resin to be functionalized. The polar linking group has increased bonding strength to the reactive sites of the filler material, i.e., to the hydroxyl groups of the silica or to the reactive surface sites of other fillers, by providing corresponding functional groups that are compatible with the reactive centers of the other fillers. Thus, the present disclosure is not limited to silica and other fillers such as carbon black as filler materials.

The disclosed silane-functionalized resins can be incorporated into rubber compounds by various methods known to those skilled in the art. For example, from 1 to 100 mole percent of the monomers, from 2 to 70 mole percent of the monomers, from 5 to 50 mole percent of the monomers bearing said functional groups as endcaps and/or pendant functionalization may be incorporated into the rubber mixture. The amount of functionalized resin in the rubber mixture may be 5 to 400phr, 10 to 375 phr, 10 to 350 phr, 10 to 325 phr, 10 to 300 phr, 10 to 275 phr, 10 to 250 phr, 10 to 225phr, 10 to 200 phr, 10 to 175 phr, 10 to 150 phr, 10 to 125phr, or 10 to 100 phr. The rubber mixture may additionally comprise an unfunctionalized resin. In addition, a mixture of functionalized and unfunctionalized resins may be incorporated into the rubber mixture. The total resin content comprising unfunctionalized resin and functionalized resin may be 5 to 400phr, 5 to 350 phr, 10 to 300 phr, 10 to 275 phr, 10 to 250 phr, 10 to 225phr, 10 to 200 phr, 10 to 175 phr, 10 to 150 phr, 10 to 125phr, or 10 to 100phr, i.e., the highly lateral functionalized resin may be incorporated into the rubber mixture to obtain a phr value of 5 to 50 upon dilution. Likewise, a mixture of the end-capping and side-functionalizing resins may be incorporated into the rubber mixture by adding the desired amount to the rubber mixture to achieve the desired phr.

According to another embodiment, the solution polymerized styrene-butadiene rubber may be present in the rubber mixture in an amount of 5 to 50 phr, 20 to 50 phr, or even 30 to 40 phr. The rubber mixtures of the present disclosure comprise from 20 to 250 phr, preferably from 30 to 150 phr, particularly preferably from 30 to 85 phr, of at least one filler. The filler may be one or more polar or non-polar fillers such as silica, carbon black, aluminosilicates, chalk, starch, magnesium oxide, titanium dioxide and/or rubber gels, or mixtures thereof. In addition, Carbon Nanotubes (CNTs) including Hollow Carbon Fibers (HCFs) and modified CNTs including one or more functional groups such as hydroxyl, carboxyl, or carbonyl groups may also be used as filler materials. In addition, graphite and graphene as well as "carbon-silica dual phase fillers" may be used as filler materials. Any type of carbon black known to those skilled in the art may be used herein.

In some embodiments, the rubber mixture contains carbon black as the sole filler or as the predominant filler, i.e., the amount of carbon black is significantly greater than the amount of any other filler present. If another filler is present in addition to the carbon black, the additional filler is preferably silica. Thus, it is also conceivable that the rubber mixtures of the invention comprise similar amounts of carbon black and silica, for example a combination of from 20 to 100phr of carbon black and from 20 to 100phr of silica. For example, the ratio of carbon black to silica can be any ratio of about 1:150 to 100: 20.

In some embodiments, the rubber mixture comprises silica as the sole filler or as the predominant filler, i.e., the amount of silica is significantly greater than the amount of any other filler present.

Thus, for application in vehicle tyres, particularly good rolling resistance index (resilience at 70 ℃) and tear properties are obtained.

When carbon black is present as a filler, preferably, the amount of carbon black in the rubber mixture is 1 to 150 phr, 2 to 100phr, 2 to 90 phr, 2 to 80 phr, 2 to 70 phr, 2 to 60 phr, 2 to 50 phr, 2 to 40 phr, 2 to 30phr, or more preferably 2 to 20 phr. However, it is preferred to use carbon blacks which have an iodine absorption value of from 30 to 180 g/kg, preferably from 40 to 180 g/kg, particularly preferably from 40 to 130 g/kg, according to ASTM D1510 and a DBP value of from 80 to 200 ml/100 g, preferably from 90 to 200 ml/100 g, particularly preferably from 90 to 150 ml/100 g, according to ASTM D2414.

The silica may be silica known to those skilled in the art to be suitable as a filler for tire rubber compounds. For example, one non-limiting embodiment includesFinely divided precipitated silicas having nitrogen surface areas (BET surface areas) (in accordance with DIN ISO9277 and DIN 66132) of from 35 to 350 m²A/g, preferably from 35 to 260 m²Per g, particularly preferably from 100 to 260 m²Per g, and most particularly preferably from 130 to 235 m²(ii)/g and a CTAB surface area (according to ASTM D3765) of 30 to 400 m²A/g, preferably from 30 to 250 m²Per g, particularly preferably from 100 to 250 m²Per g, and most particularly preferably from 125 to 230m²(ii) in terms of/g. Such silicas, when used, for example, in rubber mixtures for tire treads, give rise to particularly advantageous physical properties of vulcanizates. This may also provide advantages in the processing of the mixture by reducing the mixing time while maintaining the same product properties, which results in improved productivity. As silicas, it is possible to use, for example, silicas of the type Ultrasil VN3 (Evonik Industries AG, Essen, Germany) and highly dispersible silicas such as the above-mentioned HD silicas (e.g. Zeosil 1165 MP Rhodia-Solvay International Chemical Group, Brussels, Belgium).

To improve processability and to incorporate the silica and other polar fillers present in some embodiments into the diene rubber, silane coupling agents are used in various embodiments of the rubber compound. In such embodiments, one silane coupling agent or a plurality of different silane coupling agents in combination with each other are used. Thus, in some embodiments, the rubber compound contains a mixture of various silanes. The silane coupling agent reacts with surface silanol groups of silica or other filler polar groups such as the polar fillers disclosed above during mixing (in situ) of the rubber or rubber mixture, or even prior to adding the filler to the rubber as a pretreatment (pre-modification). In such embodiments, the silane coupling agent is any silane coupling agent known to those skilled in the art to be suitable for use in the disclosed rubber compounds. Non-limiting examples of conventional coupling agents are bifunctional organosilanes having at least one alkoxy, cycloalkoxy or phenoxy group as leaving group on the silicon atom and having a group which, after cleavage, can optionally react chemically with the double bond of the polymerThe group serves as the other functional group. In some embodiments, the latter group, for example, constitutes the following chemical group: SCN, -SH, -NH₂or-S_γ- (wherein γ is 2 to 8).

Silane coupling agents contemplated for use in such embodiments include, for example, 3-mercaptopropyltriethoxysilane, 3-thiocyanato-propyl-trimethoxysilane, or 3,3 '-bis (triethoxysilylpropyl) -polysulfide having 2 to 8 sulfur atoms, such as 3,3' -bis (triethoxysilylpropyl) tetrasulfide (TESPT), the corresponding disulfide (TESPD), or mixtures of sulfides having 1 to 8 sulfur atoms with varying amounts of the various sulfides. TESPT can also be added, for example, as a mixture with industrial carbon black (X50S, Evonik Industries AG, Essen, Germany).

In another embodiment, silane mixtures are used which contain up to 40 to 100% by weight of disulfide, particularly preferably 55 to 85% by weight of disulfide and most particularly preferably 60 to 80% by weight of disulfide. Mixtures of this type, as described for example in U.S. Pat. No. 8,252,863, are obtainable for example from Si 261 ® (Evonik Industries AG, Essen, Germany). Blocked mercaptosilanes, such as those known from WO 99/09036, may also be used as silane coupling agents. Silanes may be used, such as U.S. patent No. 7,968,633; 7,968,634, respectively; 7,968,635, respectively; and 7,968,636, and U.S. patent application publication No. 20080161486; 20080161462, respectively; and 20080161452, or any combination thereof. Suitable silanes are also, for example, those sold under the name NXT by Momentive Inc. in the U.S. in different variants, or those sold under the name VP Si 363 by Evonik Industries, Inc.

Furthermore, the rubber compound may comprise Carbon Nanotubes (CNTs), including discrete CNTs, so-called Hollow Carbon Fibers (HCFs), and modified CNTs containing one or more functional groups such as hydroxyl, carboxyl, and carbonyl groups.

Graphite, graphene and so-called "carbon-silica dual-phase fillers" are also suitable as fillers.

Furthermore, the rubber mixtures may comprise further polar fillers, for example aluminosilicates, chalk, starch, magnesium oxide, titanium dioxide or rubber gels.

In one embodiment, the rubber mixture is free of other fillers, i.e., in such an embodiment, the rubber mixture comprises 0phr of any other fillers. Thus, in the described embodiment, no second filler need be added.

For the purposes of this disclosure, zinc oxide is not considered a filler.

In one embodiment, the rubber mixture comprises 0 to 70 phr, 0.1 to 60 phr, or 0.1 to 50 phr of at least one plasticizer. These plasticizers include one or more of all plasticizers known to the person skilled in the art, such as aromatic, naphthenic or paraffinic mineral oil plasticizers, for example MES (mild extraction solvates) or TDAE (treated distilled aromatic extracts), rubber-liquid (RTL) oils or biomass-liquid (BTL) oils, factice, plasticizing resins or liquid polymers (such as liquid BR), the average molecular weight of which (determined by Gel Permeation Chromatography (GPC) on the basis of BS ISO11344: 2004) is between 500 g/mol and 20000 g/mol. If liquid polymers are used as plasticizers in the rubber mixtures according to the invention, these plasticizers are not included as rubber when calculating the composition of the polymer matrix.

In embodiments where mineral oil is used, the mineral oil is selected from one or more of DAE (distilled aromatic extract) and/or RAE (residual aromatic extract) and/or TDAE (treated distilled aromatic extract) and/or MES (solvent for mild extraction) and/or naphthenic and/or paraffinic oils.

Furthermore, the rubber mixtures disclosed herein may comprise usual additives in usual parts by weight. These additives include:

a) antioxidants, for example N-phenyl-N ' - (1, 3-dimethylbutyl) -p-phenylenediamine (6PPD), N ' -diphenyl-p-phenylenediamine (DPPD), N ' -ditolyl-p-phenylenediamine (DTPD), N-isopropyl-N ' -phenyl-p-phenylenediamine (IPPD), N ' -bis (1, 4-dimethylpentyl) -p-phenylenediamine (77PD) and 2,2, 4-trimethyl-1, 2-dihydroquinoline (TMQ),

b) activators, such as zinc oxide and fatty acids (e.g., stearic acid),

c) the amount of wax is such that,

d) functionalized resins and non-functionalized resins, particularly adhesive tackifying resins, such as rosin and the like,

e) filling aids, such as 2,2' -dibenzamidodiphenyl disulfide (DBD), and

f) processing aids, for example fatty acid salts, such as zinc soaps, fatty acid esters and derivatives thereof.

In particular, in the use of the rubber mixtures disclosed herein for the inner parts of tires or industrial rubber articles which are in direct contact with the reinforcing carrier present, suitable adhesive systems, usually in the form of adhesive tackifying resins, are usually also added to the rubber.

The proportion of further additives contained in the total amount is from 3 to 150 phr, preferably from 3 to 100phr and particularly preferably from 5 to 80 phr.

The proportions of the other additives contained in the total also comprise from 0.1 to 10phr, preferably from 0.2 to 8 phr and particularly preferably from 0.2 to 4 phr of zinc oxide (ZnO).

The zinc oxide may be of any type known to those skilled in the art, such as ZnO particles or powder. In general, conventionally used zinc oxide exhibits less than 10m²BET surface area in g. However, BET surface areas of 10 to 60 m may also be used²Per g of so-called nano zinc oxide.

Vulcanization is performed using a vulcanization accelerator in the presence of sulfur or a sulfur donor, some of which are also capable of acting as sulfur donors. In the final mixing step, the above amounts of sulfur or sulfur donor and one or more accelerators are added to the rubber mixture. Here, the accelerator is one or more of a thiazole accelerator and/or a mercapto accelerator and/or a sulfenamide accelerator and/or a thiocarbamate accelerator and/or a thiuram accelerator and/or a thiophosphate accelerator and/or a thiourea accelerator and/or a xanthate accelerator and/or a guanidine accelerator.

Sulfenamide accelerators selected from the group consisting of N-cyclohexyl-2-benzothiazolesulfenamide (CBS) and/or N, N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS) and/or N-tert-butyl-2-benzothiazolesulfenamide (TBBS) may be used.

Suitable accelerators include, for example, accelerators selected from the group consisting of N-cyclohexyl-2-benzothiazole sulfenamide (CBS) and/or N, N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS), N-tert-butyl-2-benzothiazole sulfenamide (TBBS), mercaptobenzothiazole, tetramethylthiuram disulfide, benzothiazole disulfide, diphenylguanidine, zinc dithiocarbamate, alkylphenol disulfide, zinc butylxanthate, N-dicyclohexyl-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylenebenzothiazole-2-sulfenamide, N-diphenylthiourea, dithiocarbamoyl sulfenamide, N-diisopropylbenzothiazole-2-sulfenamide, zinc-2-mercaptotoluimidazole, dithiobis (N-methylpiperazine), dithiobis (N- β -hydroxyethylpiperazine), dithiobis (dialkylamine), and combinations thereof.

In one embodiment of the disclosed rubber compound, the compound contains CBS as an accelerator. Such rubber mixtures therefore achieve particularly good tear properties.

Furthermore, network forming systems such as those commercially available under the trade names Vulkuren (Lanxess, Shanghai, PRC), Duralink (ChemLink, Schoolraft, MI, US) and Perkalink (Lanxess, Shanghai, PRC) or network forming systems such as those described in WO2010/059402 may also be used in the rubber mixtures. The system comprises a vulcanizing agent crosslinked with a functionality greater than four and at least one vulcanization accelerator. Curing agents that crosslink with a functionality greater than four have, for example, the general formula a:

wherein G is a polyvalent cyclic hydrocarbon group and/or a polyvalent heterohydrocarbon group and/or a polyvalent siloxane group containing 1 to 100 atoms; wherein each Y comprises a sulfur-containing functional group independently selected from rubber reactive groups; and wherein a, b and c are integers each independently selected from the following: a is equal to 0 to 6; b is equal to 0 to 8; and c is equal to 3 to 5.

The rubber reactive group is one or more of a thiosulfonate group, a dithiocarbamate group, a thiocarbonyl group, a mercapto group, a hydrocarbon group, and a sodium thiosulfonate group (a colored salt group). This allows highly advantageous wear and tear properties of the rubber mixtures according to the invention to be achieved.

Within the scope of the present disclosure, sulfur and sulfur donors include sulfur donating silanes, such as TESPT, curatives (cure) and curatives (cure), such as those described in EP 2288653, vulcanization accelerators as described above and curatives crosslinked with a functionality of greater than 4 as described in WO2010/059402 (e.g., curatives of formula A), as well as the aforementioned systems Vulkuren @ (Lanxess, Shanghai, PRC), Duralink @ (ChemLink, Schoolraft, US) and Perkalink @ (Lanxess, Shanghai, PRC) combined under the term "curatives".

The rubber compound according to the present disclosure may contain at least one of these vulcanizing agents. This makes it possible to produce vulcanizates from the rubber mixtures according to the disclosure, in particular for vehicle tires.

In some embodiments, a vulcanization retarder is also present in the rubber compound. As is known in the art, in tire technology there is often a "compromise" between rolling resistance and wet braking. Generally, when one of the two elements is improved, the other element is deteriorated. Therefore, an improvement in Rolling Resistance (RR) is generally accompanied by a deterioration in wet braking performance, and vice versa. This is an RR-wet braking target conflict. Accordingly, embodiments encompassed by the present disclosure include tires having surprisingly improved rolling resistance without variations in wet braking. It is therefore an object of the disclosed rubber composition to provide a vehicle tire that exhibits improved rolling resistance behavior as well as snow performance. The object is achieved in that the vehicle tyre comprises a rubber mixture according to the present disclosure in at least one component as described above. In this case, all the aforementioned embodiments of the composition and its characteristics apply.

It is a further object of the disclosed rubber composition to provide a vehicle tire exhibiting improved rolling resistance behavior and improved tear properties, in particular improved tear propagation resistance. The object is achieved in that the vehicle tyre comprises a rubber mixture according to the present disclosure in at least one component as described above. In this case, all the aforementioned embodiments of the composition and its characteristics apply.

In one embodiment, the component is a tread. As is known to those skilled in the art, the tread contributes to a relatively high degree to the overall rolling resistance of the tire. In particular, a high resistance to cracks and crack propagation in the tread is also advantageous. In one embodiment, the rubber compositions described herein may also be used in other components of a tire and may comprise various tire components and various tire component compounds. The tire may be built, shaped, molded and cured by various methods that are known and will be apparent to those skilled in the art.

It is another object of the present disclosure to improve the rolling resistance performance and tear properties of vehicle tires. According to the present disclosure, this object is achieved by using the rubber mixtures described with all of the embodiments and features described above in vehicle tires, in particular in the tread of vehicle tires and/or in the bulk mixture of vehicle tires.

Another object of the present invention is to optimize the wear behavior and tear properties of industrial rubber articles, such as belts, strips, brakes and hoses, without significantly negatively affecting other properties associated with the respective use.

The object is achieved by the use of the above-mentioned rubber mixtures for the production of technical rubber articles, such as belts (e.g. conveyor belts, automobile engine belts such as timing belts, transmission belts, etc.), strips, seals, pipes and hoses. Another such industrial rubber article is, for example, a sole for an article of walking shoes, running shoes, general training shoes, boots, slippers, etc., which is to be worn on the foot to protect the foot and associated bones and joints from damage caused by tremor or pounding actions associated with walking, running, jumping, etc., and to provide excellent slip resistance in wet and/or dry conditions. Various methods of incorporating rubber mixtures into footwear are known in the art. See, for example, U.S. patent application publication nos.: 2013/0291409, 2011/0252671, and U.S. patent No. 8,689,381 (the entire contents of which are hereby incorporated by reference herein for all purposes).

The term bulk mixture as used herein refers to a rubber mixture used for the inner components of a tire. Tire internal components include primarily flights, sidewalls, innerliners (inner layers), core profiles, belts, shoulders, belt profiles, carcass plies, bead wires, cable profiles, trumpet profiles, and bandages.

The manufacture of the rubber mixtures disclosed is carried out by the methods customary in the rubber industry, in which a base mixture having all the components except the vulcanization system (sulfur and vulcanization-acting species) is first produced in one or more mixing stages. The final mixture is prepared by adding the vulcanization system in the final mixing stage. The final mixture is further processed, for example by an extrusion process, and the corresponding form is obtained.

For use in vehicle tires, the mixture is preferably made into a tread and applied in a known manner in the production of vehicle tire blanks. However, the tread is also wound onto the tire blank in the form of a narrow strip of rubber compound. In a two-piece tread (upper: crown and lower: base), the rubber mixtures according to the invention are used both for the crown and for the base.

The production of the rubber mixtures according to the invention for use as a body mixture in vehicle tires is carried out as described above for the treads. Except that the molding is performed after the extrusion process. The form of the rubber mixture according to the invention obtained in this way for one or more different body mixtures is then used for producing tire blanks. For the use of the rubber mixtures according to the invention in belts and strips, in particular in conveyor belts, the extruded mixtures are brought into the respective form and, at the same time or thereafter, are usually provided with reinforcing carriers, for example synthetic fibers or steel cords. In most cases, a multilayer structure is obtained consisting of one and/or more layers of rubber compound, one and/or more layers of the same and/or different reinforcing carrier, and one and/or more further layers of the same and/or another rubber compound.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety for all purposes. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

Examples

A variety of functionalized resins have been prepared and tested in rubber compounds for vehicle tires, and a variety of functionalized resins have been prepared and tested in other compositions such as adhesives and the like. Synthetic routes and experimental data are provided below.