Modified diene rubber

Abstract

1. A process for making a polydiene polymer having at least 50% by weight, based on the weight of the polymer, of units derived from one or more conjugated dienes, the process comprising polymerizing at least one aliphatic conjugated diene monomer having from 4 to 25 carbon atoms, and optionally one or more comonomers ... at least one aliphatic conjugated diene monomer having from 4 to 25 carbon atoms, and optionally one or more comonomers, the at least one aliphatic conjugated diene monomer having from 4 to 25 carbon atoms, JPEG2025505528000012.jpg29170, where the functionalized comonomer is used at the beginning of the polymerization to produce an alpha-functionalized polymer, or at the end of the polymerization to produce an omega-functionalized polymer, or during the polymerization to produce a backbone modified polymer, or a combination thereof, where in Formula (1), R 1 and R 2 is one or more ether or halogen atoms, and a group represented by the formula (2) (R 3 )(R 4 )(R 5 )Si-(2), which may optionally contain a trialkylsilane residue having 1 to 12 carbon atoms, 3 , R 4 and R 5 are independently selected from alkyl residues having 3 to 32 carbon atoms, which may optionally contain one or more ether or halogen atoms; R 3 , R 4 and R 5 At least one of R is branched. 1 and R 2 At least one of is a trialkylsilane residue of formula (2). Also provided are compositions comprising the polymer obtained by this method, articles comprising the cured polymer, and methods of making the cured articles.

Description

[Technical field]

[0001] Diene rubber is widely used as a raw material for producing tires. [Background technology]

[0002] Rubber can be functionalized to contain one or more polar groups, for example, by treating the polymer with a functionalizing agent or by using a functionalizing comonomer in the polymerization reaction, or both. Functionalized rubbers are known to improve the interaction between rubber and fillers in tire compounds and thus the final properties of the tire. However, functionalized rubbers are more difficult to process than their non-functionalized counterparts, which is believed to be brought about by the interaction of the functional groups. In (Patent Document 1), functionalized rubbers are disclosed, which are obtained by using a vinylstyrene comonomer containing two functional groups selected from the group consisting of carbon, hydrogen, and silicon. As specific examples, methyl and ethyl groups were reported which may be used as phenol protecting groups, silicon-based functional groups (functional groups containing carbon, hydrogen, and silicon), such as trimethylsilyl and triethoxysilyl groups. Of these, preferred were hydrocarbon-based functional groups, preferably alkyl groups. Polymers produced with functionalized styrene were reported to have improved fuel efficiency values ​​and improved wet grip. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] US Patent Application Publication No. 2021 / 0230416A1 Summary of the Invention [Problem to be solved by the invention]

[0004] However, it was found that polymers functionalized with phenols containing fewer alkoxysilyl groups were difficult to polymerize and did not yield well-defined polymers. [Means for solving the problem]

[0005] Thus, in one aspect, there is provided a method for making a polydiene polymer having at least 51 wt. % of units derived from one or more conjugated dienes, based on the weight of the polymer, the method comprising polymerizing at least one aliphatic conjugated diene monomer having from 4 to 25 carbon atoms, and optionally one or more comonomers, the method comprising polymerizing at least one functionalized comonomer according to formula (1): [ka] wherein the functionalizing comonomer is used at the beginning of the polymerization to produce an alpha-functionalized polymer, or at the end of the polymerization to produce an omega-functionalized polymer, or during the polymerization to produce a backbone modified polymer, or a combination thereof, wherein in formula (1): R 1 and R 2 are independently selected from alkyl residues having 1 to 12 carbon atoms, which may optionally contain one or more halogen atoms or catenary ether oxygen atoms), and a trialkylsilane residue of formula (2) (R 3 )(R 4 )(R 5 )Si-(2) (In the formula, R 3 , R 4 and R 5 are independently selected from alkyl residues having 3 to 32 carbon atoms, which may optionally contain one or more halogen atoms or catenary ether oxygen atoms; R 3 , R 4 and R 5 At least one of R 1 and R 2wherein at least one of is a trialkylsilane residue of formula (2).

[0006] In another aspect, a composition is provided comprising the polymer obtained by this method.

[0007] In a further aspect, an article is provided comprising a cured composition obtained by subjecting the composition to a curing reaction.

[0008] In yet a further aspect, a method of making a cured article is provided that includes subjecting the composition to a curing reaction. [Brief description of the drawings]

[0009] [Figure 1] Figure 1 shows the GPC traces for determining the polydispersity index of the polydiene polymers obtained in the Examples section. The GPC traces of the comparative polymers obtained with TES-4VG (functionalized comonomers with linear functional groups) are very broad and therefore show poorly characterized polymers with many different molecular weight fractions. The polymers obtained with functionalized comonomers according to the present disclosure were well defined and had GPC traces similar to those of the unfunctionalized or differently functionalized reference polymers. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present disclosure is further illustrated in the detailed description that follows.

[0011] In the following description, reference may be made to specific standards (ASTM, DIN, ISO, etc.). Unless otherwise indicated, the standards are used in the version in effect on March 1, 2020. If there is no version in effect on that date, for example because the standard has expired, the reference is to the version in effect on the date closest to March 1, 2020.

[0012] All documents cited in this description are incorporated by reference unless otherwise indicated.

[0013] In the following description, the amounts of components of a composition or polymer may be interchangeably referred to as "weight percent," "wt.%," or "wt %." The terms "weight percent," "wt.%," or "wt %" are based on the total weight of the composition or polymer, respectively, which is 100% unless otherwise indicated.

[0014] The term "phr" means "parts per hundred of rubber," i.e., the weight percentages of components of a composition containing one or more rubbers are based on the total amount of rubber, which is set at 100% by weight. Thus, the total weight of the composition is usually greater than the amount of rubber, and may be greater than 100% by weight.

[0015] Ranges identified in this disclosure are meant to include and disclose all values ​​between the endpoints of the range, as well as those endpoints, unless otherwise stated.

[0016] The terms "comprising", "containing" and "having" are used in an open, non-limiting sense. For example, the phrase "a composition comprising components A and B" means that the composition includes components A and B, but may also have other components. In contrast to the use of "comprising", "containing" or "having", the word "consisting of" is used in a narrow, limiting sense. The phrase "a composition consisting of components A and B" is meant to describe a composition that has components A and B and no other components.

[0017] Functionalized Comonomers The functionalized comonomer according to the present disclosure corresponds to the general formula (1): [ka] wherein the functionalizing comonomer is used at the beginning of the polymerization to produce an alpha-functionalized polymer, or at the end of the polymerization to produce an omega-functionalized polymer, or during the polymerization to produce a backbone modified polymer, or a combination thereof, wherein in formula (1): R 1 and R 2 are independently selected from alkyl residues having 1 to 12 carbon atoms, optionally containing one or more halogen atoms or catenary ether oxygen atoms, and a trialkylsilane residue of formula (2): (R 3 )(R 4 )(R 5 )Si-(2), In the formula, R 3 , R 4 and R 5 are independently selected from alkyl residues having 3 to 32 carbon atoms, which may optionally contain one or more halogen atoms or catenary ether oxygen atoms; R 3 , R 4 and R 5 At least one of R 1 and R 2 At least one of the branched alkyl residues corresponds to the general formula (3): (R')(R'')(R'')C-(CH2) n -(3), wherein n represents 0, 1, or 2, and R', R'', and R''', independently of one another, are selected from H or alkyl of 1 to 10 carbon atoms, which may optionally contain one or more halogen atoms or catenary ether oxygen atoms, with the proviso that not more than one of R', R'', and R''', is H. Preferably, R', R'', and R''', independently of one another, are selected from alkyl of 1 to 5 carbon atoms. Preferably, n is 0.

[0018] In one embodiment of the present disclosure, the trialkylsilane residue is selected from (R')(R")(R"')Si-, where R' and R" are both selected from methyl, ethyl, propyl, butyl, and R'" is selected from tert-butyl, sec-butyl, neopentyl, isopropyl. In another embodiment of the present disclosure, R', and preferably R' and R" are tert-butyl.

[0019] In another embodiment of the present disclosure, the trialkylsilane residue is selected from (R')(R")(R"')Si-, where R' is selected from methyl, ethyl, propyl, butyl, and both R" and R"' are independently selected from tert-butyl, sec-butyl, neopentyl, isopropyl. In another embodiment of the present disclosure, R', preferably R' and R" are tert-butyl.

[0020] In one embodiment of the present disclosure, R 1 or R 2 Preferably, R 1 is a linear or branched alkyl group having 1 to 6 carbon atoms, preferably a methyl or ethyl group.

[0021] Specific examples include, but are not limited to, tert-butyldimethylsilyloxy-4-vinyl-2-methoxybenzene; 2-tert-butyldimethylsilyloxy-4-vinyl-1-methoxybenzene; tert-butyldimethylsilyloxy-4-vinyl-2-ethoxybenzene; 2-tert-butyldimethylsilyloxy-4-vinyl-1-ethoxybenzene; 2-tert-butyldimethylsilyloxy-4-vinyl-1-propoxybenzene, tert-butyldimethylsilyloxy-4-vinyl-2-propoxybenzene, and combinations thereof.

[0022] A functionalized comonomer is used in the reaction with a conjugated diene monomer to produce a polydiene polymer. The functionalized comonomer can be used at the beginning of the polymerization reaction to produce an alpha-functionalized polydiene polymer, or at the end of the polymerization to produce an omega-functionalized polydiene polymer, or during the polymerization to produce a backbone-modified polydiene polymer, or combinations thereof. The functionalized monomer contains the functional group -OR 1 -OR 2 is introduced into the polymer. 1 -OR 2 Since at least one of the groups is a siloxane group, they can be converted, for example, to -OH or -OM groups (where M is a cation) by a treatment that includes reacting at least one of the groups with an acidic reagent. Acidic reagents include Bronsted acids and Lewis acids. -OR 1 -OR 2 A polydiene polymer that has been treated to convert the residue R to a carboxylic acid or both is referred to herein as a "converted polymer." In one embodiment, the method according to the present disclosure comprises treating the polydiene polymer with at least one acidic agent to convert the residue R to a carboxylic acid or both. 1 and R 2 with a hydrogen or a cation.

[0023] In one embodiment of the present disclosure, the functionalized monomer reacts with itself to produce a second functionalized comonomer comprising repeat units derived from the functionalized comonomer according to formula (1). This second functionalized monomer, also referred to herein as a "multifunctionalized monomer", can be used in a polymerization reaction with one or more conjugated dienes and other copolymerizable comonomers to produce a polydiene polymer according to the present disclosure. Such a second functionalized monomer can be produced in essentially the same manner as described below to make a polymer, except that only a small amount of repeat units, for example, 2 to 1,000 or 10 to 100 repeat units, can be used. The multifunctionalized comonomer can be added before, during, or at the end of the polymerization reaction with the conjugated monomer. Preferably, at least one functionalized monomer is first reacted to produce a second functionalized comonomer before the conjugated diene is reacted in the polymerization reaction, because this can increase the conversion rate of the diene, thus resulting in faster polymerization.

[0024] The amount of functional comonomer used may include, for example and without limitation, an amount of 0.001% to 10% by weight, or 0.1% to 1% by weight, based on the total weight of the polymer. Thus, a polydiene polymer according to the present disclosure may contain 0.001 to 10% by weight of units derived from one or more functional comonomers according to formula (1) or converted forms thereof, -OR 1 -OR 2 At least one of is replaced by -OH or -OM, where M represents an organic or inorganic cation.

[0025] Polydiene Polymer The polydiene polymers according to the present disclosure preferably contain at least 51% by weight, based on the total weight of the polymer, of units derived from one or more conjugated diene monomers. The conjugated diene monomers may have from 4 to 25 carbon atoms.

[0026] The polymer may be a homopolymer or a copolymer and comprises units derived from at least one conjugated diene monomer. Suitable diene monomers include, but are not limited to, 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, 1,3-hexadiene, myrcene, ocimene, farnesene, and combinations thereof. Preferably, the polymer comprises or consists of units derived from 1,3-butadiene.

[0027] In one embodiment of the present disclosure, the polymer is a copolymer obtained by a process comprising a polymerization reaction comprising at least two conjugated dienes. In another embodiment of the present disclosure, the polymer is a copolymer obtained by a process comprising polymerizing at least one conjugated diene monomer and at least one vinyl aromatic comonomer. Examples of suitable vinyl aromatic comonomers include, but are not limited to, styrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, para-tertbutylstyrene, vinylnaphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene, and combinations thereof. Styrene is particularly preferred.

[0028] In one embodiment of the present disclosure, the polymer is a butadiene polymer, including homopolymers and copolymers of 1,3-butadiene. Preferably, the polymer according to the present disclosure contains at least 50% by weight, preferably at least 60% by weight, of units derived from 1,3-butadiene, based on the weight of the polymer. In one embodiment of the present disclosure, the diene polymer contains at least 60% by weight, or at least 75% by weight, of units derived from 1,3-butadiene.

[0029] In one embodiment of the present disclosure, the diene polymer contains from 0 to 49 wt. %, or from 0 wt. % to 40 wt. %, of units derived from one or more comonomers, based on the total weight of the polymer.

[0030] In one embodiment of the present disclosure, the diene polymer contains at least 60%, or at least 70%, by weight of units derived from 1,3-butadiene and 0-40%, or 0-30%, by weight of units derived from one or more comonomers.

[0031] In one embodiment, the diene polymers of the present disclosure contain from 0 to 20 weight percent units derived from one or more conjugated dienes other than 1,3 butadiene.

[0032] In one embodiment, the polydiene polymers according to the present disclosure contain at least 50 wt. % and preferably at least 60 wt. % of units derived from 1,3-butadiene and up to 49 wt. % of units derived from one or more vinyl aromatic comonomers, preferably 5 wt. % to 40 wt. %, or 10 wt. % to 35 wt. % of units derived from one or more vinyl aromatic comonomers, based on the weight of the polymer.

[0033] In one embodiment, a polymer according to the present disclosure comprises at least 75% or at least 95% by weight of units derived from one or more conjugated diene monomers. In one embodiment, a polymer according to the present disclosure comprises from 55% to 92% by weight of units derived from one or more conjugated diene monomers and from 5.8% to 45% by weight of units derived from a vinyl aromatic comonomer.

[0034] Suitable copolymerizable comonomers further include one or more alpha-olefins, such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and combinations thereof.

[0035] In one embodiment, the diene polymers according to the present disclosure contain from 0 to 20 weight percent of units derived from ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and combinations thereof.

[0036] Suitable comonomers also include one or more other copolymerizable comonomers that introduce functional groups (other than the functional comonomers listed above), including, but not limited to, crosslinking sites, branching sites, branching, or functionalizing groups. In one embodiment of the present disclosure, the diene polymer contains 0% to 10% or 0% to 5% by weight of units derived from one or more of such other comonomers.

[0037] Combinations of one or more comonomers of the same chemical type as described above, as well as combinations of one or more comonomers from different chemical types may be used.

[0038] Diene polymers according to the present disclosure may have a Mooney viscosity ML1+4 at 100° C. of from 10 to 200 Mooney units, for example, from 30 to 150 or from 35 to 85 Mooney units.

[0039] The diene polymer according to the present disclosure may have a number average molecular weight (Mn) of 10,000 g / mol to 2,000,000 g / mol, or 100,000 to 1,000,000 g / mol, for example, 100,000 to 400,000 g / mol or 200,000 to 300,000 g / mol. In one embodiment of the present disclosure, the polymer has a Mn of 150 kg / mol to 320 kg / mol.

[0040] The diene polymer according to the present disclosure may have a dispersity (also referred to herein as molecular weight distribution or MWD) of 1.03 to 25, for example, 1.03 to 5. In one embodiment of the present disclosure, the polymer has an MWD of 1.03 to 3.5 or 1.03 to 2.40. MWD is the ratio of weight average molecular weight (Mw) to number average molecular weight Mn, i.e., MWD is equal to Mw / Mn.

[0041] The diene polymers according to the present disclosure are typically rubbers and typically have a glass transition temperature of less than 20° C. They may have a glass transition temperature (Tg) of, for example, −120° C. to less than 20° C. In preferred embodiments of the present disclosure, the polymers have a Tg of 0° C. to −110° C. or −10° C. to −80° C. In one embodiment of the present disclosure, the butadiene polymer has a glass transition temperature of about −90° to −110° C.

[0042] In one embodiment of the present disclosure, the diene polymer has a number average molecular weight of 100,000 to 1,000,000, a Mooney viscosity ML1+4 at 100°C of 30 to 150 units, and a glass transition temperature of -110°C to 0°C.

[0043] In one embodiment, the diene polymer according to the present disclosure has a Mooney viscosity ML1+4 at 100° C. of 30 to 150 units, a number average molecular weight of 100,000 to 400,000 g / mol, a glass transition temperature of −110° C. to 0° C., and a molecular weight distribution (MWD) of 1.03 to 2.40.

[0044] The polydiene polymer according to the present disclosure may be further functionalized and may contain one or more functional groups introduced by one or more functionalizing agents. Typically, such groups, preferably terminal groups, contain, in addition to C and H atoms, at least one heteroatom selected from Si, S, N, O and combinations thereof, in particular a combination of Si and O atoms, Si and S atoms, or Si, O and N atoms. Such further functionalized polymers can be obtained, for example, by a reaction comprising reacting a reactive polymer chain end with at least one functionalizing agent containing, in addition to C and H atoms, at least one heteroatom selected from Si, S, N, O and combinations thereof. If necessary, the reaction product of the functionalization reaction can be subsequently treated to introduce at least one -OH, -SH or -COOH group or combinations thereof, or -O. - , -S - , -COO -Such treatment may include, for example, performing a hydrolysis reaction by adding an alcohol or an acid, or reacting with a first functionalizing reagent to remove at least one -OH, -SH, or -COOH group or a combination thereof, or to remove at least one -O ... - , -S - , -COO - The anionic forms thereof include those of the formula (I) and (II) which are selected from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28

[0045] Alternatively, or in addition, coupling agents may be used to link the polymer chains, as known in the art. Exemplary coupling agents known in the art include, but are not limited to, tetraalkoxysilane and tetrachlorosilane.

[0046] Methods for making polymers The homopolymers or copolymers of the present disclosure can be prepared by methods known in the art. The polymerization can be carried out to produce statistical polymers, also called random copolymers, block copolymers, gradient copolymers, or combinations thereof, including linear and branched structures as known to those skilled in the art.

[0047] The polymers can be obtained by a process comprising anionic polymerization or catalytic polymerization using one or more coordination catalysts. Coordination catalysts in this context comprise Ziegler-Natta catalysts or single metal catalyst systems. Preferred coordination catalysts are those based on Ni, Co, Ti, Zr, Nd, V, Gd, Cr, Mo, W or Fe. Preferably, the polymerization reaction comprises anionic solution polymerization. The initiator for anionic solution polymerization preferably comprises an organometallic based on an alkali or alkaline earth metal. Examples include, but are not limited to, methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, pentyllithium, n-hexyllithium, cyclohexyllithium, octyllithium, decyl-lithium, 2-(6-lithio-n-hexoxy)tetrahydropyran, 3-(tert-butyldimethylsiloxy)-1-propyllithium, phenyllithium, 4-butylphenyllithium, 1-naphthyllithium, p-toluyllithium and allyllithium compounds derived from tertiary N-allylamines, e.g., [1 -(dimethylamino)-2-propenyl]lithium, [1-[bis(phenylmethyl)amino]-2-propenyl]lithium, [1-(diphenylamino)-2-propenyl]lithium, [1-(1-pyrrolidinyl)-2-propenyl]lithium, lithium amides of secondary amines, such as lithium pyrrolidide, lithium piperidide, lithium hexamethyleneimide, lithium 1-methylimidazolidide, lithium 1-methylpiperazide, lithium morpholide, lithium dicyclohexylamide, lithium dibenzylamide, lithium diphenylamide. Allyl lithium compounds and lithium amides can also be prepared in situ by reacting organolithium compounds with the respective tertiary N-allyl amines or with the respective secondary amines. Bifunctional and polyfunctional organolithium compounds, such as 1,4-dilithiobutane, dilithium piperazide, can also be used. Preferably, n-butyl lithium, sec-butyl lithium or combinations thereof are used.The initiator generates an anionically reactive monomer, and the polymerization is propagated by reaction of the reactive carbanionic monomer with other monomers to generate reactive carbanionic polymer chain ends. In the case of polymerization using one or more coordination catalysts, the reactive chain ends are generated by the catalyst. Preferably, the polydiene polymer is modified at the beginning of the polymer chain, i.e., at the alpha position, when a functionalizing monomer or a multifunctionalizing monomer or both are present at the start of the polymerization reaction before the conjugated diene is added.

[0048] Randomizers and control agents as known in the art can be used in the polymerization to control the structure of the polymer, in particular to avoid aggregation or to increase random structure. Such agents include, for example, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-butyl ether, ethylene glycol di-tert-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, diethylene glycol di-tert-butyl ether, 2-(2-ethoxyethoxy)-2-methyl-propane, triethylene glycol diethyl ... Examples of suitable randomizing agents include potassium and sodium salts of ethylene glycol dimethyl ether, tetrahydrofuran, ethyl tetrahydrofurfuryl ether, hexyl tetrahydrofurfuryl ether, 2,2-bis(2-tetrahydrofuryl)propane, dioxane, trimethylamine, triethylamine, N,N,N',N'-tetramethyl-ethylenediamine, N-methylmorpholine, N-ethylmorpholine, 1,2-dipiperidinoethane, 1,2-dipyrrolidinoethane, 1,2-dimorpholinoethane, alcohols, phenols, carboxylic acids, sulfonic acids, and combinations thereof. In one embodiment of the present disclosure, the polymer is a random polymer, and preferably, at least one randomizing agent is used in the polymerization reaction.

[0049] In one embodiment of the present disclosure, the polymer is a random polymer. In one embodiment, the polymer is a block copolymer. For the production of block copolymers, the polymerization preferably starts with one monomer, followed by the addition of other (co)monomers, depending on the size of the block to be carried out. The order of monomer addition can be adapted depending on what blocks of different monomers are desired to be produced. In one embodiment of the present disclosure, such blocks are produced at the beginning of the polymerization or at the end of the polymerization, or both.

[0050] In one embodiment, the polymerization is carried out in the presence of at least one solvent, preferably in solution. Preferred solvents for solution polymerization include inert aprotic solvents, such as aliphatic hydrocarbons. Specific examples include, but are not limited to, butane, pentane, hexane, heptane, octane, decane, and cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, 1,4-dimethylcyclohexane, and combinations thereof, including their isomers. Further examples include alkenes, such as 1-butene, or aromatic hydrocarbons, such as benzene, toluene, ethylbenzene, xylene, diethylbenzene, or propylbenzene, and combinations thereof. These solvents can be used individually or as mixtures. Preferred solvents include cyclohexane, methylcyclopentane, and n-hexane. The solvent can also be mixed with a polar solvent, if appropriate.

[0051] The polymerization can be carried out by first introducing the (co)monomer and solvent and then initiating the polymerization by adding an initiator or catalyst. The polymerization can also be carried out in a feed process, where the polymerization reactor is filled by adding the monomer and solvent. The initiator or catalyst is introduced or added together with the monomer and solvent. Variations can be used, such as introducing the solvent into the reactor, adding the initiator or catalyst, followed by adding the monomer. The polymerization can be carried out in a continuous mode or batchwise. Additional monomer and solvent can be added during or at the end of the polymerization. When a functionalized comonomer is added or present during the polymerization, the functionalized comonomer is incorporated into the polymer backbone, resulting in a backbone-modified polydiene polymer.

[0052] The polymerization can be carried out at normal pressure or at elevated pressure (e.g., 1-10 bar) or at reduced pressure. Typical reaction temperatures include room temperature, but depending on the nature and amount of comonomer, the reaction temperature can be above or below room temperature. Typical ranges include, for example, -12°C to 140°C in a continuous adiabatic process, or 50-120°C in a batch process.

[0053] The polymerization reaction results in reactive polymer chain ends, preferably anionic chain ends. To generate functional groups at the polymer chain ends (omega positions), functionalized comonomers or functionalizing agents according to the present invention may be added to the polymerization medium near the end of the reaction. Thus, the method according to the present disclosure may further comprise a step of reacting the polymer with at least one functionalizing reagent for introducing at least one functional group into the polymer. Typically, such functionalizing agents are aliphatic compounds that contain, in addition to carbon and hydrogen atoms, heteroatoms selected from Si, O, S and N, preferably combinations of heteroatoms selected from Si and O, combinations of Si, O and S, and combinations of Si, O and N, or combinations of N and O. Typically, they result directly or by hydrolysis or reaction with another functionalizing agent or both, in a polymer with at least one polar group selected from -OH, -COOH, -SH or salts thereof and combinations thereof. Preferably, the functionalizing agent has a molecular weight of less than 5,000 g / mol or even less than 2,000 g / mol.

[0054] Functionalizing agents as known in the art may be used. Examples of functionalizing agents include, but are not limited to, linear or branched alkoxysilanes, as well as those described in US Patent Application Publication No. 2013 / 0281605A1, US Patent Application Publication No. 2013 / 0338300A1, US Patent Application Publication No. 2013 / 0280458A1, US Patent Application Publication No. 2016 / 0075809A1, US Patent Application Publication No. 2016 / 0083495A1, WO 2021 / 009154A1, US Patent No. 4,894,409, and WO 2021 / 009156. Preferred functionalizing agents are linear or branched alkoxysilanes, linear or branched silanes, and [ka] and combinations thereof.

[0055] In one embodiment of the present disclosure, the functionalizing reagent is a linear or branched silane or siloxane. In another embodiment of the present disclosure, the functionalizing reagent is a cyclic reagent. In one embodiment of the present disclosure, the functionalizing reagent is cyclic and has a 4-7 membered aliphatic cyclic ring, more preferably a 5- or 6-membered aliphatic cyclic ring, where the ring has at least 2, preferably at least 3 carbon atoms, and at least one heteroatom selected from N, O, S, Si, or a combination thereof. In another embodiment of the present disclosure, the functionalizing reagent is cyclic and has a 3-20 membered ring structure, where the ring has at least 2, preferably at least 3 -Si(R1R2)-O- units, where R1 and R2 are each independently a C1-C cyclic ring that may optionally contain one or more heteroatoms selected from H; O, N, S, Si, or a combination thereof. 10 Preferably, R1 and R2 are selected from the group consisting of methyl, ethyl, propyl and butyl.

[0056] Functionalizing reagents according to formula (6): The reagent according to formula (6) includes cyclosiloxane-based functionalizing reagents. In formula (6), R1 and R2 may be the same or different and may be H, C1-C 10 Saturated or unsaturated hydrocarbon residues, preferably C1-C corresponding to methyl, ethyl, propyl, butyl and vinyl or allyl. 10 The saturated or unsaturated hydrocarbon residue optionally contains one or more heteroatoms selected from O, N, S, Si, or combinations thereof, where n is an integer selected from 3 to 10, preferably 4 to 6. Specific examples of reagents according to formula (6) include, but are not limited to, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, and as described, for example, in U.S. Patent Application Publication No. 2016 / 0075809 A1, the reagents according to formula (6) can be directly or indirectly (e.g., via subsequent hydrolysis) converted to silanols (-Si(R1)(R2)-OH) or silanolates (-Si(R1)(R2)-O-H). - ) groups.

[0057] Functionalizing reagents according to formula (7): Reagents according to formula (7) include silalactone-based functionalizing reagents. In formula (7), R 1 and R 2 are the same or different and are each selected from H or a residue having 1 to 20 carbon atoms, preferably selected from alkyl, alkoxy, cycloalkyl, cycloalkoxy, aryl, aryloxy, alkaryl, alkaryloxy, aralkyl, or aralkoxy; R 3 , R 4 are the same or different and each is selected from H or a residue having 1 to 20 carbon atoms, preferably from alkyl, cycloalkyl, aryl, alkaryl or aralkyl, A is preferably a divalent organic group having 1 to 26 carbon atoms, which may contain, in addition to hydrogen atoms, heteroatoms selected from O, N, S and Si.

[0058] Preferably, R 1 , R 2 are the same or different and may contain H, optionally one or more heteroatoms selected from O, N, S or Si, (C1-C 24 )-Alkyl, (C1-C 24 )-Alkoxy, (C3-C 24 )-Cycloalkyl, (C3-C 24 )-Cycloalkoxy, (C6-C 24 )-aryl, (C6-C 24 )-aryloxy, (C6-C 24 )-Alkaryl, (C6~C 24 )-alkaryloxy, (C6-C 24 )-Aralkyl or (C6-C 24 )-aralkoxy groups.

[0059] Preferably, R 3 , R 4are the same or different and contain one or more heteroatoms selected from H, optionally O, N, S or Si, (C1-C 24 )-Alkyl, (C3-C 24 )-Cycloalkyl, (C6-C 24 )-aryl, (C6-C 24 )-alkaryl or (C6-C 24 )-aralkyl groups.

[0060] In one embodiment of the present disclosure, A is -Xn-(CY1H)m-(CY2Y3)o-(CY1H)p- wherein: n is 1 or 0, m is 1, 2, 3 or 4, o is 0, 1 or 2 and p is 0, 1 or 2, preferably the sum of n, m, o and p is 2 or 3; X is O, S, NR, R is H or C1-C3 alkyl, or X is N(Si(alkyl)3), each "alkyl" independently represents C1-C6 alkyl, -oxyalkyl, or alkoxy; Y1 is H or a C1-C3 alkyl, Y2 is H or a C1-C3 alkyl, and Y3 is H or a C1-C3 alkyl, and preferably, at least one of Y2 and Y3 is H.

[0061] Specific non-limiting examples of A include: -CH2-;-CH2CH2-;-CH2CH2CH2-;-C(CH3)-CH2-;-CH2-C(CH3)-CH-;-CH(CH3)-C(CH3)H-; -CH(CH3)-CH2-C(CH3)H-;-CH2-C(CH3)HC(CH3)H-;-CH(CH3)-C(CH3)H-CH2-;-O-CH2-; -O-CH2CH2-;-O-CH2CH2-CH2-;-OC(CH3)H-;-O-CH2CH2-;-OC(CH3)H-CH2-; -O-CH2-C(CH3)H-;-O-CH2-C(CH3)H-CH2-;-O-CH2CH2-C(CH3)H-;-OC(CH3)H-CH2-CH2-; -S-CH2-;-S-CH2CH2-;-S-CH2CH2-CH2-;-SC(CH3)H-;-S-CH2CH2-;-SC(CH3)H-CH2-; -S-CH2-C(CH3)H-;-S-CH2-C(CH3)H-CH2-;-S-CH2CH2-C(CH3)H-;-SC(CH3)H-CH2-CH2-; -NH-CH2-;-NH-CH2CH2-;-NH-CH2CH2-CH2-;-NH-C(CH3)H-CH2-;-NH-CH2-C(CH3)H-; -NH-CH2-C(CH3)H-CH2-;-NH-CH2CH2-C(CH3)H-;-NH-C(CH3)H-CH2-CH2-; -N(CH3)-CH2-;-N(CH3)-CH2-;-N(CH3)-CH2CH2-;-N(CH3)-CH2CH2-CH2-; -N(CH3)-C(CH3)H-CH2-;-N(CH3)-CH2-C(CH3)H-;-N(CH3)-CH2-C(CH3)H-CH2-; -N(CH3)-CH2CH2-C(CH3)H-;-N(CH3)-C(CH3)H-CH2-CH2-; N(Si(alkyl)3)-CH2-;-N(Si(alkyl)3)-CH2CH2-;N(Si(alkyl)3)-CH2CH2CH2-; -N(Si(alkyl)3)-C(CH3)H-;-N(Si(alkyl)3)-CH2CH2-;-N(Si(alkyl)3)-C(CH3)H-CH2-; -N(Si(alkyl)3)-CH2-C(CH3)H-;-N(Si(alkyl)3)-CH2-C(CH3)H-CH2-; -N(Si(alkyl)3)-CH2CH2-C(CH3)H-;-N(Si(alkyl)3)-C(CH3)H-CH2-CH2- Includes:

[0062] Examples of reagents according to formula (7) include 2,2-dimethyl-1-oxa-2-silacyclohexane-6-one, 2,2,4-trimethyl-1-oxa-2-silacyclohexane-6-one, 2,2,5-trimethyl-1-oxa-2-silacyclohexane-6-one, 2,2,4,5-tetramethyl-1-oxa-2-silacyclohexane-6-one, 2,2-diethyl-1-oxa-2-silacyclohexane-8-one, 2,2-diethoxy-1-oxa-2-silacyclohexane-6-one, 2,2-dimethyl-1,4- Dioxa-2-silacyclohexane-6-one, 2,2,5-trimethyl-1,4-dioxa-2-silacyclohexane-6-one, 2,2,3,3-tetramethyl-1,4-dioxa-2-silacyclohexane-6-one, 2,2-dimethyl-1-oxa-4-thia-2-silacyclohexane-6-one, 2,2-diethyl-1-oxa-4-thia-2-silacyclohexane-6-one, 2,2-diphenyl-1-oxa-4-thia-2-silacyclone-6-one, 2-methyl-2-ethenyl-1-oxa- 4-Thia-2-silacyclohexan-6-one, 2,2,5-trimethyl-1-oxa-4-thia-2-silacyclohexan-6-one, 2,2-dimethyl-1-oxa-4-aza-2-silacyclohexan-6-one, 2,2,4-trimethyl-1-oxa-4-aza-2-silacyclohexan-6-one, 2,4-dimethyl-2-phenyl-1-oxa-4-aza-2-silacyclohexan-6-one, 2,2-dimethyl-4-trimethylsilyl-1-oxa-4-aza-2-silacyclohexan-8-one, 2 ,2-diethoxy-4-methyl-1-oxa-4-aza-2-silacyclohexan-6-one, 2,2,4,4-tetramethyl-1-oxa-2,4-disilacyclohexan-8-one, 3,4-dihydro-3,3-dimethyl-1H-2,3-benzoxasilin-1-one, 2,2-dimethyl-1-oxa-2-silacyclopentan-5-one, 2,2,3-trimethyl-1-oxa-2-silacyclopenten-5-one, 2,2-dimethyl-4-phenyl-1-oxa-2-silacyclopentan-5-one, 2,24(tert-butyl)-1-oxa-2-silacyclopentan-5-one, 2-methyl-2-(2-propen-1-yl)-1-oxa-2-silacyclopentan-5-one, 1,1-dimethyl-2,1-benzoxasirol-3(1H)-one, 2,2-dimethyl-1-oxa-2-silacycloheptan-7-one.

[0063] Reagents according to formula (7) are described, for example, in US Patent Application Publication No. 2016 / 0075809A1, in particular in paragraphs

[0034] to

[0042] . The use of such a reagent, either alone or by adding it to another functionalizing reagent, for example a reagent according to formula (6), can be used to form silacarboxylate groups, for example those of the general formula -Si(R 1 )(R 2 )-C(R 3 )(R 4 )-A-COO - This can result in the generation of radicals according to the formula:

[0064] Functionalizing reagents according to formula (8): The reagent according to formula (8) comprises an oxa-silacycloalkane. 1 , R 2 , R 3 , R 4and A are the same as described for formula (7). Examples of specific reagents according to formula (8) include 2,2-dimethyl-1-oxa-2-silacyclohexane, 2,2-diethyl-1-oxa-2-silacyclohexane, 2,2-dipropyl-1-oxa-2-silacyclohexane, 2-methyl-2-phenyl-1-oxa-2-silacyclohexane, 2,2-diphenyl-1-oxa-2-silacyclohexane, 2,2,5,5-tetramethyl-1-oxa-2-silacyclohexane, 2,2,3-trimethyl-1-oxa-2-silacyclohexane, 2,2-dimethyl- These include 1-oxa-2-silacyclopentane, 2,2,4-trimethyl-1-oxa-2-silacyclopentane, 2,2-dimethyl-1,4-dioxa-2-silacyclohexane, 2,2,5,5-tetramethyl-1,4-dioxa-2,5-disilacyclohexane, 2,2,4-trimethyl-1-oxa-4-aza-2-silacyclohexane, benzo-2,2-dimethyl-1,4-dioxa-2-silacyclohexane, and benzo-2,2,4-trimethyl-1-oxa-4-aza-2-silacyclohexane. Reagents according to formula (8) are described, for example, in US 2013 / 0281605 A1. The use of reagents according to formula (8) can be achieved by the addition of a compound of formula -S(R 1 )(R 2 )-C(R 3 )(R 4 ) -A-OH may result in a carbinol group corresponding to

[0065] Functionalizing reagents according to formula (9): The reagent according to formula (9) comprises a bis(trialkylsilyl)peroxide. 1 , R 2 , and R 3 may be the same or different and are selected from linear, branched or cyclic alkyls which may optionally contain heteroatoms selected from O, N, S, and Si and combinations thereof. Preferably, they are selected from C1-C10 linear alkyls, and preferably, they are all the same. Preferably, R 1 , R 2 and R 3At least one of is methyl, and more preferably all are methyl.

[0066] Functionalizing reagents according to formula (10): The reagent according to formula (10) comprises a cyclic urea. In formula (10), R3 represents a divalent saturated or unsaturated, linear or branched, preferably aliphatic, hydrocarbon group having 1 to 20 carbon atoms, which may contain, in addition to C and H, one or more heteroatoms, preferably selected independently from O, N, S or Si. Preferably, R3 represents a group of the general formula (11): -[CHX 1 ] o -[CHX 2 ] p -[O] z -[CHX 3 ] q -(11) wherein z is 1 or 0, and o, p, and q are independently selected from 0, 1, and 2, with the proviso that at least one of o, p, and q is not 0. 1 , X 2 and X 3 are independently selected from H, linear or branched alkyl, alkylaryl and aryl groups having 1 to 12 carbon atoms, and from aminoalkyl (NR) groups, where R is a linear, branched or cyclic alkyl or alkylaryl residue having 1 to 12 carbon atoms; X 1 and X 2 may represent chemical bonds forming carbon-carbon bonds that achieve unsaturation in the carbon chain. 1 , X 2 and X 3 is selected such that the total number of carbon atoms is 20 or less.

[0067] In one embodiment of the present disclosure, R3 is selected from substituted alkylene, for example, substituted alkylene corresponding to formula (11), where X 1 , X 2 and X 3 At least one of them is not H.

[0068] In one embodiment of the present disclosure, R3 is selected from unsubstituted alkylene, for example, unsubstituted alkylene corresponding to formula (11), where X 1 , X 2 and X 3 is H. In a preferred embodiment, R3 is -[(CH)2] n In the formula, n is an integer of 1 to 5, preferably 1 to 3, and more preferably 1 or 2.

[0069] In one embodiment of the present disclosure, R3 is selected from unsaturated substituted or unsubstituted alkylene, for example corresponding to formula (IIa), where X 1 and X 2 together form a carbon-carbon bond. Examples of unsaturated alkylenes include, but are not limited to, -CH=CH- or -CH2-CH=CH-.

[0070] In formula (10), R1 and R2 may be the same or different and represent a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, where the hydrocarbon group may contain, in addition to C and H atoms, preferably one or more heteroatoms selected from the group consisting of O, N, S and Si. For example, R1 and R2 may be the same or different and may contain, preferably one or more heteroatoms independently selected from O, N, S or Si, -(C1-C 20 )-Alkyl, -(C3-C 20 )-Cycloalkyl, -(C6-C 20 )-Aryl, -(C6-C 20 )-alkaryl or -(C6~C 20 Preferably, R1, R2 are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, trialkylsilyl (with alkyl groups of 1 to 4 carbon atoms per alkyl group), phenyl, and phenyl independently substituted with 1, 2 or 3 methyl-, ethyl-, propyl, and / or -butyl residues.

[0071] Preferred examples of agents according to formula (10) include, but are not limited to, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1-methyl-3-phenyl-2-imidazolidinone, 1,3-diphenyl-2-imidazolidinone, 1,3,4-trimethyl-2-imidazolidinone, 1,3-bis(trimethylsilyl)-2-imidazolidinone, 1,3-dihydro-1,3-dimethyl-2H-imidazol-2-one, tetrahydrofuran ... These include 1,3-dimethyl-2(1H)-pyrimidinone, tetrahydro-1-methyl-3-phenyl-2(1H)-pyrimidinone, tetrahydro-1,3,5-trimethyl-2(1H)-pyrimidinone, tetrahydro-3,5-dimethyl-4H-1,3,5-oxadiazin-4-one, tetrahydro-1,3,5-trimethyl-1,3,5-triazin-2(1H)-one, hexahydro-1,3-dimethyl-2H-1,3-diazepin-2-one. A particularly preferred example is 1,3-dimethyl-2-imidazolidinone, also called DMI, i.e. R3 is -CH2-CH2- and / or R1 and R2 are both -CH3.

[0072] Reagents according to formula (10) are described, for example, in U.S. Pat. No. 4,894,409, and WO 2021 / 009154 and WO 2021 / 009156.

[0073] The above functionalizing reagents are capable of reacting with the reactive chain ends of the polymer and are therefore also referred to herein as "omega-functionalizing reagents". Instead of or in addition to adding an omega-functionalizing reagent, an "alpha-functionalizing agent" may be added at the beginning of the polymerization, for example as a functionalizing initiator. This typically results in an alpha-functionalized polymer, i.e. a polymer with a polar group at the beginning of the chain. Examples of alpha-functionalizing reagents are described in EP 2 847 264 A1 and EP 2 847 242 A1.

[0074] If the polymerization reaction is not terminated by reaction with one or more omega functionalizing agents, the polymerization reaction may be terminated, for example, by quenching. Quenching agents known in the art may be used. Exemplary quenching agents for terminating polymerization include alcohols, such as octanol.

[0075] The polymer may be post-treated and isolated as known in the art. Thus, the method according to the present disclosure may further comprise at least one of the following steps: terminating the polymerization, adding at least one stabilizer, adding at least one extender oil, isolating the polymer, adding at least one filler, shaping the polymer. Extender oils used for diene rubber, such as TDAE (treated distillate aromatic extract)-, MES (light extractive solvate)-, RAE (residual aromatic extract)-, TRAE (treated residual aromatic extract)-, naphthenic oil and heavy naphthenic oil, can be added to the reaction mixture before or during post-treatment to provide oil-extended rubber. Solvents can be removed from the reaction mixture by conventional methods including distillation, distillation with steam, or by applying vacuum or reduced pressure at high temperature, if necessary. Typically, the solvent is recycled. The polymer crumbs can be further dried on a mill or processed on a mill, for example, into sheets or powder, or pressed, for example, into bales, or extruded into granules.

[0076] Polymer Compounds The polymers according to the present disclosure can be used to produce polymeric compounds, particularly rubber compounds. The rubber compounds can be prepared by a process that includes mixing at least one polymer according to the present disclosure with at least one filler. The rubber compounds can be vulcanizable and further include one or more curing agents. The curing agents can crosslink (cure) the diene polymers and are referred to herein as "crosslinking agents" or "vulcanizing agents". Suitable curing agents include, but are not limited to, sulfur, sulfur-based compounds, and organic or inorganic peroxides. Instead of a single curing agent, a combination of one or more curing agents may be used, or a combination of one or more curing agents with one or more curing accelerators or curing catalysts may be used. Examples of sulfur-containing compounds that act as sulfur donors include, but are not limited to, sulfur, sulfur halides, dithiodimorpholine (DTDM), tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), and dipentamethylenethiuram tetrasulfide (DPTT). Examples of cure accelerators include, but are not limited to, amine derivatives, guanidine derivatives, aldehyde amine condensation products, thiazoles, thiuram sulfides, dithiocarbamates, and thiophosphates.

[0077] In another embodiment of the present disclosure, the curing agent comprises a peroxide. Examples of peroxides used as vulcanizing agents include, but are not limited to, di-tert-butyl-peroxide, di-(tert-butyl-peroxy-trimethyl-cyclohexane), di-(tert-butyl-peroxy-isopropyl-)benzene, dichloro-benzoyl peroxide, dicumyl peroxide, tert-butyl-cumyl-peroxide, dimethyl-di(tert-butyl-peroxy)hexane and dimethyl-di(tert-butyl-peroxy)hexyne and butyl-di(tert-butyl-peroxy)valerate. Sulfenamide type, guanidine type, or thiuram type vulcanization accelerators can be used together with the vulcanizing agent as necessary.

[0078] If added, the vulcanizing agent is typically present in an amount of from 0.5 to 10 parts by weight, preferably from 1 to 6 parts by weight, per 100 parts by weight of rubber.

[0079] Conventional fillers can be used. Conventional fillers include silica and carbon-based fillers, such as carbon black. The fillers can be used alone or in mixtures. In a particularly preferred embodiment, the rubber composition contains a mixture of silica filler and carbon black. The weight ratio of silica filler to carbon black can be from 0.01:1 to 50:1, preferably from 0.05:1 to 20:1.

[0080] Preferably, the filler has a molecular weight of 5 to 1,000, preferably 20 to 400 m 2 The fillers include silica-containing particles having a BET surface area (nitrogen absorption) of 1000 nm to 4000 nm. Such fillers may be obtained, for example, by precipitation from a solution of silicates or by flame hydrolysis of silicon halides. The silica-containing filler particles may have a particle size of 10 to 400 nm. The silica-containing fillers may also contain oxides of Al, Mg, Ca, Ba, Zn, Zr or Ti. Other examples of fillers based on silicon oxide are aluminum silicates, alkaline earth metal silicates, for example, preferably 20 to 400 m. 2 Examples of fillers include magnesium or calcium silicates having a BET surface area of ​​100 / g and a primary particle diameter of 10-400 nm, natural silicates such as kaolin, and other naturally occurring silicates including clays (layered silica). Further examples of fillers include fillers based on glass particles such as glass beads, microspheres, glass fibers and glass fiber products (mats, strands).

[0081] Polar fillers, such as silica-containing fillers, may be modified to make them more hydrophobic. Suitable modifying agents include silanes or silane-based compounds. Typical examples of such modifying agents include, but are not limited to, compounds corresponding to the general formula (11): (R 1 R 2 R 3O)3Si-R 4 -X(11) wherein each R 1 , R 2 , R 3 are each independently an alkyl group, preferably R 1 , R 2 , R 3 is all methyl or all ethyl, R 4 is an aliphatic or aromatic linking group having 1 to 20 carbon atoms, and X is a sulfur-containing functional group selected from -SH, -SCN, -C(=O)S, or a polysulfide group.

[0082] Instead of, or in addition to, silica modified as described above, such modification can also occur in situ when making the rubber compound, for example by adding a modifying agent, preferably a silane or silane-based modifier, including, for example, one according to formula (11), during compounding, or during the process of making the tire or a component thereof.

[0083] Fillers based on metal oxides other than silicon oxide include, but are not limited to, zinc oxide, calcium oxide, magnesium oxide, aluminum oxide, and combinations thereof. Other fillers include metal carbonates, such as magnesium carbonate, calcium carbonate, zinc carbonate, and combinations thereof, metal hydroxides, such as aluminum hydroxide, magnesium hydroxide, and combinations thereof, alpha-beta-unsaturated fatty acids, including zinc acrylate, zinc diacrylate, zinc methacrylate, zinc dimethacrylate, and mixtures thereof, and salts of acrylic or methacrylic acids having 3 to 8 carbon atoms.

[0084] In another embodiment of the present disclosure, the rubber compound contains one or more carbon-based fillers, such as one or more carbon blacks. The carbon black may be produced, for example, by the lamp black process, the furnace black process, or the gas black process. Preferably, the carbon black has a molecular weight of 20 to 200 nm. 2 / g BET surface area (nitrogen adsorption). Suitable examples include, but are not limited to, SAF, ISAF, HAF, FEF and GPF black.

[0085] Other examples of suitable fillers include carbon-silica dual phase fillers, lignin or lignin based materials, starch or starch based materials, and combinations thereof.

[0086] In a preferred embodiment, the filler includes one or more of silicon oxide, carbon black, or a combination thereof.

[0087] Typical amounts of filler include 5 to 200 parts per 100 parts rubber, such as 10 to 150 parts by weight, or 10 to 95 parts by weight per 100 parts by weight rubber.

[0088] The rubber compound may further contain one or more additional rubbers other than the diene rubber according to the present disclosure, and one or more rubber additives. Additional rubbers include, for example, natural and synthetic rubbers. When present, they may be used in an amount ranging from 0.5 to 95% by weight, preferably ranging from 10 to 80% by weight, based on the total amount of rubber in the composition. Examples of suitable synthetic rubbers include BR (polybutadiene), acrylic acid alkyl ester copolymer, IR (polyisoprene), E-SBR (styrene-butadiene copolymer produced by emulsion polymerization), S-SBR (styrene-butadiene copolymer produced by solution polymerization), IIR (isobutylene-isoprene copolymer), NBR (butadiene-acrylonitrile copolymer), HNBR (partially or fully hydrogenated NBR rubber), EPDM (ethylene-propylene-diene terpolymer) and mixtures thereof. Natural rubber, E-SBR and S-SBR with a glass temperature above -60°C, polybutadiene rubber with a high cis content (>90%) produced with catalysts based on Ni, Co, Ti or Nd, polybutadiene rubber with a vinyl content of up to 80%, and mixtures thereof, are particularly important for the production of automobile tires.

[0089] The rubber compound may also include one or more rubber additives. A rubber additive is an ingredient that may improve the processing properties of a rubber composition, help crosslink the rubber composition, improve the physical properties of the vulcanizate produced from the rubber, improve the interaction between the rubber and the filler, or help bond the rubber to the filler. Rubber auxiliaries include, but are not limited to, accelerators, antioxidants, heat stabilizers, light stabilizers, ozone stabilizers, processing aids, plasticizers, tackifiers, foaming agents, dyes, pigments, waxes, extenders, organic acids, silanes, retarders, metal oxides, extender oils such as DAE (distillate aromatic extract)-, TDAE (treated distillate aromatic extract)-, MES (light extract solvates)-, RAE (residual aromatic extract)-, TRAE (treated residual aromatic extract)-, naphthenic and heavy naphthenic oils, and activators.

[0090] The total amount of rubber additives can range from 1 to 300 parts by weight, preferably 5 to 150 parts by weight, based on 100 parts by weight of total rubber in the composition.

[0091] The rubber composition can be prepared in conventional processing equipment for making and processing (vulcanizable) rubber compounds, including rollers, kneaders, internal mixers or mixing extruders. The rubber composition can be produced in a single or multi-stage process, with 2-3 mixing stages being preferred. The crosslinking agent, e.g., sulfur, and accelerators may be added in separate mixing stages, e.g., on a roller, with temperatures in the range of 30°C to 90°C being preferred. The crosslinking agent, e.g., sulfur, and accelerators are preferably added in the final mixing stage.

[0092] Purpose The rubber composition according to the present disclosure can be used to produce a rubber vulcanizate, in particular to produce a tire, in particular a tire tread. The rubber vulcanizate can be obtained by providing a vulcanizable composition comprising a polydiene polymer according to the present disclosure and subjecting the composition to at least one curing reaction. The composition can be subjected to molding before, during or after the curing reaction. The molding can be carried out by process steps including molding, extrusion and combinations thereof. The (vulcanizable) composition provided herein is also suitable for the manufacture of other articles, for example, cable sheaths, hoses, drive belts, conveyor belts, roll linings, shoe soles, sealing rings and damping elements. EXAMPLES

[0093] The following examples are provided to further illustrate the present disclosure, but are not intended to limit the disclosure to the embodiments described in these examples.

[0094] method The number average molecular weight Mn, weight average molecular weight, dispersity D=Mw / Mn (also referred to herein as molecular weight distribution or MWD) and degree of coupling of the polymers were determined at 35° C. using gel permeation chromatography (GPC) (THF as solvent, and polystyrene calibration).

[0095] Mooney viscosity was measured according to DIN ISO 289-1 (2018) under measurement conditions ML(1+4) at 100° C. Mooney stress relaxation (MSR) was determined from the same measurement according to ASTM D1646-00.

[0096] The dynamic properties of the vulcanized compounds were determined on an Eplexor 500N from Gabo-Testanlagen GmbH, Ahlden, Germany, in the temperature range from -100 °C to +100 °C at 10 Hz with a heating rate of 1 K / min according to DIN 53513-1990 (samples: l * w * t=60mm * 10mm *2 mm; free length between the sample holders 30 mm). The following properties can thus be determined: tan δ(60°C), i.e. the loss factor at 60°C (E'' / E'); and tan δ(0°C), i.e. the loss factor at 0°C (E'' / E'). tan δ(60°C) is a measure of the hysteresis loss from the tire under operating conditions. As tan δ(60°C) decreases, the rolling resistance of the tire decreases. tan δ(0°C) is a measure for the wet grip of the material. As tan δ(0°C) increases, the wet grip increases.

[0097] Elasticity was determined according to DIN 53513-1990. An elastomer test system (MTS Systems GmbH, 831 Elastomer Test System) was used. Measurements were performed in double shear mode with no static prestrain in the shear direction and approximately zero oscillation on cylindrical specimens (2 specimens of 20 x 6 mm each, pre-extruded to a thickness of 5 mm) and a measurement frequency of 10 Hz in the strain range of 0.1 to 40%. Using this method, the following properties were obtained: G'(0.5%): dynamic modulus at 0.5% amplitude sweep, G'(15%): dynamic modulus at 15% amplitude sweep, G'(0.5%)-G'(15%): difference in dynamic modulus at 0.5% for 15% amplitude sweep, tan δ(max): maximum loss factor (G'' / G') over the entire measurement range at 60°C.

[0098] The difference G'(0.5%)-G'(15%) is an indication of the Payne effect of the mixture. The lower the value, the better the distribution of the filler in the mixture and the better the rubber-filler interaction. Tan δ(max) is another measure of the hysteresis loss from the tire under operating conditions. As tan δ(max) decreases, the rolling resistance of the tire decreases.

[0099] The rebound resilience was determined according to DIN 53512 at 60°C.

[0100] Synthesis Examples: Triethylsilyloxy-4-vinyl-2-methoxybenzene (TES-4VG) and tert-butyldimethylsilyloxy-4-vinyl-2-methoxybenzene (TBDMS-4VG) were prepared as described in H. Takeshima et al., Macromolecules, 2017, 50, 4206-4216.

[0101] Example 1 (comparative): Preparation of a non-functionalized reference polymer. A moisture-free, nitrogen-flushed 20 L reactor was charged with 8500 g hexane, 1185 g butadiene, 315 g styrene and 5.43 mmol DTHFP (2,2-bis(2-tetrahydrofuryl)propane). The reaction mixture was heated to 33° C. and the adiabatic polymerization was initiated by adding 9.8 mmol butyllithium and allowed to react for 60 min. The maximum temperature was 60.4° C. The polymerization was terminated by adding 10 mmol 1-octanol and stabilized with 4.5 g IRGANOX 1520. The polymer was isolated by steam distillation and drying under reduced pressure at 60° C.

[0102] Example 2 (comparative): Omega silane-functionalized reference polymer. A moisture-free, nitrogen-flushed 20L reactor was charged with 8500g hexane, 1185g butadiene, 315g styrene and 5.43mmol DTHFP. The reaction mixture was heated to 33°C and adiabatic polymerization was initiated by adding 9.8mmol BuLi (T Max 60.8°C) and allowed to react for 60 minutes. In a second step, the polymer was treated to produce silane-containing carboxylate end groups as described in US Patent Publication No. 2016 / 0075809A1. The reaction was terminated with 10mmol 1-octanol and stabilized with 4.5g IRGANOX1520. The polymer was isolated by steam distillation and drying under reduced pressure at 60°C.

[0103] Example 3 (comparative): Polymer backbone modified with triethylsilsilyloxy-4-vinyl-2-methoxybenzene. A moisture-free, nitrogen-flushed 20 L reactor was charged with 8500 g hexane, 1185 g butadiene, 315 g styrene, 5.43 mmol DTHFP, and 22.7 mmol triethylsilyloxy-4-vinyl-2-methoxybenzene (TES-4VG). The reaction mixture was heated to 33°C and adiabatic polymerization was initiated by adding 9.8 mmol butyllithium (T Max 46°C). The reaction was terminated by adding 1-octanol and stabilized with 4.5 g IRGANOX 1520. The polymer was isolated by precipitation in ethanol and dried under reduced pressure at 60°C.

[0104] Example 4: Backbone functionalized polymer. A moisture-free, nitrogen-flushed 20 L reactor was charged with 8500 g hexane, 1185 g butadiene, 315 g styrene, 5.43 mmol DTHFP, and 37.8 mmol TBDMS-4VG. The reaction mixture was heated to 33° C. and adiabatic polymerization was initiated by adding 9.8 mmol butyllithium (T Max 60.3° C.). After polymerization, the reaction was terminated by adding 10 mmol 1-octanol and stabilized with 4.5 g IRGANOX 1520. The polymer was isolated by steam distillation of 5 kg polymer cement and drying under reduced pressure at 60° C.

[0105] Example 5: Transformation of backbone functionalized polymers by treatment with Lewis acids. 5 kg of the polymer cement prepared in Example 4 was reacted with 24 mmol of tert-butylammonium fluoride for 24 hours at ambient temperature. The polymer was isolated by steam distillation followed by drying under reduced pressure at 60° C.

[0106] Example 6: Backbone functionalized polymer further functionalized with omega silane groups. A moisture-free, nitrogen-flushed 20 L reactor was charged with 8500 g hexane, 1185 g butadiene, 315 g styrene, 5.43 mmol DTHFP, and 22.69 mmol TBDMS-4VG.

[0107] The reaction mixture was heated to 33° C. and the adiabatic polymerization was initiated by adding 9.8 mmol of butyllithium (T Max 59.23° C.) and allowed to react for 60 min. In the second step, the polymer was treated to generate silane-containing carboxylate end groups as described in Example 2.

[0108] Example 7: Omega-functionalized polymers. The polymer was prepared by the same procedure as in Example 1. Furthermore, after polymerization, 5.7 mmol of tert-butyldimethylsilyloxy-4-vinyl-2-methoxybenzene was added to the living polymer solution and reacted for another 30 minutes at 60°C. The reaction was terminated by adding 10 mmol of 1-octanol and stabilized with 4.5 g of IRGANOX1520. The polymer was isolated by steam distillation of 5 kg of polymer cement and drying under reduced pressure at 60°C.

[0109] Example 8: Alpha-functionalized polymer and its transformation by treatment with Lewis acids. A moisture-free, nitrogen-flushed reactor was charged with 8500 g of hexane, 5.43 mmol of DTHFP, and 25.1 mmol of tert-butyldimethylsilyloxy-4-vinyl-2-methoxybenzene. 12.57 mmol of butyllithium was added and the reaction mixture was held at 33° C. for 15 minutes. Subsequently, 1185 g of butadiene and 315 g of styrene were added simultaneously to the reaction mixture, which was then polymerized at 60° C. for 60 minutes. The reaction was terminated by adding 13 mmol of 1-octanol and stabilized with 4.5 g of IRGANOX 1520. The polymer cement was reacted with 50 mmol of tert-butylammonium fluoride at ambient temperature for 24 hours. The polymer was isolated by steam distillation and drying under reduced pressure at 60° C.

[0110] Example 9: Alpha-functionalized polymer further functionalized with omega silane groups and its transformation by treatment with Lewis acids. A moisture-free, nitrogen-flushed reactor was charged with 8500 g hexane, 5.43 mmol DTHFP, and 25.1 mmol tert-butyldimethylsilyloxy-4-vinyl-2-methoxybenzene. 12.57 mmol butyllithium was added and the reaction mixture was held at 33° C. for 15 minutes. Then, 1185 g butadiene and 315 g styrene were added simultaneously and the reaction mixture was polymerized at 60° C. for 60 minutes. In a second step, the polymer was treated to produce silane-containing carboxylate end groups as described in Example 2. The reaction was terminated by adding 13 mmol 1-octanol and stabilized with 4.5 g IRGANOX 1520. The polymer cement was reacted with 50 mmol tert-butylammonium fluoride at ambient temperature for 24 hours. The polymer was isolated by steam distillation and drying at 60° C. under reduced pressure.

[0111] [Table 1]

[0112] [Table 2]

[0113] Compound Research (Examples 10-17) Rubber compositions (Examples 10-17) containing the polymers produced in Examples 1, 2, and 4-9 were prepared in a 1.5 L kneader with the ingredients shown in Table 3 using the mixing protocol shown in Table 2. The compositions thus obtained were vulcanized at 160° C. for 30 minutes. The properties of the vulcanizates are summarized in Table 3.

[0114] [Table 3]

[0115] [Table 4]

[0116] [Table 5]

[0117] Comparison of Example 3 with other examples shows that the use of TES-4VG results in less defined polymers, as shown by the broad GPC trace of Example 3 in Figure 1. The broad GPC trace shows the presence of various poorly defined high molecular weight fractions, contrary to the GPC traces of the other polymers. This also shows that compared to monomers with linear substituents as TES-4VG, monomers according to the present disclosure with their branched and therefore bulkier substituents can also be polymerized at high temperatures, for example at temperatures of 50°-70°C or even higher, producing well-defined polymers, as shown by the GPC traces with narrow peaks and therefore narrow PDI ranges, as shown in the figure. Polymerization at high temperatures allows for a faster and therefore more economical production process.

[0118] Example 2 is a polymer that is end-group modified to contain polar silane end groups. Such polymers are known to improve properties in tires, but are also known to have higher Mooney viscosities than their non-functionalized counterparts (Example 1) and are more difficult to process. Comparison of Example 2 with a polymer according to the present disclosure shows that modification with functionalized comonomers according to the present disclosure results in a functionalized polymer with reduced Mooney viscosity. Functionalized comonomers can also be used to reduce the Mooney viscosity of the silane-functionalized polymer of Comparative Example 2.

[0119] The results of the compound study presented in Table 3 show that this effect was maintained in the rubber compound. The compound Mooney of the polymer modified according to the invention was similar to that of the compound obtained with the non-functionalized reference polymer, while other compound properties did not change significantly. The same applies when a functionalized comonomer is used in combination with a functionalizing agent. The advantageous properties introduced by the functionalizing agent were maintained, but the Mooney viscosity was reduced, which indicates improved compound processing properties.

Claims

1. 1. A process for making a polydiene polymer having at least 51 wt. % of units derived from one or more conjugated dienes, based on the weight of the polymer, comprising polymerizing at least one aliphatic conjugated diene monomer having from 4 to 25 carbon atoms, and optionally one or more comonomers, and at least one functionalized comonomer according to formula (1): 【Chemistry 1】 wherein the functionalizing comonomer is used at the beginning of the polymerization to produce an alpha-functionalized polymer, or at the end of the polymerization to produce an omega-functionalized polymer, or during the polymerization to produce a backbone-modified polymer, or a combination thereof, wherein in formula (1): R １ and R ２ are independently selected from alkyl residues having 1 to 12 carbon atoms, which may optionally contain one or more halogen atoms or catenary ether oxygen atoms), and a trialkylsilane residue of formula (2): (R ３ )(R ４ )(R ５ )Si- (2) (In the formula, R ３ , R ４ and R ５ are independently selected from alkyl residues having 3 to 32 carbon atoms, which may optionally contain one or more halogen atoms or catenary ether oxygen atoms; R ３ , R ４ and R ５ At least one of R is branched; １ and R ２ wherein at least one of is a trialkylsilane residue of formula (1).

2. 2. The method of claim 1, comprising reacting the functionalized comonomer with itself to produce a second functional comonomer comprising repeat units derived from the functionalized comonomer according to formula (1), and subjecting this second comonomer to a polymerization reaction with the at least one aliphatic conjugated diene monomer and, optionally, the one or more comonomers.

3. R ３ , R ４ and R ５ At least one of the following corresponds to general formula (3): (R’)(R’’)(R’’’)C-(CH ２ ) ｎ - (3) wherein n represents 0, 1, or 2; and R', R'', and R''' are independently selected from H or alkyl of 1 to 10 carbon atoms which may optionally contain one or more halogen atoms or catenary ether oxygen atoms, with the proviso that not more than one of R', R'', and R''' is H.

4. R ３ , R ４ and R ５ At least one of the following corresponds to general formula (3): (R’)(R’’)(R’’’)C-(CH ２ ) ｎ - (3) 2. The method of claim 1, wherein n represents 0, and R', R'', and R''' are independently selected from alkyl of 1 to 5 carbon atoms.

5. R １ or R ２ 2. The method of claim 1, wherein is a linear or branched alkyl group having 1 to 6 carbon atoms.

6. 2. The method of claim 1, wherein the conjugated diene monomer is selected from 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene, and combinations thereof.

7. 10. The method of claim 1, wherein the polymerization further comprises copolymerizing one or more comonomers selected from copolymerizable vinyl aromatic comonomers.

8. The method of claim 1 , wherein the polymerization comprises anionic polymerization.

9. Treatment with at least one acidic agent provides the residue R １ and R ２ 10. The method of claim 1, further comprising exchanging at least one of the following with a hydrogen or a cation, wherein the acidic agent comprises a Lewis acid and a Bronsted acid.

10. 10. The method of claim 1, further comprising reacting the polymer with at least one functionalizing agent to produce polar functional end groups having, in addition to C and H atoms, at least one heteroatom selected from Si, S, N, O, and combinations thereof.

11. 10. The method of claim 1, further comprising at least one of the following steps: terminating the polymerization, adding at least one stabilizer, adding at least one extender oil, isolating the polymer, adding at least one filler, and shaping the polymer.

12. A composition comprising a polymer obtainable by the method according to any one of claims 1 to 11.

13. 13. The composition of claim 12, comprising at least one curing agent capable of curing the polymer.

14. 13. An article comprising a cured composition obtained by subjecting the composition of claim 12 to a curing reaction.

15. A method of making a cured article comprising subjecting the composition of claim 12 to a curing reaction.

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