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.小贝克 T.R.卡瓦诺 J.J.沙普莱特 郑伟民 邓榴 J.G. 于 2018-04-09 设计创作，主要内容包括：提供极性硅烷连接基,其添附到树脂上以形成硅烷官能化树脂。所述官能化树脂可键合到二氧化硅粒子表面的羟基上以改进二氧化硅粒子在橡胶混合物中的可分散性。还公开了提供硅烷官能化树脂的合成路线以及获益于硅烷官能化树脂的出乎意料的性质的各种用途和最终产品。硅烷官能化树脂赋予各种橡胶组合物,如轮胎、皮带、软管、制动器等卓越的性质。包含所述硅烷官能化树脂的汽车轮胎据显示在平衡滚动阻力、轮胎磨损和湿制动性能的性质中具有优异的结果。(Polar silane linkers are provided that attach to the resin to form a silane-functionalized resin. The functionalized resin may be bonded to hydroxyl groups on the surface of the silica particles to improve dispersibility of the silica particles in the rubber compound. Also disclosed are various uses and end products that provide synthetic routes to silane-functionalized resins and that benefit from the unexpected properties of silane-functionalized resins. Silane-functionalized resins impart excellent properties to various rubber compositions, such as tires, belts, hoses, brakes, and the like. Vehicle tires comprising the silane-functionalized resins are shown to have excellent results in balancing the properties of rolling resistance, tire wear, and wet braking performance.)

1. A functionalized resin comprising formula I:

resin- [ Z ]_k-X_n-R¹-(CH₂)_m-Si(R²)_p]_q(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 a combination thereof;

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

wherein each R²Are the same or different and are 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 functionalized resin of claim 1, wherein the resin is obtained by polymerizing or copolymerizing one or more of an unsaturated aliphatic monomer, terpene, rosin acid, unsaturated cyclic aromatic monomer, unsaturated alicyclic monomer, unsaturated fatty acid, methacrylate, unsaturated aromatic monomer, vinyl aromatic monomer, and/or unsaturated aliphatic/aromatic monomer mixture, and/or

Wherein the resin is hydrogenated, partially hydrogenated, or unhydrogenated.

3. The functionalized resin of claim 1, wherein q is an integer from 2 to 8, and/or wherein n is an integer from 1 to 4.

4. The functionalized resin of claim 1, wherein- [ Z ] 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 in blocks throughout the functionalized resin, present in segments of the functionalized resin, present at least once per functionalized resin, present at least twice per functionalized resin, and/or present in the middle of each functionalized resin.

5. The functionalized resin of claim 2, wherein:

the aromatic and/or vinyl aromatic monomers comprise one or more of styrene, vinyl toluene, alpha-methylstyrene and/or diisopropylbenzene, or

Wherein the aliphatic monomer comprises C₅One or more of piperylene, coumarone, indene and/or dicyclopentadiene.

6. The functionalized resin of claim 1, wherein:

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

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

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

z is a 6-membered aryl, or a saturated or unsaturated cycloaliphatic radical.

7. The functionalized resin of claim 1, wherein X is oxygen or carbonyl.

8. The functionalized resin of claim 1, wherein each R²Independently selected from methoxy, hydroxy, ethoxy and propoxy.

9. The functionalized resin of claim 1, wherein the amount of silane-containing groups grafted to the 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%.

10. The functionalized resin of claim 1, wherein the resin has a molecular weight of from about 200 to about 200,000 g/mol, from about 200 to about 50,000 g/mol, from about 200 to about 20,000 g/mol, or from about 200 to about 15,000 g/mol.

11. The functionalized resin of claim 1, wherein the resin has a polydispersity index (PDI) of about 1 to 10, and/or the resin has a glass transition temperature Tg of less than about 200 ℃.

12. The functionalized resin of claim 1, wherein the Tg is less than about 160 ℃.

13. The functionalized resin of claim 1, wherein the amount of silane groups grafted to the resin is from about 0.01 to about 30 mole percent or from about 0.01 to about 50 mole percent.

14. The functionalized resin of claim 1, wherein the resin has a molecular weight of from about 200 g/mol to about 50,000 g/mol, from about 200 g/mol to about 20,000 g/mol, or from about 200 g/mol to about 15,000 g/mol.

15. The functionalized resin of claim 14, wherein the resin has a molecular weight of from about 400 g/mol to about 2,000 g/mol.

16. The functionalized resin of claim 1, wherein the polydispersity index (PDI) is from about 1 to about 5.

17. The functionalized resin of claim 1, wherein the PDI is from 1 to 2.

18. The functionalized resin of claim 1, wherein the functionalized resin is at least one-R²The groups are bonded to the silica particles through the Si-O-Si moieties after hydrolysis.

19. The functionalized resin of claim 1, wherein the functionalized resin molecule is at least one-R²The group is hydrolyzed and then bonded to the second functionalized resin molecule through the Si-O-Si moiety.

20. The functionalized resin of claim 1, wherein

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)₂One or more of and

R³is an aliphatic or aromatic C which is optionally branched and/or optionally contains one or more heteroatoms₁To C₈A carbon chain.

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 blocked silane containing resins by phenol functionalization. FIG. 1C shows the synthesis of a pendant silane containing resin by phenol functionalization with an 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 a blocked silane containing resin by phenol functionalization with succinic anhydride. FIG. 1H shows the synthesis of blocked silane containing resins from chloro-silanes via phenol functionalization. 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 blocked silane containing resins by phenol functionalization with glycidoxysilane. FIG. 1K shows the synthesis of a blocked silane containing resin by acid functionalization with glycidoxysilane. FIG. 1L shows the synthesis of blocked silane containing resins by phenol functionalization with glycidoxysilane. FIG. 1M shows the synthesis of a blocked silane containing resin by phenol functionalization with phthalic anhydride and glycidoxysilane.

Figure 2A schematically shows a prior art resin simply embedded in a polymer matrix. FIG. 2B schematically shows the bonding of a functionalized resin to SiO particles₂Of (2) is provided.

Figure 3 shows a representative fourier transform infrared (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.

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

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

Figure 9 shows a representative FT-IR spectrum of the functionalized resin synthesis product of step 1C (synthesis of a pendant silane-functionalized resin by functionalization 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 from 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 from carboxylic acid group functionalization) 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 from 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 functionalized with phenolic groups) 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 functionalized with a phenol group) as described in example 1.2.

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

FIG. 16 shows a representative FT-IR spectrum of a 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 end-capped 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 end-capped silane-functionalized resin functionalized with carboxylic acid groups) as described in example 1.2.

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

FIG. 20 shows the functionalized resin synthesis of step 2B (Synthesis of end-capped silane-functionalized resin functionalized by functionalization with carboxylic acid groups) as described in example 1.2Representative of the object¹³C Nuclear Magnetic Resonance (NMR) trace.

FIG. 21 shows a representation of the functionalized resin synthesis product of step 2B (synthesis of end-capped silane-functionalized resin functionalized by functionalization with carboxylic acid groups) as described in example 1.2²⁹Si NMR trace.

FIG. 22 shows a representative FT-IR spectrum of a 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.

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

Figure 28 shows a representative GPC trace of the functionalized resin synthesis product of step 4A (synthesis of a pendant carboxylic acid functionalized resin modified with an anhydride silane from a phenol) 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 succinic anhydride grafted 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 succinic anhydride grafted 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 succinic anhydride grafted onto Kristalex ™ 3085) as described in example 1.4.

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

FIG. 33 shows a representation of the functionalized resin synthesis product of step 4B (synthesis of a pendant silane-functionalized resin derived from succinic anhydride grafted onto Kristalex ™ 3085) as described in example 1.4¹H NMR trace.

FIG. 34 shows a representative of the functionalized resin synthesis product of step 4B (synthesis of a pendant silane-functionalized resin derived from succinic anhydride grafted onto Kristalex ™ 3085 (Eastman Chemical, Ltd., Kingsport, TN, US)) as described in example 1.4¹³C NMR trace.

FIG. 35 shows a representation of the functionalized resin synthesis product of step 4B (synthesis of a pendant silane-functionalized resin derived from succinic anhydride grafted onto Kristalex ™ 3085) as described in example 1.4²⁹Si NMR trace.

Figure 36 shows a representative GPC trace of the functionalized resin synthesis product of step 5A (synthesis of a pendant silane functionalized resin from free radical copolymerization with methacrylate silanes) 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 methacrylate silane) as described in example 1.5¹H NMR trace.

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

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

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

FIG. 42 shows a representation of blocked silane-containing resins prepared with chloro-silanes via phenol functionalization as described in example 1.7²⁹Si NMR trace.

FIG. 43 shows a representation of pendent silane-containing resins synthesized by the 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 the copolymerization of isobornyl methacrylate and 3- (trimethoxysilyl) propyl methacrylate as described in example 1.8.

FIG. 45 shows a representation of pendent silane-containing resins synthesized by the 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 the copolymerization of isobornyl methacrylate and 3- (trimethoxysilyl) propyl methacrylate as described in example 1.8.

Figure 47 shows a resulting representative TGA trace of the end product of the blocked silane containing resin obtained by phenol functionalization with glycidoxysilane as described in example 1.9.

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

FIG. 49 shows the phenol functionalization with glycidoxysilanes as described in example 1.9Obtained representative of blocked silane-containing resin end products¹H-NMR trace.

Figure 50 shows the resulting representative GPC trace of the blocked silane-containing resin end product obtained by phenol functionalization with glycidoxysilane as described in example 1.9.

Figure 51 shows the resulting representative GPC trace of the blocked silane-containing resin obtained by acid functionalization with glycidoxysilane as described in example 1.10.

FIG. 52 shows the resulting representative of blocked silane-containing resins obtained by acid functionalization with glycidoxysilane as described in example 1.10¹H-NMR trace.

Figure 53 shows a resulting representative TGA trace of a blocked silane-containing resin obtained by acid functionalization with a glycidoxysilane as described in example 1.10.

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

FIG. 55 shows a representative GPC trace of a blocked silane-containing resin obtained by phenol functionalization with glycidoxysilane as described in example 1.11.

FIG. 56 shows a representation 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 blocked silane-containing resin obtained by phenol functionalization with glycidoxysilane as described in example 1.11.

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

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

Detailed description of the invention

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

Definition of

Certain terms used throughout this disclosure are defined below to facilitate understanding of the invention. Further definitions are set forth throughout this disclosure.

Terms not explicitly defined in the present application should be understood to have the meaning commonly accepted by those skilled in the art. If the term is to be interpreted as nonsensical or substantially nonsensical in this context, the term is to be defined from a standard dictionary.

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

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

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

The term "comprising" (and grammatical variants thereof) as used herein is used in an inclusive sense of "having" or "including" rather than in an exclusive sense of "consisting only of …".

The terms "a" and "an" as used herein are understood to encompass one or more components, both in the plural and the singular.

The designation "phr" refers to parts by weight per hundred parts of rubber and is used in this specification to denote the amounts conventionally designated in the rubber industry for blend formulations. The parts by weight amounts of the individual substances are always based here on 100 parts by weight, based on the total weight of all rubbers present in the blend. The above resins should not be considered as rubbers in the context of the present disclosure.

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

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

The term "vulcanization" as used herein refers to subjecting a chemical composition, such as a polymer, e.g., an elastomeric and/or thermoplastic polymer composition, to a chemical process that includes the addition of sulfur or other similar vulcanizing agents, activators and/or accelerators at elevated temperatures (see, e.g., WO 2007/033720, WO 2008/083242 and PCT/EP 2004/052743). Vulcanizing agents and accelerators are used to form crosslinks or chemical bridges between individual polymer chains. The vulcanizing agents are generally referred to as sulfur vulcanizing agents and vulcanization accelerators. Suitable sulfur vulcanizing agents include, for example, elemental sulfur (free sulfur) or a sulfur-donating vulcanizing agent that provides sulfur for vulcanization at a temperature of from about 140 ℃ to about 190 ℃. Suitable examples of sulfur donating vulcanizing agents include amino disulfides, polymeric polysulfides, and sulfur olefin adducts. The vulcanizable polymer compositions described herein may also include, in some embodiments, one or more vulcanization accelerators. Vulcanization accelerators control the time and/or temperature required for vulcanization and affect the properties of the vulcanizate. The vulcanization accelerator includes a main accelerator and a secondary accelerator. Suitable accelerators include, for example, mercaptobenzothiazole, tetramethylthiuram disulfide, benzothiazole disulfide, diphenylguanidine, zinc dithiocarbamate, alkylphenol disulfide, zinc butylxanthate, N-dicyclohexyl-2-benzothiazolesulfenamide, N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylenebenzothiazole-2-sulfenamide, N, n-diphenylthiourea, dithiocarbamyl sulfenamide, N, one or more of N-diisopropylbenzothiazole-2-sulfenamide, 2-mercaptomethylbenzimidazole zinc (zinc-2-mercapto tolimidazole), dithiobis (N-methylpiperazine), dithiobis (N-beta-hydroxyethylpiperazine), and dithiobis (dibenzylamine). Other vulcanization accelerators include, for example, thiuram and/or morpholine derivatives. In addition, the vulcanization compound in some embodiments also includes one or more silane coupling agents, such as a difunctional organosilane having at least one alkoxy, cycloalkoxy, or phenoxy group on the silicon atom as a leaving group and, as another function, a group that can chemically react with the double bond of the polymer, optionally after cleavage. The latter group may for example constitute the following chemical group: SCN, -SH, -NH 2 or-Sx- (wherein x is 2 to 8). Thus, the vulcanization product, i.e., the mixture to be vulcanized, in some embodiments includes various combinations of exemplary silane coupling agents as described in more detail below, such as 3-mercaptopropyltriethoxysilane, 3-thiocyanato-propyl-trimethoxysilane, or 3,3 '-bis (triethoxysilylpropyl) -polysulfide having 2 to 8 sulfur atoms, for example, 3' -bis (triethoxysilylpropyl) tetrasulfide (TESPT), the corresponding disulfide (TESPD), or mixtures of sulfides having 1 to 8 sulfur atoms in varying amounts with various sulfides.

"weight average molecular weight (M)_w) "measured 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 usually determined by sedimentation equilibrium (ultracentrifugation) and light scattering. 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. This value is used in some cases as an indicator of the high molecular weight tail (tail) in the thermoplastic resin.

"glass transition temperature (Tg)" is the temperature range over which an amorphous material can reversibly change from a hard, rigid, or "glass-like" solid state to a more pliable, flexible, or "rubber-like" viscous state, and is measured in degrees celsius or ° f. Tg is different from the melting point temperature. Tg can be determined using Differential Scanning Calorimetry (DSC) as disclosed below in example 2.

The terms end-capped and terminating capped are used interchangeably herein to indicate that a polymer has a terminal end or ends with a silane group located at the end or ends of the polymer. The silane molecules of formula I can be located at the end points or ends of the resin polymer to create a terminated resin 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 the end points, to create a multi-derivatized (multi-derivitized) polymer resin. When the polymer chain units to which the silane-functional moieties are attached occupy positions inward from either end of the polymer backbone, the silane-functional moieties of formula I are attached to the pendant positions of the polymer, while the terminal or terminal silane moieties are attached to the final chain units at either end of the polymer (resin). Types of silane-functionalized polymers suitable for use in accordance with the method 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 containing various attachments (appendages) are disclosed. The functionalized resins disclosed herein have different structures and can be prepared or synthesized using a number of methods, routes, and strategies. For example, several possible synthetic routes for the functionalized resins disclosed herein are schematically shown in fig. 1A through 1M. That is, fig. 1A through 1M provide schematic depictions of several exemplary embodiments of synthetic strategies for producing the silane-containing resins disclosed herein.

As a non-limiting example thereof, a phenolic-containing resin (having an intrachain functional group or functional monomer from copolymerization with acetoxystyrene) may be used to provide a starting material for silane functionalization. For example, the resin used as a raw material may include any one or more of known styrene-based resins or poly (alpha-methyl) styrene (AMS) resins. Other resins useful as starting materials and functionalized in accordance with embodiments disclosed herein include any resin known to the skilled artisan, including fully hydrogenated resins, partially hydrogenated resins, and unhydrogenated resins. For example, suitable resins known in the art and useful as starting materials for the disclosed processes for making silane-functionalized resins include, but are not limited to, pure monomer thermoplastic resins (PMR), C5 thermoplastic resins, C5/C9 thermoplastic resins, C9 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, and indene-coumarone (IC) thermoplastic resins.

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 to produce resins having one or more end-functionalized groups. As another exemplary embodiment, the phenolic groups can be reacted in a Williamson ether synthetic route followed by a mixed anhydride reaction to produce a silane-containing resin as shown in fig. 1C. The reaction of phenolic-based resins with anhydride-containing silanes was also successful. Other synthetic strategies produce pendant functionalized resins that can produce the desired degree of functionalization at an internal position.

The functionalized resin may be in the form of a block copolymer, or the silane portion of the functionalized resin may be randomly distributed 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 block copolymerization processes and functionalization of the formed resin, thereby forming a resin having random monomers functionalized throughout the resin backbone. Further, the functionalized resins disclosed herein can be synthesized starting from resin monomers, where the resin monomers are reacted directly with silane moieties in one step to form the functionalized resin as shown in scheme 5. The functionalized resin may also be synthesized starting with a fully formed resin, such as those disclosed in schemes 1-4, examples 1 and 2 below.

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

resin- [ Z ]_k-X_n-R¹-(CH₂)_m-Si(R²)_p]_q(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 a combination thereof;

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

wherein each R²Are the same or different and are 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.

Typically, in the heteroatom group R¹With silane groups 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 the reaction of a phenol or hydroxyl containing resin with a silyl isocyanate (triethoxysilylpropyl isocyanate) to yield a compound having the formula: resin-OCONH- (CH)₂)₃-Si(OCH₂CH₃)₃The functionalized resin of (1). Reacting a phenol or hydroxyl based resin with an anhydride silane, such as 3- (triethoxysilyl) propyl succinic anhydride, results in the formation of an ester linkage to form a resin having the formula: resin-O-CO-CH (CH)₂COOH)((CH₂)₃-Si(OCH₂CH₃)₃) The functionalized resin of (1). Ester linkages to the resin may also be obtained by esterification or transesterification. The silane can be functionalized directly with an alkyl halide via the resin-OH, for example Cl- (CH)₂)₃Si(O CH₂CH₃)₃The Williamson ether synthesis of (A) generates an ether linkage to the backbone via an oxygen to form the resin-O- (CH)₂)₃-Si(OCH₂CH₃)₃. For 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 the resin-CO-NH- (CH)₂)₃-Si(OCH₂CH₃)₃. For example, by using a road-signThe succinic anhydride is grafted onto styrene or alpha-methylstyrene with a silicic 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 bonds to obtain the resin-CO-NH- (CH) by ring opening of the anhydride with triethoxysilylpropylamine₂)₃-Si(OCH₂CH₃)₃。

The copolymer may include any number of other comonomers, but most likely includes resins of styrene or alpha-methylstyrene or mixtures thereof. A preferred embodiment is that the resin comprises styrene and/or alpha-methylstyrene or mixtures thereof. The phenol can be attached to the resin at any position on the ring, for example and including para, ortho and meta.

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

In yet another exemplary embodiment, X is oxygen or carbonyl. In a further embodiment, X may be sulfur. In a particular embodiment, the vinyl aromatic monomer may be styrene or alpha-methylstyrene or mixtures thereof. In another particular embodiment, heteroatom-containing linking group X comprises a para-, meta-, or ortho-appended 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 to covalently link the silane group and/or carbonate. In yet another specific embodiment, X_nR¹-(CH₂)_mComprising one or more groups containing carbamate, ester, ether, ketone, amide, and propyl groups.

In general, each R²Are the same or different andindependently 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 can 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., both capped and pendant. In end-capped functionalized resin embodiments, 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%, 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)_pTo the same linking group X or R¹The above. The silane groups on the same linking group may be the same or different. Further, the functionalized resins disclosed herein comprise R containing branch points¹And X moiety, the branch points may also contain one or more silane functionalities (see e.g. example 1.3 below)Scheme 3）。

In particular, the resin may have a molecular weight (Mw) of 200 to 200,000 g/mol, more typically 200 to 175,000 g/mol, more typically 200 to 150,000 g/mol, 200 to 125,000g/mol, 200 to 100,000 g/mol, 200 to 75,000 g/mol, most typically 200 to 50,000 g/mol. In another exemplary embodiment, the resin has a molecular weight of 400 to 200,000 g/mol, more typically 400 to 175,000 g/mol, more typically 400 to 150,000 g/mol, 400 to 125,000g/mol, 400 to 100,000 g/mol, 400 to 75,000 g/mol, most typically 400 to 50,000 g/mol. In yet another exemplary embodiment, the resin has a molecular weight of 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 exemplary 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 and other additives at this temperature.

In one embodiment, the resin has a glass transition temperature Tg of 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 contains one or more terminal functional groups- [ Z [ ]_k-X_n-R¹-(CH₂)_m-Si(R²)_p]_q. Furthermore, the resin is generally prepared by side-bonding one or more (q) moieties Z to the backbone of the resin of random, segmented or block structure_k-X_n-R¹-(CH₂)_m-Si(R²)_pAnd (4) functionalizing. In another embodiment, the side chains are end-capped. In yet another embodiment, the side chains are a mixture of capped and pendant.

In particular, the functionalized resin is functionalized at least one of-R²The groups are hydrolyzed and then bonded to the silica particles via Si-O-Si chains (links). Also particularly, the functionalized resin molecule is at least one-R²The groups are hydrolyzed and then attached to the second functionalized resin molecule via a Si-O-Si chain (link). In addition, can be shapedBridging side chains in which the Si group is via one, two or three R²The group is covalently bonded 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-、-CO-NH-R³-(CH₂)₂Or mixtures thereof, and R³Is an aliphatic or aromatic C which is optionally branched and/or optionally contains one or more heteroatoms₁To C₈A carbon chain. 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. Further, 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 between these, 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. As an example, some non-limiting embodiments of the functionalized resin comprise the following structure:

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(s) and the silane addition 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 group is added at the end or side of the resin chain or a mixture 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, e.g. styrene or a benzene ring structure, or containing a long C₁To C₁₈An aliphatic chain, and wherein the silane attachment number "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, attached at the end or side of the resin chainFlour or a mixture thereof. In these embodiments, k may be an integer of 0 or 1.

Other 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。

Additional exemplary silane structures can be obtained, and thus additional silane-functionalized resins provided, by sol-gel chemistry, by hydrolysis or with Si (OH)_nSubstituted Si (R)²)_pTo produce, wherein for one or more silanes R²And n is an integer of 1 to 3. In waterAfter dissociation, any two Si (OH) s may occur_nCondensation of the groups to form Si-O-Si structures linking resin-resin, resin-other commercial silanes, resin-functionalized rubber grades, or resin-fillers. Can select-Si (R)²)_pR of (A) to²The group serves as, for example, a heteroatom-containing or carbon chain linker to another similar resin, a linker to another type of silane-functionalized resin, a linker to another small molecule silane, or a silane polysulfide, such as bis [3- (triethoxysilyl) propyl ] can be used]Tetrasulfide (e.g. Si69, Evonik Industries AG, Essen, Germany) or bis [3- (triethoxysilyl) propyl ] propyl]Disulfides (e.g., Si266, Evonik Industries AG, Essen, Germany), linkages to filler particles or to functionalized rubber grades. These non-limiting exemplary structures include Si-O-Si bonds. Any known combination of condensation resin-resin is possible, i.e. forming interchain bonds between two different silane-containing groups and/or forming intrachain bonds within the same silane-containing groups, resin-other silanes, resin-functionalized rubber grades or resin-filler structures are possible whereby Si (oh) condenses onto Si-O-Si to link the two Si-containing groups. In another embodiment, the functionalized resin may include an aryl group (Ar) as the Z group, for example to yield the structure: 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 form a hydroxystyrene containing resin. The carbonyl (C = O) linkage may come from a group grafted onto styrene or alpha-methylstyrene, for example, using succinic anhydride or another anhydride and a lewis acid catalyst, such as aluminum chloride. Exemplary embodiments where X is carbonyl (C = O) may be obtained from several possible methods, such as grafting maleic anhydride onto the backbone of an unsaturated C5 or C5 copolymer resin.

Compositions comprising silane-functionalized resins

The functionalized resins described above can be incorporated into a variety of chemical compositions having many uses. The chemical composition is, for example, a solvent-based, aqueous, emulsion, 100% solids, or hot melt composition/adhesive. For example, alkoxysilane low molecular weight polymers (Mw < 30000) may be blended with other polymers. 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 alpha-polyolefins, Reactor-Ready type 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. Several non-limiting examples of how the disclosed functionalized resins can be incorporated into a variety of products to impart beneficial and useful properties not previously available for these products are provided below.

In one embodiment, the functionalized resin is blended with an alkoxysilane low molecular weight polymer that can be used as an additive to be used in the same manner as typical low molecular weight polymers. The presence of the functionalized resins disclosed herein in the alkoxysilane low molecular weight polymer containing compositions enhances processability (higher melt flow rate, lower viscosity) and promotes adhesion. The alkoxysilane low molecular weight polymer is further reacted after processing, thereby producing a crosslinked polymer that enhances the performance of the final article comprising such a blended resin in terms of temperature and chemical resistance. If the modified polymer has alkoxysilane functionality, the low molecular weight polymer may be grafted onto the modified polymer in addition to being self-crosslinking. In addition, the ability to react further is beneficial in filled systems (particles, fibers, etc.) where the alkoxysilane is chemically bonded to the surface groups of various fillers.

In another embodiment, styrene-ethylene/butylene-styrene block copolymers (e.g., Kraton G1650, Kraton Polymers U.S., LLC, Houston, TX, US) are blended/processed with about 20 weight percent alkoxysilane functionalized polystyrene at a temperature below the activation temperature for hydrolysis and crosslinking of the alkoxysilane. 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, and gaskets, high temperature compression set and chemical resistance are improved. For tape applications, chemical crosslinking can be triggered in the same manner, with consequent increase in shear resistance, shear failure temperature and chemical resistance.

In another embodiment, a disposable hygiene article is disclosed comprising an adhesive comprising the disclosed silane-functionalized resin that exhibits improved adhesive and cohesive strength as compared to such articles without the disclosed silane-functionalized resin, by improved values in peel adhesion testing of laminate constructions, improved peel adhesion after aging at body temperature, reduced elastic strand creep over time, and improved core stability in the final hygiene article. The articles have improved chemical resistance and barrier properties, particularly with respect to exposure to fluids such as bodily fluids.

The polymer composition further optionally includes a polyolefin comprising amorphous or crystalline homopolymers or copolymers of two or more different monomers derived from an alpha-monoolefin 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-propene, 3-methyl-i-pentene, 4-methyl-i-pentene, 5-methyl-i-hexene, and combinations thereof. Additional 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, polybutylene, and olefinic block copolymers. The polyolefin copolymer also includes a major part by weight 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, and the like. Typically, the polyolefin copolymer comprises less than about 30 wt% non-olefin monomers, less than 20 wt%, or less than about 10 wt% non-olefin monomers. Polyolefin polymers and copolymers are available from sources including, but not limited to, Chevron, Dow chemical, DuPont, Exxon Mobil, REXtac, LLC, Ticona, and Westlake Polymer under various names.

Migration and volatilization of low molecular weight components of currently marketed thermoplastic resins used to modify elastomeric compounds, such as adhesives, thermoplastic elastomer (TPE) compounds, molding compounds, mastics (cements), and the like, results in the release of unpleasant odors, volatiles, fogging, product defects, reduced product cohesive strength, reduced adhesion, and reduced performance over time.

TPE compositions comprising the silane-functionalized or modified resins described herein are, in some embodiments, molded into various articles as is well understood by those of ordinary skill in the art. For example, the TPE composition is reprocessed into a final article and embodiments thereof, such as by pressing, compression molding, injection molding, calendering, thermoforming, blow molding, or extrusion. 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 forming into the desired articles of various shapes and sizes. The end user of the TPE composition benefits from the processing advantages described throughout this disclosure.

Any polymer known in the art may be mixed with the silane-functionalized resins described herein to make compositions useful in the various end products described herein, such as adhesives. For example, in one embodiment, TPEs include, but are not limited to, block copolymers, thermoplastic/elastomer blends and alloys, such as styrenic block copolymers (TPE-S), metallocene-catalyzed polyolefin polymers and elastomers, and reactor-made thermoplastic polyolefin elastomers. Block copolymers include, but are not limited to, styrenic 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. Two-phase TPEs are combined with the disclosed modified thermoplastic resins in some embodiments in these end uses 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, the disclosed modified silane resins are used in some embodiments to modify the properties of thermoplastic elastomer (TPE) compositions. Embodiments thus include TPE compositions comprising at least one thermoplastic elastomer and at least one modified silane resin. Early versions of TPEs were thermoset rubbers, which were also used in such compositions. TPEs are known to be widely used in various industries to modify the properties of rigid thermoplastics to provide improved impact strength. This is quite common for sheet materials and general purpose molded TPEs. Thus, the addition of the modified silane resins described herein to these compositions imparts superior properties to these compositions and their standard end-use applications.

TPE compositions comprising the disclosed silane-functionalized resins comprise 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, styrenic 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, a hard thermoplastic phase is mechanically or chemically coupled to a soft elastomer phase to produce a TPE having a combination of the properties of the two phases.

Styrenic block copolymers (TPE-S) are based on two-phase block copolymers with hard and soft segments. Exemplary styrenic 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). Styrene-butadiene-styrene is known to be commonly incorporated in compositions for footwear, adhesives, asphalt modification and lower gauge seals and clamps (grips), where chemical and aging resistance is not a focus of end use. Monoprene, Tekron and Elexar products from Teknor Apex Company (Pawtucket, RI, US) are examples of fully formulated TPE-S compounds which are hydrogenated styrenic block copolymers. Styrene- [ ethylene- (ethylene/propylene) ] -styrene (SEEPS) block polymers are available from Kuraray co. Styrene-ethylene/butylene-styrene (SEBS) block copolymers are available from Kraton Performance Polymers.

Table 1 shows the performance enhancements expected from the incorporation of silane-functionalized resins in various applications where these attributes are likely to be advantageous. The capital "X" in table 1 refers to the attributes likely to be achieved and desired in each application by incorporation of the silane-functionalized resins disclosed herein into the indicated compositions.

TABLE 1

Polymer modification uses of thermoplastic elastomers using the silane-functionalized resins include, but are not limited to, roofing uses, particularly asphaltene modifiers (asphalt modifiers) in modified asphalt roofing materials (modified asphalt roofing), waterproofing membranes/compounds, roofing underlayments (underlayments), cable impregnation/filling compounds, caulks and sealants, polymer compounds/blends, films (e.g., cling film, TPE films, etc.), molded articles, rubber additives/processing aids, carpet backings (e.g., high performance precoats, thermoplastic compounds, etc.), wires and cables, power and hand tools, pen covers (pen grids), air bag bags, handles and grips, seals and laminates (e.g., paper lamination, water activated hot melt adhesive coated scrim reinforced tapes, etc.). When the silane-functionalized resins described herein are incorporated into these end uses, the silane-functionalized resin is in some cases 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.

Accordingly, other embodiments include adhesives for packaging, product assembly, woodworking, automotive assembly, and other uses that are composed of ethylene vinyl acetate, ethylene butyl acrylate, semi-crystalline single site catalyzed (metallocene) polyolefins, amorphous poly-alpha-olefins such as ziegler natta catalyzed polymers, acrylic resins, and styrenic block copolymers. These products may exhibit improved adhesive and cohesive strength as measured by peel failure temperature (PAFT) testing, fiber tear testing, peel testing on adhered structures, shear failure temperature (SAFT) testing, IoPP (institute of Packaging properties) test T-3006 Heatstress Resistance of Hot Melt Adhesives and shear holding power (shear hold power). The adhesive embodiments comprising the disclosed functionalized resins may exhibit improved heat resistance as evidenced by fiber tear or peel adhesion testing at elevated temperatures, such as 60 ℃. Improved chemical resistance can be manifested as a reduction in adhesive and cohesive strength degradation upon exposure to selected chemicals.

As determined by any of the above test methods at and above room temperature: PAFT, SAFT, peel, fiber tear, and shear holding power demonstrate that compositions comprising the disclosed functionalized resins can act as a barrier to plasticizer migration, as shown by adhesion characteristics over time, particularly after heat aging, as compared to compositions that do not include the disclosed functionalized resins. Similarly, the compositions adhere well to difficult surfaces or substrates having migrating components (e.g., slip aids or plasticizers) as compared to adhesives that do not contain the disclosed functionalized resins, as demonstrated by the adhesion tests listed above.

Wax compositions for investment casting comprising the disclosed functionalized resins have excellent rheology to consistently produce parts as evidenced by compositional rheology (stress-strain curve). The excellent performance of the dimensional stability of the wax casting composition and the stability of the casting composition during the manufacture of the mold is confirmed by the improved tolerances on the cast product.

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

In a further embodiment, disclosed are sealant compositions comprising the disclosed functionalized resins that exhibit reduced fogging of sealed windows after aging as compared to the performance of sealants without the disclosed functionalized resins.

The 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.

For sealants, gaskets, structural adhesives, cement, asphalt (bitumen) and asphaltene (asphalit) adhesives, thermoplastic elastomer (TPE) compounds and pressure sensitive adhesives, vibration and acoustic damping improvements can be measured by ASTM E756.

Also provided are compositions containing the disclosed functionalized resins, such as mastics containing asphalt (bitumen), asphaltenes (asphalit), or similar materials. Such compositions have a lower viscosity than compositions without the disclosed functionalized resins and are therefore easier to process while exhibiting excellent adhesion to aggregate components, fillers and substrates, such as stone or cement, as demonstrated by tensile testing on adhered stone or cement samples. Such mastics can be used in the production of bridge deck (bridge stripping), flooring, road construction and roofing materials.

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 species from the adhesive composition or article component into the facestock or substrate. As a result, the facestock or substrate may become contaminated over time and the construction may lose some adhesion. Such migration or penetration of some or all of the components of the adhesive, composite film, or other composition comprising the thermoplastic resin may also leave a residue on the adhesive surface, e.g., upon removal with the protective film, or may cause unwanted surface contamination, skin irritation, and the like. More importantly for adhesive applications, compounds comprising thermoplastic resins or multilayer films, migration or "penetration" of chemical components towards the adhesive interface, e.g. adhesive-substrate or film-adhesive-nonwoven, can result in immediate or delayed reduction or elimination of adhesive strength, damage to the adhesive or laminate, and/or reduced adhesion with aging.

The above-described compositions comprising silane-functionalized thermoplastic resins further comprise, in some embodiments, at least one polymer and from about 0 to about 75 weight percent 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, for example, be one or more of hydrogenated and/or non-hydrogenated styrenic 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 compositions described herein exhibit a viscosity at 177 ℃ of from about 50 to about 10,000 cP and a softening point of from about 60 to about 180 ℃ and are suitable adhesives.

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.

In various embodiments, the composition comprises 10, 20, 30, or 40 and/or no more than 90, 80, 70, or 55 weight percent of at least one polymer component. Exemplary polymer 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, polyurethanes, poly (acrylates), ethylene acrylic acid copolymers, polyetheretherketones, polyamides, styrenic block copolymers, random styrenic copolymers, hydrogenated styrenic block copolymers, styrene butadiene copolymers, natural rubber, polyisoprene, polyisobutylene, atactic polypropylene, polyethylene, including atactic polypropylene, ethylene-propylene polymers, propylene-hexene polymers, ethylene-butene polymers, ethylene octene polymers, propylene-butene polymers, propylene-octene polymers, metallocene catalyzed polypropylene polymers, ethylene vinyl acetate copolymers, styrene butadiene, metallocene-catalyzed polyethylene polymers, ethylene-propylene-butene terpolymers, copolymers made from propylene, ethylene and various C4-C10 alpha-olefin monomers, polypropylene polymers, functional polymers such as maleated polyolefins, butyl rubbers, polyester copolymers, copolyester polymers, isoprene, terpolymers formed from the monomers ethylene, propylene and a bicycloalkene (known as "EPDM"), isoprene-based block copolymers, butadiene-based block copolymers, acrylate copolymers such as ethylene acrylic acid copolymers, butadiene acrylonitrile rubbers and/or polyvinyl acetate.

The compositions disclosed herein contain, in various embodiments, polymers, tackifier resins, and other additives such as, but not limited to, oils, waxes, plasticizers, antioxidants, and fillers, depending on the end use. 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, tackifier resin, and/or other additives per 100 parts of modified thermoplastic resin. For example, in one embodiment, the compositions disclosed herein contain from about 50 to about 300 parts of elastomer per 100 parts of silane-functionalized resin.

As noted above, in some embodiments, the composition comprises additives that are particularly suited for a particular end use. For example, if the adhesive is intended to function as a hot melt packaging adhesive as described above, the composition further comprises a wax in this embodiment. 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 made by the fischer-tropsch process, vegetable waxes, functionalized waxes (maleated, fumarated or functional waxes), and the like. In such embodiments, the wax is included in the composition in an amount of from about 10 to about 100 parts wax per 100 parts polymer component.

Various oils are added to the adhesive composition in Pressure Sensitive Adhesive (PSA) composition embodiments, such as adhesives for tapes, mastics, and labels, and in nonwoven applications of 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 is free of 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, such as dibutyl and dioctyl phthalates, 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 and Eastman 168 (Eastman chemical company, Kingsport, TN, US).

In other embodiments, the composition comprising 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 amine-based antioxidants such as alkyldiphenylamines, phenylnaphthylamines, alkyl or aralkyl substituted phenylnaphthylamines, alkylated p-phenylenediamines, tetramethyl-diaminodiphenylamines, 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; tetrakis [ (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, IRGANOX 1076 (BASF Corp., LA, US) and combinations thereof. When used, the amount of antioxidant in the composition can be about greater than 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 of the total weight of the composition. In another such embodiment, the adhesive composition comprises from about 0.1 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 antioxidant.

In another embodiment of the composition, the compositionOne 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 further embodiments, 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, i.e., a combination of silica and oxygen (SiO)₂) Are manufactured by known methods and are commercially available as white powders in pure or relatively pure form. The silica typically formed by precipitation is a synthetic crystalline amorphous (crystalline amorphous) form of silica derived from quartz sand. Such silicas and silicates are in some embodiments 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 as filler is used together with an organosilane as coupling agent, a silica-silane system is established which is commonly used or incorporated in industrial rubber articles requiring high reinforcement and processability to make white or colored products. In such cases and embodiments, Silica is incorporated as a filler to improve tear resistance, and in some embodiments, the Silica-silane system reduces heat accumulation (see Uhrland, s., "Silica," in Encyclopedia of Chemical Technology, Kirk-Othmer, John Wiley&Sons, inc., 2006). Instead, the clay consists of a fine-grained clay mineral and is essentially a combination of silica, alumina and water to produce a hydrated aluminum silicate with bound alkali and alkaline earth elements. Such clays are raw materials present in clay deposits (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 the sealant due toHigh swelling provides water resistance and resists water migration. The clay incorporated into the cement 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 within the clay that are different and distinct from synthetic silica and, in some embodiments, are also incorporated as fillers in the composition (see also for reference)Id"Clays, Uses" and "Clays, Survey").

Additionally, other tackifier resins, optionally in the form of physical blends, are present in various embodiments of the composition. Tackifying resins added to the composition in this embodiment include, but are not limited to, cycloaliphatic hydrocarbon resins, C5 hydrocarbon resins, C5/C9 hydrocarbon resins, aromatic modified C5 resins, C9 hydrocarbon resins, neat monomer resins (e.g., copolymers of styrene with alpha-methylstyrene, vinyltoluene, p-methylstyrene, indene, and methylindene), DCPD resins, dicyclopentadiene-based/containing resins, cyclopentadiene-based/containing resins, terpene phenol resins, terpene styrene resins, rosin esters, modified rosin esters, liquid resins of fully or partially hydrogenated rosin, fully or partially hydrogenated DCPD 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 DCPD resins, Fully or partially hydrogenated dicyclopentadiene based resins, fully or partially hydrogenated cyclopentadiene based resins, fully or partially hydrogenated aromatically modified C5 resins, fully or partially hydrogenated C9 resins, fully or partially hydrogenated pure monomer resins (e.g., copolymers of styrene with alpha-methylstyrene, vinyltoluene, p-methylstyrene, indene, and methylindene), fully or partially hydrogenated C5/cycloaliphatic resins, fully or partially hydrogenated C5/cycloaliphatic/styrene/C9 resins, fully or partially hydrogenated cycloaliphatic resins, and mixtures thereof.

In some embodiments, the compositions described herein include other conventional plastic additives in an amount sufficient to obtain the desired processing or performance properties of the adhesive. The amount should not be wasteful of the additive nor detrimental to the processing or performance of the adhesive. One skilled in the art of thermoplastic compounding can choose from many different types of additives to incorporate into the compounds described herein without undue experimentation and with reference to monographs such as Plastics additives database (2004) from Plastics Design Library (www.elsevier.com). Non-limiting examples of optional additives include adhesion promoters; antimicrobial agents (antibacterial, antifungal and antifungal agents), antifogging agents; an antistatic agent; binders, foaming agents and foaming agents; a dispersant; fillers and extenders; fire and flame retardants and smoke suppressants; 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 antiblock agents; stabilizers (e.g., Irganox 1010 and Irganox 1076, BASFCcorporation, LA, US); a stearate; an ultraviolet absorber; a viscosity modifier; a wax; and combinations thereof. Antioxidants are particularly useful in these compounds to provide additional durability.

Such compositions are made in one embodiment by blending a silane-functionalized resin with an elastomer (at least one polymer) to form an adhesive. That is, the adhesive compositions described herein are prepared in one embodiment by combining the silane-functionalized resin, elastomer, and additives using conventional techniques and equipment. As non-limiting exemplary embodiments, the components of the compositions described herein are blended in a mixer, such as a Sigma blade mixer, a plasticorder, a Brabender mixer, a twin screw extruder, and/or an in-can blend can (pint can). 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 at different speeds via different nozzle configurations 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 for coating substrates with the composition. Substrates include, for example, textiles, fabrics, paper, glass, plastics, and metal materials. Typically, about 0.1 to 100 g/m2 of the adhesive composition is applied to a substrate.

The silane-functionalized resins described herein are incorporated in some embodiments into various types of compositions, including but not limited to hot melt or solvent-based pressure sensitive adhesives (e.g., tapes, labels, mastics, HVAC, etc.), hot melt nonwoven adhesives (e.g., those used in the construction industry, for elastic attachments, or for stretchings), and hot melt packaging adhesives. Furthermore, the silane-functionalized resins described herein incorporate in another embodiment different polymeric systems as explained above to provide such polymeric systems with excellent physical and chemical properties in terms of processability, stability, thermal properties, barrier properties, viscoelasticity, vibration damping, rheology, volatility, fogging profiles and/or adhesion and mechanical properties. 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 (e.g., tread compositions, sidewalls, innerliners, innertubes (inner-tubes), and various other pneumatic tire components).

Although the discussion above is primarily directed to adhesive applications comprising the silane-functionalized resins described herein, these principles are generally extensible and applicable to other polymer compositions comprising silane-functionalized resins for use in various end products. For example, polymer modification uses that include the silane-functionalized resins described herein include, but are not limited to, roofing uses (such as asphaltene modifiers in modified asphalt roofing materials), waterproofing membranes/compounds, roofing underlayments, cable impregnation/filling compounds, caulks and sealants, structural adhesives, polymer compounds/blends, films (e.g., cling film, TPE films, biaxially oriented polypropylene (BOPP) films, and the like), molded articles, rubber additives/processing aids, carpet backings (e.g., high performance precoats, thermoplastic compounds, and the like), wire and cable, power and hand tools, pen covers, air bag bags, handles and grips, seals, and laminated articles (e.g., paper laminates, water activated hot melt adhesive coated scrim reinforced tapes, and the like). When incorporated into these various end uses, the silane-functionalized resin is in some embodiments 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 above-described 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. According to one or more embodiments, the adhesive therefore 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, the adhesive in other embodiments comprises 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, these hot melt adhesives may, in certain embodiments, further comprise 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 tackifier resin different from the silane-functionalized resins described herein. Further, the adhesive in other embodiments comprises 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 tackifier resins include pure monomeric 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 Monomeric (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. Further, the adhesive in such embodiments comprises about 10 to 90, 20 to 80, 30 to 70, or about 40 to 60 weight percent of at least one tackifier. Suitable tackifiers contemplated herein include, for example, cycloaliphatic hydrocarbon resins, C5 hydrocarbon resins; C5/C9 hydrocarbon resin; aromatic modified C5 resin; c9 hydrocarbon resin; pure monomer resins, such as copolymers of styrene with alpha-methylstyrene, vinyltoluene, p-methylstyrene, indene, methylindene, C5 resin and C9 resin; a terpene resin; a terpene-phenol resin; terpene styrene resin; rosin esters; modified rosin esters; liquid resins of fully or partially hydrogenated rosins; fully or partially hydrogenated rosin esters; fully or partially hydrogenated modified rosin resins; fully or partially hydrogenated rosin alcohols; indene-coumarone (IC) thermoplastic resins, dicyclopentadiene (DCPD) thermoplastic resins, hydrogenated or partially hydrogenated dicyclopentadiene (DCPD) thermoplastic resins, fully or partially hydrogenated C5 resins; fully or partially hydrogenated C5/C9 resin; fully or partially hydrogenated aromatic modified C5 resin; fully or partially hydrogenated 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 treesLipids (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 adhesive comprises about 2 to 40, 5 to 30, 8 to 25, or about 10 to 20 weight percent of at least one processing oil. 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. One skilled in the art will recognize that the processing oil may also include extender oils commonly used in adhesives. The use of oil in the adhesive is desirable in some cases if the adhesive is to be used as a Pressure Sensitive Adhesive (PSA) to make a tape or label or as an adhesive for bonding nonwoven articles. In certain additional embodiments, the adhesive is free of 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 about 1 to 40, 5 to 30, 8 to 25, or 10 to 20 weight percent of at least one wax. Suitable waxes may include those known in the art, such as microcrystalline waxes, paraffin waxes, waxes made by the fischer-tropsch process, functionalized waxes (maleated, fumarated or functional waxes, etc.), and vegetable waxes. If the adhesive is to be used as a hot melt packaging adhesive, the use of wax in the adhesive may be desirable in some circumstances. In certain embodiments, the adhesive is free of 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 about 0.1 to 20, 1 to 10, 2 to 8, or 3 to 5 weight percent of at least one antioxidant. In other embodiments, the adhesive is free of antioxidants.

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 about 0.5 to 20, 1 to 10, 2 to 8, or 3 to 5 weight percent of at least one plasticizer. 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 (Eastman Chemical Co., Kingsport, TN, US) plasticizers.

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 about 1 to 90, 20 to 80, 30 to 70, or 40 to 55 weight percent of at least one filler. 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 comprising the disclosed functionalized resins for use in, for example, automotive components such as, but not limited to, tires and tire components, automotive belts, hoses, brakes, and the like, as well as non-automotive and/or mechanical devices, including technical rubber articles such as belts (bels) (as in conveyor belts), such as belts (straps), brakes, and hoses or tubing, and the like, as well as apparel articles such as, but not limited to, shoes, boots, slippers, and the like. The disclosed silane-functionalized resins can act 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 to many silane functions covalently attached to the polymer or resin structure via a polar group-containing linker (fig. 2B). In fig. 2A, element 110 corresponds to a polymer, and 100B corresponds to a resin. This is a theoretical depiction of the normal alignment that exists in such compositions using non-functionalized resins. In FIG. 2B, again, the polymer-equivalent element 110 and the equivalent polymer are shownAn element 100B of the resin, and an element 100A corresponding to a linker as contemplated herein. That is, in FIG. 2B, elements 100A and 100B together in a schematic diagram are equivalent to formula I, where the "resin" in formula I corresponds to portion 100B, and the remainder of the formula I equation, i.e., - [ Z ]_k-X_n-R¹-(CH₂)_m-Si(R²)_p]_qCorresponding to element 100A in fig. 2B.

Thus, a rubber composition comprising an elastomer, a filler, and the silica-functionalized resin disclosed herein is disclosed. The elastomer may be one or more of natural rubber, polyisoprene, styrene-butadiene rubber, polybutadiene, halobutyl rubber and nitrile rubber or functionalized rubber grades or rubber mixtures 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 comprises various polymers such as, but not limited to, polyisoprene (synthetic or natural), styrene-butadiene copolymers or butadiene polymers, and the like. Such rubber polymers may contain various modifications and/or functionalizations at the chain end or at pendant positions along the polymer chain. These modifications may contain 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 the skilled artisan, such as metal atoms, can also be included in the rubbery polymers used to make the disclosed tires and other rubber-containing components disclosed herein.

The rubber mixtures according to the disclosure also contain from 5 to 80 phr, preferably from 5 to 49 phr, particularly preferably from 5 to 30phr, very particularly preferably from 5 to 20 phr, of at least one additional diene rubber.

The at least one additional rubber is in this case 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 rubber One or more of a diene copolymer and/or a hydrated styrene-butadiene rubber.

In particular, nitrile rubber, hydrated acrylonitrile butadiene rubber, neoprene rubber, butyl rubber, halobutyl rubber, or ethylene-propylene-diene rubber is used in the production of technical rubber articles, such as belts, and hoses.

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

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

The rubber mixture may also contain at least one additional 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 with the reactive sites of the filler, i.e., with the hydroxyl groups of the silica or with 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 fillers.

The disclosed silane-functionalized resins can be incorporated into rubber mixtures by various methods known to the skilled artisan. For example, from 1 to 100 mole percent monomer, from 2 to 70 mole percent monomer, from 5 to 50 mole percent monomer bearing the functional group as end-capping and/or pendant functionalization may be incorporated into the rubber mixture. The amount of functionalized resin in the rubber mixture may be 5 to 400 phr, 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, mixtures of functionalized and unfunctionalized resins may be incorporated into the rubber mixture. The total resin content, including unfunctionalized resin and functionalized resin, may be 5 to 400 phr, 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., a highly pendant functionalized resin may be incorporated into the rubber mixture to achieve a phr value of 5 to 50 by dilution. Likewise, a mixture of end-capped and side-capped functionalized 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 amount of solution polymerized styrene-butadiene rubber present in the rubber mixture may be 5 to 50phr, 20 to 50phr, 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 of a polar or non-polar filler, such as silica, carbon black, aluminosilicate, chalk, starch, magnesium oxide, titanium dioxide and/or rubber gel 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 fillers. In addition, graphite and graphene, as well as "carbon-silica dual-phase filler" may be used as the filler. It is possible here to use any type of carbon black known to the person skilled in the art.

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. It is therefore also conceivable for the rubber mixtures according to the invention to comprise similar amounts of carbon black and silica, for example 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 about 1:150 to 100: 20.

In some embodiments, the rubber mixture contains 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 achieving particularly good rolling resistance index (resilience at 70 ℃) and tear properties for use in motor vehicle tyres.

When carbon black is present as filler, the amount of carbon black in the rubber mixture is preferably 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 50phr, 2 to 40 phr, 2 to 30phr, or more preferably 2 to 20 phr. However, preference is given to using carbon blacks having an iodine adsorption number according to ASTM D1510 of from 30 to 180 g/kg, preferably from 40 to 180 g/kg, particularly preferably from 40 to 130 g/kg, and a DBP number according to ASTM D2414 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.

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 includes having a thickness of 35 to 350 m²A/g, preferably from 35 to 260 m²Per g, particularly preferably from 100 to 260 m²Per g, most particularly preferably from 130 to 235 m²Nitrogen surface area (BET surface area) in g (according to DIN ISO 9277 and DIN 66132) and from 30 to 400 m²G, preferably from 30 to 250 m²Per g, particularly preferably from 100 to 250 m²Per g, most particularly preferably from 125 to 230 m²Finely divided, precipitated silica having a CTAB surface area per gram (according to ASTM D3765). Such silicas, when used in rubber mixtures such as tire treads, produceParticularly advantageous physical properties of the vulcanizate. 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, both those of the type Ultrasil VN3 (Evonik Industries AG, Essen, Germany) and the highly dispersible silicas such as the HD silicas described above (e.g. Zeosil 1165 MPRhodia-Solvay International Chemical Group, Brussels, Belgium).

In order to improve processability and to bond the silica and other polar fillers present in some embodiments to the diene rubber, silane coupling agents are used in various embodiments of the rubber mixtures. In such embodiments, one silane coupling agent or a plurality of different silane coupling agents in combination with each other are used. The rubber mixture, in some embodiments, therefore 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 discussed above, during mixing (in situ) of the rubber or rubber mixture or even prior to adding the filler to the rubber as a pre-treatment (pre-modification). In such embodiments, the silane coupling agent is any of those known to those skilled in the art to be suitable for use in the disclosed rubber mixtures. Non-limiting examples of conventional coupling agents are bifunctional organosilanes having on the silicon atom at least one alkoxy, cycloalkoxy or phenoxy group as leaving group and, as further function, a group which can chemically react with the double bond of the polymer, optionally after cleavage. The latter group in some embodiments, 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 in varying amounts with various sulfides. For example, TESPT may also be added as a mixture with industrial carbon black (X50S, Evonik Industries AG, Essen, Germany).

In a further 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, most particularly preferably 60 to 80% by weight of disulfide. Mixtures of this type, described for example in U.S. Pat. No. 8,252,863, are obtainable for example with 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 also be used, such as those described in U.S. patent nos. 7,968,633; 7,968,634, respectively; 7,968,635, respectively; and 7,968,636, and U.S. patent application publication nos. 20080161486; 20080161462, respectively; and 20080161452, or any combination thereof. Also suitable silanes are for example Momentive, the USA company under the name NXT, sold in different variants, or the Evonik Industries company under the name VP Si 363 @.

Furthermore, the rubber compound may contain 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 contain other 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 this embodiment, the rubber mixture contains 0phr of any other fillers. In this embodiment, it is therefore not necessary to add any secondary filler.

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

In one embodiment, the rubber mixture contains 0 to 70 phr, 0.1 to 60 phr, or 0.1 to 50phr of at least one plasticizer. These 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 (medium extraction solvent) or TDAE (treated distilled aromatic extract), rubber-to-liquid (RTL) or biomass-to-liquid (BTL) oils, factice (surfactants), plasticizing resins or liquid polymers (such as liquid BR), which have an average molecular weight (determined by Gel Permeation Chromatography (GPC) on the basis of iso bs 11344: 2004) of from 500 to 20000 g/mol. If liquid polymers are used as plasticizers in the rubber mixtures according to the invention, these are not counted as rubbers when calculating the composition of the polymer matrix.

In embodiments where mineral oils are used, the mineral oils are selected from one or more of DAE (distilled aromatic extracts) and/or RAE (residual aromatic extracts) and/or TDAE (treated distilled aromatic extracts) and/or MES (medium solvent extracted oils) and/or naphthenic and/or paraffinic oils.

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

a) antioxidants, for example N-phenyl-N ' - (1, 3-dimethylbutyl) -p-phenylenediamine (6 PPD), N ' -diphenyl-p-phenylenediamine (DPPD), N ' -ditolyl-p-phenylenediamine (DTPD), N-isopropyl-N ' -phenyl-p-phenylenediamine (IPPD), N ' -bis (1, 4-dimethylpentyl) -p-phenylenediamine (77 PD) 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 and non-functionalized resins, particularly adhesive tackifying resins, such as rosin and the like,

e) plasticizing adjuvants, e.g. 2, 2' -dibenzoyl-benzene-dicarbonamide-diphenyl-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 internal components of tyres or technical rubber articles in direct contact with the reinforcing support present, a suitable adhesive system (generally in the form of an adhesive tackifying resin) is also generally added to the rubber.

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

The proportion of the additional additives contained in the total also comprises 0.1 to 10 phr, preferably 0.2 to 8 phr, particularly preferably 0.2 to 4 phr, of zinc oxide (ZnO).

Such zinc oxide may be of any type known to the person skilled in the art, such as ZnO particles or powder. In general, conventionally used zinc oxides exhibit less than 10 m²BET surface area in g. However, a film having 10 to 60 m may also be used²So-called nano zinc oxide with BET surface area/g.

Vulcanization is carried out using a vulcanization accelerator in the presence of sulfur or a sulfur donor, some of which are also capable of acting as sulfur donors. Sulphur or a sulphur donor and one or more accelerators are added to the rubber mixture in the last mixing step in the amounts indicated above. 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, those selected from the group consisting of N-cyclohexyl-2-benzothiazolesulfenamide (CBS) and/or N, N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS), N-tert-butyl-2-benzothiazolesulfenamide (TBBS), mercaptobenzothiazole, tetramethylthiuram disulfide, benzothiazole disulfide, diphenylguanidine, zinc dithiocarbamate, alkylphenol disulfide, zinc butylxanthate, N-dicyclohexyl-2-benzothiazolesulfenamide, N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylenebenzothiazole-2-sulfenamide, N-diphenylthiourea, dithiocarbamoylsulfenamide, N-diisopropylbenzothiazole-2-sulfenamide, N-dimethylthioureas, 2-mercaptomethylbenzimidazole zinc, dithiobis (N-methylpiperazine), dithiobis (N- β -hydroxyethylpiperazine), dithiobis (dibenzylamine), and combinations thereof. Other vulcanization accelerators include, for example, thiuram and/or morpholine derivatives.

In one embodiment of the disclosed rubber compound, the compound contains CBS as an accelerator. Particularly good tear properties are thus achieved for such rubber mixtures.

Furthermore, network forming systems may also be used in the rubber mixtures, such as those available under the trade names Vulkuren (Lanxess, Shanghai, PRC), Duralink (ChemLink, Schoolraft, MI, US) and Perkalink ® (Lanxess, Shanghai, PRC) or as described in WO 2010/059402. This system contains a vulcanizing agent crosslinked with a functionality greater than 4 and at least one vulcanization accelerator. Curing agents that crosslink with a functionality greater than 4 have, for example, the general formula a:

G[C_aH_2a—CH₂—S_bY]_cA

wherein G is a polyvalent cycloalkyl and/or a polyvalent heteroalkyl and/or a polyvalent siloxane group containing 1 to 100 atoms; wherein each Y contains 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 groups are one or more of thiosulfonate groups, dithiocarbamate groups, thiocarbonyl groups, mercapto groups, hydrocarbyl groups, and sodium thiosulfonate (colored salt groups). This enables very advantageous wear and tear properties of the rubber mixtures according to the invention to be achieved.

Within the scope of this disclosure, sulfur and sulfur donors include sulfur donating silanes, such as TESPT, vulcanizing agents and vulcanizing agents (cures), such as those described in EP 2288653, vulcanization accelerators as described above and vulcanizing agents crosslinked with a functionality of greater than 4 as described in WO 2010/059402, such as vulcanizing agents of formula A), and the above systems Vulkuren [ (Lanxess, Shanghai, PRC), Duralink [ (ChemLink, Schoolraft, MI, US) and Perkalink [ (Lanxess, Shanghai, PRC) are combined under the term "vulcanizing agents (vulcanating agents)".

Rubber compounds according to the present disclosure may include at least one of these vulcanizing agents. It is possible to manufacture vulcanized products, in particular for motor vehicle tyres, from rubber mixtures according to the present disclosure.

In some embodiments, a vulcanization retarder is also present in the rubber compound. As is known in the art, there is often a "compromise" in tire technology between rolling resistance and wet braking. Typically, when one of the two elements is modified, the other element deteriorates. Therefore, an improvement in Rolling Resistance (RR) is often accompanied by a deterioration in wet braking performance, and vice versa. This is an RR-wet braking target conflict. Embodiments encompassed by the present disclosure thus include tires having surprisingly improved rolling resistance without wet braking variation. It is therefore an object of the disclosed rubber compositions to provide motor vehicle tires that exhibit improved rolling resistance behavior as well as snow performance. This object is achieved in that the motor vehicle tire contains a rubber mixture according to the present disclosure in at least one component as described above. In this respect, all the above-described embodiments of the ingredients and their properties apply.

It is a further object of the disclosed rubber composition to provide a motor vehicle tire exhibiting improved rolling resistance behavior and improved tear properties, in particular an increased tear propagation resistance. This object is achieved in that the motor vehicle tire contains a rubber mixture according to the present disclosure in at least one component as described above. In this respect, all the above-described embodiments of the ingredients and their properties apply.

In one embodiment, the component is a tread. As is known to those skilled in the art, the tread affects the overall rolling resistance of the tire to a relatively high degree. In particular, high resistance to cracking 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 include various tire components and various tire component compounds. The tire may be built, shaped, molded and cured by various methods 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 motor vehicle tires. According to the present disclosure, this object is achieved by using the above-described rubber mixtures (with all embodiments and features) in motor vehicle tires, in particular in motor vehicle tire treads and/or body mixtures (body mix) of motor vehicle tires.

Another object of the present disclosure is to optimize the wear behavior and tear properties of technical rubber articles, such as belts, brakes and hoses, without significant negative impact on other properties associated with the respective use.

This object is achieved by the use of the above-described rubber mixtures for the production of technical rubber articles, such as belts (e.g.conveyor belts, automobile engine belts, such as timing belts, conveyor belts, etc.), belts, seals, pipes and hoses. Another such technical rubber article is a shoe sole, e.g. for leisure shoes, running shoes, training shoes, boots, slippers and the like, an article to be worn on the foot to protect the foot and the associated bones and joints from damage caused by the vibrating or percussive movements associated with walking, running, jumping and the like and to provide excellent slip resistance in wet and/or dry conditions. Various methods are known in the art for incorporating rubber compounds into footwear. See, for example, U.S. patent application publication nos. 2013/0291409, 2011/0252671, and 8,689,381 (all of which are incorporated herein by reference in their entirety for all purposes).

The term body mix as used herein refers to a rubber mix for the inner components of a tire. The internal tire component basically includes a tie bar (squeegee), sidewalls, an inner liner (inner layer), a core profile (core profile), a belt (belt), shoulders, a belt profile (belt profile), a carcass ply, bead wires (bead wire), a cord profile (cable profile), a tread profile (horn profile), and a carcass tube (bag).

The production of the rubber mixtures disclosed is carried out by the methods customary in the rubber industry, in which a base mixture having all the constituents except the vulcanization system (sulfur and substances which influence vulcanization) is first produced in one or more mixing stages. The final mixture is made by adding the vulcanization system in the final mixing stage. The final mixture is further processed, for example by means of extrusion, and brought into the corresponding form.

For use in motor vehicle tyres, the mixture is preferably made into a tread and applied in a known manner in the manufacture of motor vehicle tyre blanks. However, the tread may also be wound onto the green tire in the form of a narrow strip of rubber compound. In a two-part tread (upper: crown and lower: base tread), the rubber mixtures according to the present disclosure may be used for both the crown and base tread.

The manufacture of the rubber mixtures according to the present disclosure for use as host mixtures in motor vehicle tires is carried out as described above for the treads. Except that it is molded after the extrusion process. The form of the rubber mixture according to the disclosure obtained in this way for one or more of the various body mixtures is then used for the manufacture of a green tire. For use of the rubber mixtures according to the disclosure in belts and belts, 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 supports, such as 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 supports and one and/or more additional 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, these materials, methods, and examples are illustrative only and not intended to be limiting.

Examples

Various functionalized resins have been prepared and tested in rubber mixtures for motor vehicle tires and in other compositions, such as adhesives and the like. Synthetic routes and experimental data are provided below.