Functionalized diene rubbers prepared using unsaturated siloxane coupling agents.

Abstract

A method for producing a polydiene rubber, comprising (i) polymerizing at least one aliphatic conjugated diene monomer, preferably having 4 to 25 carbon atoms, to produce a polymer having reactive polymer chain ends, (ii) reacting at least a portion of the reactive polymer chain ends with a coupling agent comprising 2 to 20 unsaturated siloxane units, preferably 3 to 15 units, more preferably 3 to 10 units, and (iii) using at least one functionalizing agent to introduce at least one functional group into the polymer, the functional group preferably having at least one heteroatom selected from Si, S, N, O, or combinations thereof in addition to C and H atoms, where (iii) is performed before, after, or during step (ii). Also provided are polydiene rubbers obtained by this method, curable compositions comprising the polydiene rubber, and compositions comprising the cured polydiene rubber.

Description

[Background technology]

[0001] Diene rubber is widely used as a raw material for manufacturing tires. Coupling agents can be used to improve the processing of diene rubber. Coupling agents link the polymer chains of rubber together to form branched or star-shaped polymer structures. This broadens the molecular weight distribution of the polymer, reduces the Mooney viscosity of compounds containing them, and makes them easier to process. Examples of known coupling agents include silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, tin tetrachloride, dibutyltin dichloride, tetraalkoxysilanes, derivatives of ethylene glycol diglycidyl ether, and 1,2,4-tris(chloromethyl)benzene. (Patent Document 1) reports the use of substituted silasesqquioxanes, polycyclic substituted polysiloxanes as coupling agents. However, it has been found that the properties of the polymer can be improved by using certain coupling agents in combination with additional functionalizing agents. [Prior art documents] [Patent documents]

[0002] [Patent Document 1] US Patent Application Publication No. 2005 / 0107541A1 Summary of the Invention [Means for solving the problem]

[0003] Thus, in one aspect, there is provided a method for producing a polydiene rubber, comprising the steps of: (i) polymerizing at least one aliphatic conjugated diene monomer, preferably having from 4 to 25 carbon atoms, to produce a polymer having a reactive polymer chain end; (ii) reacting at least a portion of the reactive polymer chain ends with a coupling agent containing 2 to 20 unsaturated siloxane units, preferably 3 to 15 units, and more preferably 3 to 10 units; (iii) using at least one functionalizing agent to introduce at least one functional group into said polymer, said functional group preferably having at least one heteroatom selected from Si, S, N, O or a combination thereof in addition to C and H atoms, wherein (iii) is carried out before, after or during step (ii).

[0004] In another aspect, there is provided a polydiene rubber obtained by the above process.

[0005] In a further aspect, there is further provided a curable composition comprising the polydiene rubber described above and further comprising at least one vulcanizing agent for curing the polydiene rubber.

[0006] In yet another aspect, there is provided a composition comprising a cured polydiene rubber obtained by curing the above-described curable composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] The present disclosure is further explained in the detailed description that follows.

[0008] In the following description, certain standards (ASTM, DIN, ISO, etc.) may be referenced. Unless otherwise indicated, these standards are used in the version that was valid on March 1, 2020. If there is no version valid on that date, for example if the standard has expired, the version that was valid on the date closest to March 1, 2020 will be referenced.

[0009] All documents mentioned in this description are incorporated by reference unless otherwise indicated.

[0010] In the following description, the amount of a component 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.

[0011] The term "phr" means "parts per hundred rubber", i.e., the weight percentage values ​​of components of a composition that contain 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 will usually be greater than the amount of rubber and may exceed 100% by weight.

[0012] Unless otherwise specified, ranges specified in this disclosure are meant to include and disclose all values ​​between the endpoints of the range, and those endpoints.

[0013] The term "comprising" is used in an open and non-limiting sense. The phrase "a composition comprising components A and B" means that the composition contains components A and B, but the composition may have other components. Contrary to the use of "comprising", the word "consisting of" is used in a narrow and limiting sense. The phrase "a composition consisting of components A and B" is meant to represent a composition of components A and B without other components.

[0014] Siloxane coupling agent The coupling agent according to the present disclosure comprises at least two unsaturated siloxane units, preferably at least 2-20, more preferably 3-15, most preferably 4-10 unsaturated siloxane units. Thus, the coupling agent according to the present disclosure comprises, in addition to the -Si-O- units, at least two, preferably at least three, more preferably at least four units having at least one carbon-carbon double bond, preferably a vinyl group (-CH=CH2 group). Typically, these units are linked to the silicon atom of the Si-O- units. Thus, these units are referred to herein as "unsaturated siloxane units" or "unsaturated -Si-O units". The coupling agents may be linear or branched, acyclic, cyclic, e.g. monocyclic or polycyclic. Preferably, they are cyclic, preferably they have at least one cyclic structure, preferably a cyclic siloxane structure, i.e. a cyclic structure having at least one unsaturated -Si-O- unit as described above. Preferably, the siloxane-based coupling agent is cyclic and has a cyclic structure having at least two unsaturated siloxane units, more preferably at least three unsaturated siloxane units.

[0015] The coupling agents according to the present disclosure are preferably used for coupling of polydiene rubbers, i.e. for linking polymer chains to each other, preferably forming branched, e.g. multi-arm or star-shaped, polymer structures. The coupling of the polymers can be confirmed by an increase in molecular weight, measured for example by GPC. The degree of coupling can be determined by comparing the chromatogram of the coupled polymer with that of its precursor polymer. The coupling results in the appearance of a high molecular weight fraction in the chromatogram. The ratio of the integral of the coupled fraction to the integral of the total molecular weight distribution is the degree of coupling (wt % of polymer coupled).

[0016] The advantage of using the coupling agent according to the present disclosure in the manufacture of polydiene rubber is that it allows fine tuning of the polymer structure. When the siloxane-based reagents are used in molar excess of their unsaturated units relative to the polymer chain, the coupled polymer may contain unreacted unsaturated units from the coupling agent that can participate in crosslinking (vulcanization) reactions. However, if the presence of unsaturated groups from the coupling agent in the polymer is undesirable, their presence can be avoided or reduced by using the coupling agent in equimolar or less than equimolar amounts (based on the molar ratio of unsaturated units of the coupling agent to the polymer chain). In this case, it can be assumed that all the unsaturated units of the coupling agent are consumed by the coupling reaction. It can be assumed that the molar amount of reactive polymer chains produced during the polymerization reaction is equal to the molar amount of polymerization initiator used during the polymerization reaction.

[0017] Coupling agents according to the present disclosure have the general formula (1): [ka] The compound contains 2 to 20 unsaturated siloxane units corresponding to the above formula (1), preferably 3 to 15 unsaturated siloxane units, and more preferably 4 to 10 unsaturated siloxane units.

[0018] In formula (1), each R1 independently represents an alkenyl group, preferably selected from the group consisting of vinyl (-CH=CH2), allyl (-CH-CH2-CH=CH2), n-propenyl (-CH2CH=CH2), n-butenyl (-CH2CH2CH=CH2), isobutenyl (-CH2(CH3)CH=CH2); n-pentenyl (-CH2CH2CH2CH=CH2), isopentenyl (-CH2(CH3)CH2CH=CH2, -CH2CH2(CH3)CH=CH2), and each R2 independently represents H, OH, or an organic residue, preferably having 1 to 20 carbon atoms and optionally further having one heteroatom selected from O, S, Si, N, and combinations thereof. The hydrocarbon residue may be unsubstituted or substituted, in which case at least one hydrogen atom is replaced by a substituent. Suitable substituents include siloxane, polysiloxane, silyl, aminosilyl, aminosiloxane, alkylamino groups, halogens, and combinations thereof. Preferably, the hydrocarbon residue is aliphatic. Preferably, the hydrocarbon residue is selected from an alkenyl, preferably having 2 to 10 carbon atoms, an alkyl, preferably having 1 to 10 carbon atoms, where the alkyl or alkenyl chain or both may be interrupted once or more than once by an ether oxygen atom, or R2 is selected from a siloxane or polysiloxane having up to 10 silicon atoms, where the siloxane or polysiloxane may have at least one silicone atom with at least one aliphatic substituent, optionally selected from an alkyl group, an alkylene group, or an alkenyl group, or a combination thereof. Preferably, at least one R2 represents methyl or ethyl. Preferably, all R2 represent methyl or ethyl or a combination thereof.

[0019] In one preferred embodiment of the present disclosure, the siloxane coupling agent has the general formula (2): [ka] wherein R corresponds to R2 in formula (1) above. Preferably, R is selected from alkyl having 1 to 10 carbon atoms, which may optionally further contain one oxygen ether atom, which may be an alkoxy or polyalkoxy residue, or which may optionally contain one or more silane, siloxane, or polysiloxane groups, which may contain 1 to 3 alkyl or alkenyl residues on the silicon atom, the maximum number of silicon atoms being preferably less than 10. Preferably, R is selected from C1-C 10 -alkyl group, more preferably a C1-C7-alkyl group, most preferably R is methyl.

[0020] In another preferred embodiment of the present disclosure, the unsaturated siloxane coupling agent is cyclic and has the formula (3): [ka] where n is 1, 2, 3 or 4, preferably n is 1 or 2, and each R1 is as described in formula (1), preferably at least one, more preferably all R1 represent a vinyl (-CH=CH2) group. Each R2 is as described in formula (1) above. Preferably at least one R2 is a C1-C7-alkyl group, more preferably at least one R2 is methyl. Most preferably all R2 represent a methyl group.

[0021] In one embodiment of the present disclosure, the unsaturated siloxane coupling agent has the general formula (4): [ka] where n is an integer from 1 to 20, m is an integer from 1 to 20, and each residue R is selected independently of the others and is as described above with respect to formula (2); R3 is H, OH, a saturated or unsaturated hydrocarbon having 1 to 10 carbon atoms, a monovalent siloxane, polysiloxane, or silane, or R3 is bonded to R5 to form a cyclic compound and represents a divalent siloxane or polysiloxane having 1 to 10 silicon atoms, one or at least one of said silicon atoms having one or more alkyl or alkenyl residues having 1 to 10 carbon atoms, or R3 and R5 together form a chemical bond to form a cyclic compound; R4 is a linker group selected from (i) an aliphatic hydrocarbon having 1 to 20 carbon atoms, which may optionally contain one or more oxygen ether groups, (ii) one or more silane or siloxane groups, or combinations thereof, in which one or more silicon atoms may carry one or more aliphatic hydrocarbon groups having 1 to 10 carbon atoms, or a combination of (i) and (ii); R5 is H, OH, a saturated or unsaturated hydrocarbon having 1-10 carbon atoms, a monovalent siloxane, polysiloxane, or silane; or R5 is bonded to R3 to form a cyclic compound and represents a divalent siloxane or polysiloxane having 1-10 silicon atoms, one or at least one of said silicon atoms having one or more alkyl or alkenyl residues having 1-10 carbon atoms; or R5 is bonded to R3 to form a cyclic compound and represents a divalent siloxane or polysiloxane having 1-10 silicon atoms, one or at least one of said silicon atoms having one or more alkyl or alkenyl residues having 1-10 carbon atoms; or R3 and R5 together form a chemical bond to form a cyclic compound.

[0022] In another preferred embodiment of the present disclosure, a polycyclic coupling agent is used. Suitable examples of polycyclic agents include those represented by formula (5): [ka] Examples of such materials include those corresponding to the following:

[0023] In formula (5), Ra, Rb, Rc, Rd, Re, Rf, Rg, and Rh are the same or different, and each independently represents a C1-C 10 -Alkyl, C2-C6-alkenyl, -O-Si-(R 1’ R 2’ R 3’ R1', R2', and R3' are each independently selected from C1-C 10 -alkyl, C2-C6-alkenyl, preferably vinyl, preferably at least one of R1', R2', and R3' comprises a vinyl unit, preferably all of R1', R2', and R'3 are vinyl (-CH=CH2). At least one, preferably at least two, more preferably at least three of Ra, Rb, Rc, Rd, Re, Rf, Rg, and Rh comprise C2-C6-alkenyl, preferably vinyl (-CH=CH2). In one embodiment of the polycyclic coupling agent according to formula (5), at least four of Ra to Rh are vinyl or at least one of the residues Ra to Rh is -O-Si(vinyl)3. In another embodiment of the compound according to formula (5), all of Ra to Rh are vinyl. The compound according to formula (5) is also known as polyhedral oligomeric silsesquioxanes or POSS. These materials are commercially available or can be prepared, for example, as described in Quirk, Cheng et al, Macromolecules 2012, 45, 21, 8571-8579.

[0024] Preferably, the coupling agent according to the present disclosure has a molecular weight of 5000 g / mol or less. Preferably, the coupling agent has a molecular weight of less than 2000 g / mol.

[0025] Particularly preferred examples of coupling agents according to the present disclosure include: [ka] (1,3,5,7-Tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane) [ka] (1,3,5-trivinyl, 1,3,5-trimethylcyclotrisiloxane), [ka] (Octavinylsilasesquioxane), [ka] (Substituted silasesqquioxane) where the residues Rb to Rg independently represent C1-C7-alkyl, preferably cyclopentyl, and Ra is -O-Si(-CH=CH2)3. Not only one or a combination of coupling agents according to the present disclosure, but also a combination of one or more coupling agents of the present disclosure with one or more other coupling agents can be used.

[0026] polymer In one aspect of the present disclosure, there is provided a polymer obtainable by a process comprising: (i) polymerizing at least one conjugated diene monomer to produce a polymer having reactive chain ends; and (ii) reacting at least a portion of said reactive polymer chain ends with at least one siloxane-based coupling agent according to the present disclosure. The conjugated diene monomer preferably has 4 to 25, more preferably 4 to 20 carbon atoms.

[0027] The polymer may be a homopolymer or 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 units derived from 1,3-butadiene or consists of units derived from 1,3-batdiene.

[0028] In one embodiment of the present disclosure, the polymer is a copolymer obtained by a process comprising a polymerization reaction involving at least two conjugated dienes. In another embodiment, the present disclosure, the polymer is a copolymer obtained by a process comprising the polymerization of at least one conjugated diene monomer and at least one vinyl aromatic comonomer. Examples of suitable vinyl aromatic comonomers include styrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, para-tertbutylstyrene, vinylnaphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene and combinations of 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, a-methylstyrene, 2,4-diisopropyl-styrene and 4-tert-butylstyrene, stilbene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethylether, N,N-dimethylaminoethylstyrene, tert-butoxystyrene, vinylpyridine or amino-substituted derivatives (N,N -dimethylaminomethylstyrol) or copolymerizable vinylsilanes or multivinylsilanes with amino groups (e.g. 1,4-bis[dimethyl(vinyl)silyl]piperazine), vinylaminosiloxane or butadienylaminodisiloxane monomers such as 4-[3-(tert-butyl)-1,3,3-trimethyl-1-vinyldisiloxanyl]morpholine, 3-(tert-butyl)-N,N-diethyl-1,3,3-trimethyl-1-vinyl-disiloxane-1-amine, and the 3-(tert-butyl)-N,N-dibutyl-1,3,3-trimethyl-1-vinyldisiloxane-1-amine, but are not limited thereto. Styrene is particularly preferred.

[0029] In one embodiment of the disclosure, the polymer is a butadiene polymer, including homopolymers and copolymers of 1,3-butadiene. Preferably, the polymer according to the disclosure comprises at least 51% 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 disclosure, the diene polymer comprises at least 60% by weight, or at least 75% by weight, of units derived from 1,3-butadiene.

[0030] In one embodiment of the disclosure, the diene polymer comprises 0 to 49 weight percent, or 0 to 40 weight percent, of units derived from one or more comonomers, based on the total weight of the polymer.

[0031] In one embodiment of the disclosure, the diene polymer comprises at least 60% by weight, or at least 70% by weight, of units derived from 1,3-butadiene and 0-40% by weight, or 0-30% by weight, of units derived from one or more comonomers.

[0032] In one embodiment, the diene polymers of the present disclosure contain from 0 to 20 weight percent of units derived from one or more conjugated dienes other than 1,3 butadiene.

[0033] In one embodiment, diene polymers according to the present disclosure contain up to 49 wt.% of units derived from one or more vinyl aromatic comonomers, preferably 5 wt.% to 40 wt.% of units derived from one or more vinyl aromatic comonomers. Preferably, diene polymers of the present disclosure contain up to 49 wt.%, or 0 to 40 wt.%, of units derived from styrene, based on the weight of the polymer.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] Suitable comonomers also include, but are not limited to, one or more other copolymerizable comonomers that introduce functional groups, including crosslinking sites, branching sites, branching, or functionalized groups. In one embodiment of the present disclosure, the diene polymer comprises 0 to 10% or 0 to 5% by weight of units derived from one or more such other comonomers.

[0038] Combinations of one or more comonomers of the same chemical type as those mentioned above, as well as combinations of one or more comonomers of different chemical types, can be used.

[0039] The 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.

[0040] 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 Mn of the polymer is 150 kg / mol to 320 kg / mol.

[0041] The diene polymers 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 polymers have an MWD of 1.03 to 3.5 or 1.03 to 2.0. MWD is the ratio of weight average molecular weight (Mw) to number average molecular weight Mn, i.e., MWD is equal to Mw / Mn.

[0042] The diene polymers according to the present disclosure are rubbers and typically have a glass transition temperature below 20° C. They may have a glass transition temperature (Tg) of, for example, −120° C. to below 20° C. In a preferred embodiment of the present disclosure, the polymer has 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 −50 to −80° C.

[0043] 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.

[0044] In one embodiment, the diene polymer according to the present disclosure has a Mooney viscosity ML1+4 at 100° C. of 30-150 units, a number average molecular weight of 100,000-400,000 g / mol, a glass transition temperature of −110° C.-0° C., and a molecular weight distribution (MWD) of 1.03-20.

[0045] The diene polymer according to the present disclosure may be further functionalized and may contain one or more functional groups, preferably terminal groups, containing, in addition to C and H atoms, at least one heteroatom selected from Si, S, N, O, and combinations thereof. Preferably, the functional group has 1 to 20 carbon atoms. Thus, to prepare the polymer according to the present disclosure, at least one functionalizing agent is used to introduce a functional group. The functionalizing agent may be selected from a functionalized copolymerizable comonomer, an alpha-functionalizing agent, such as a functionalizing initiator, or a non-copolymerizable functionalizing agent capable of introducing a functional group at the end (omega position) of the polymer, or a combination thereof.

[0046] Such further functionalized polymers can be obtained, for example, by a reaction comprising reacting a reactive polymer chain end with at least one functionalizing reagent comprising, in addition to C and H atoms, at least one heteroatom selected from Si, S, N, O, and combinations thereof. The at least one functionalizing reagent can be reacted with the polymer before, during or after, preferably after, the reaction of the polymer with the coupling agent. If necessary, the reaction product of this functionalization reaction can be subsequently treated to remove at least one -OH group, -SH group, -COOH -NR2H group, -COOH -NR2H group, -SH ... + group, -NR3 + group, -NH3 + groups, or combinations thereof, or -O - group, -S - group, -COO - The anionic form thereof may be selected from the group consisting of -OH, -SH, or -COOH, or a combination thereof, in the case of an amino group, or a non-ionic form, in the case of an amino group, or a combination thereof. - , -S - , -COO -Such treatments can include hydrolysis reactions, for example by adding an alcohol or an acid, steam distillation, or treatment with at least one other functionalizing reagent that reacts with the first functionalizing reagent to generate their anionic forms selected from the group consisting of:

[0047] Polymer manufacturing method The homopolymers or copolymers of the present disclosure can be prepared by methods known in the art. Polymerization can be carried out to produce statistical polymers, also called random copolymers, block copolymers, gradient copolymers, or combinations thereof, and can include linear and branched structures known to those skilled in the art.

[0048] The polymers can be obtained by a process involving anionic or catalytic polymerization using one or more coordination catalysts. Coordination catalysts in this context include Ziegler-Natta catalysts or monometallic catalyst systems. Preferred coordination catalysts are based on Ni, Co, Ti, Zr, Nd, V, Gd, Cr, Mo, W, or Fe. Preferably, the polymerization reaction involves anionic solution polymerization. Initiators for anionic solution polymerization include organometallics, preferably based on alkali metals or alkaline earth metals. Examples include 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, [3-(dibutylamino)propyl]lithium, [(dibutylamino)-dimethylsilyl]-methyllithium, phenyllithium, 4-butylphenyllithium, 1-naphthyllithium, p-toluyllithium, and allyllithium derived from tertiary N-allylamines. Lithium compounds such as, but not limited to, [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, but not limited to, lithium pyrrolidide, lithium piperidide, lithium hexamethyleneimide, lithium 1-methylimidazolidide, lithium 1-methylpiperazide, lithium morpholide, lithium dicyclohexylamide, lithium dibenzylamide, and lithium diphenylamide. The above allyllithium compounds and the above lithium amides can also be prepared in situ by reacting an organolithium compound with the respective tertiary N-allylamine or the respective secondary amine. Bifunctional and polyfunctional organolithium compounds such as 1,4-dilithiobutane, dilithium piperazide can also be used. Preferably, n-butyllithium, sec-butyllithium, or a combination thereof is used.The initiator forms an anionically reactive monomer, which propagates the polymerization by reaction of the reactive carbanion monomer with another monomer to form a reactive carbanion polymer chain end, or, in the case of polymerizations using one or more coordination catalysts, the catalyst forms the reactive chain end.

[0049] Randomizers and control agents known in the art can be used during polymerization to control the structure of the polymer, in particular to avoid agglomeration or to randomize the monomer distribution. 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 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 dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-tert-butyl ether, 2-(2-ethoxyethoxy)-2-methyl-propane, triethylene glycol diethyl ether ... 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, potassium and sodium salts including the potassium and sodium salts of 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 randomizer is used in the polymerization reaction.

[0050] In one embodiment of the present disclosure, the polymer is a random polymer. In one embodiment, the polymer is a block copolymer. To produce a block copolymer, the polymerization is preferably started with one monomer, followed by the addition of another (co)monomer, depending on the size of the block to be produced. The order of monomer addition can be adapted depending on which blocks of different monomers are desired to be formed. In one embodiment of the present disclosure, such blocks are formed at the beginning or end of the polymerization, or both.

[0051] 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. If appropriate, these solvents can also be mixed with polar solvents.

[0052] The polymerization can be carried out by introducing the (co)monomer and the 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 the solvent. The initiator or catalyst is introduced or added together with the monomer and the solvent. Variations such as introducing the solvent into the reactor, adding the initiator or catalyst, followed by the monomer can be used. The polymerization can be carried out in a continuous or batch mode. Additional monomer and solvent can be added during or at the end of the polymerization.

[0053] The polymerization can be carried out at normal or elevated pressure (e.g., 1-10 bar) or reduced pressure. Typical reaction temperatures include room temperature, but depending on the nature and amount of comonomer, the reaction temperature may be higher or lower than 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.

[0054] The polymerization reaction results in reactive polymer chain ends, preferably anionic chain ends. At a desired degree of progress of the polymerization reaction, for example when a desired conversion rate of the polymer or a desired molecular weight range has been achieved, the polymerization mixture or solution containing the reactive polymer chain ends is contacted with at least one siloxane-based coupling agent according to the present disclosure. Typically, it is desirable to carry out the coupling reaction at the end of the polymerization reaction, for example after at least 90%, or at least 95% of the monomer has been consumed. For example, the coupling agent can be added before or after the monomer feed is stopped or interrupted. The coupling agent can be added as a pure substance or as a solution or dispersion. Although not preferred or necessary, coupling agents other than the unsaturated siloxane according to the present disclosure can be further used. Typically, the addition of the coupling agent is carried out at a reaction temperature of 20°C to 130°C, or 50°C to 130°C.

[0055] Another advantage of using siloxane coupling agents to make diene rubbers is that the polymers obtained therefrom can be further functionalized to make diene rubbers with additional functional groups, preferably end groups, preferably end groups suitable for use in tire applications, such as tire tread compositions. In one embodiment of the present disclosure, the polymers are omega-functionalized, alpha-functionalized, or alpha and omega-functionalized. The polymers may be in-chain functionalized, for example, by using functionalizing comonomers that introduce functional groups into the polymer backbone or as pendant side groups.

[0056] Omega Functionalization: In one embodiment of the present disclosure, the method according to the present disclosure may further comprise the step of reacting the polymer with at least one functionalizing agent for introducing at least one functional group into the polymer, which may be performed before, after or during step (ii).

[0057] Typically, functionalizing agents capable of introducing functional groups at the end of a polymer, i.e., at the omega position, 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 selected from Si, O, and S, and combinations of Si, O, and N, or combinations of N and O. Typically, these can be used to introduce functional groups into the polymer, either directly, or by hydrolysis or reaction with another functional agent, or both, such as -OH, -COOH, -SH, -NR2H, -N2H, -N3H, -N4H, -N5H, -N6H, -N7H, -N8H, -N9H, -N10H, -N11H, -N12H, -N13H, -N14H, -N15H, -N16H, -N17H, -N18H, -N19H, -N2H + , -NR3 + , -NH3 +or the respective ionic or non-ionic forms and salts thereof, and combinations thereof. Preferably, R independently represents an organic residue, preferably an alkyl group, having 1 to 12 carbon atoms. Typically, the functionalizing agent has a molecular weight of less than 5,000 g / mol, or even less than 2,000 g / mol. Typically, the functionalizing agent is not a comonomer. Functionalizing agents known in the art can be used. Examples of functionalizing agents include, but are not limited to, linear or branched alkoxysilanes and those described in U.S. Patent Application Publication No. 2013 / 0281605A1, U.S. Patent Application Publication No. 2013 / 0338300A1, U.S. Patent Application Publication No. 2013 / 0280458A1, U.S. Patent Application Publication No. 2016 / 0075809A1, U.S. Patent Application Publication No. 2016 / 0083495A1, WO 2021 / 009154A1, U.S. Patent No. 4,894,409, U.S. Patent Application Publication No. 2018 / 0037674A1, and WO 2021 / 009156.

[0058] Preferred functionalizing reagents include reagents having at least one functional group selected from carboxylic anhydride groups, cyclic carbamide ((O=)C(NR'-)(NR'-)) groups, tertiary alkylamino groups ((R')2N-), linear or branched cyclic or acyclic siloxanes, cyclic, acyclic, linear or branched silanes, and combinations thereof. Preferred silanes or siloxanes include molecules having at least one (R)3Si-N- group, (R3)Si- group; (R)3Si-S- group; (R)2Si(-O-)- group, or combinations thereof. In the above formula, each R independently represents an alkyl, alkoxy having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and R' represents an alkyl or alkylsilyl having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms. Preferably, the reagent is aliphatic. "X-" indicates that the atom "X" is attached to an organic residue, e.g., a carbon atom of an organic residue, e.g., an alkyl, alkylene, heteroalkyl, or heteroalkylene, which may be cyclic or acyclic, e.g., an azaalkylene or a thiaalkylene. Heteroalkyl or heteroalkylene refers to an alkyl or alkylene group having at least one heteroatom-containing functional group. The heteroatom is preferably selected from Si, S, O, and N.

[0059] Preferred functionalizing agents include anhydrides, linear or branched, cyclic or acyclic alkoxysilanes (siloxanes), linear or branched silanes, linear or branched, preferably cyclic carbamides. [ka] ((RO) x (R) y Si-R''-S-(R')(12);(RO) x (R) y Si-R″-N(-R′)2 (13), and combinations thereof.

[0060] 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, having a 4-7 membered aliphatic cyclic ring, more preferably a 5- or 6-membered aliphatic cyclic ring, any of which 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, having a 3-20 membered ring structure, the ring has at least 2, preferably at least 3 -Si(R1R2)-O- units, where R1 and R2 are each independently selected from H, C1-C1-C2 ... 10 C1-C2 saturated hydrocarbon residues that may optionally contain one or more heteroatoms selected from O, N, S, Si, or combinations thereof. 10 Preferably, R1 and R2 are selected from methyl, ethyl, propyl, and butyl. In one embodiment of the present disclosure, the polymer does not have an amino end group. In another embodiment of the present disclosure, the polymer does not have a thiol end group.

[0061] Functionalizing reagents according to formula (6): Reagents according to formula (6) include cyclosiloxane-based functionalizing reagents. In formula (6), R1 and R2 are the same or different and are H, C1-C 10 Corresponding to saturated hydrocarbon residues, preferably methyl, ethyl, propyl, and butyl, where C1-C 10The saturated e 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, which can be converted directly or indirectly (e.g., via subsequent hydrolysis) to silanols (-Si(R1)(R2)-OH) or silanolates (-Si(R1)(R2)-OH) by reagents according to formula (6), as described, for example, in U.S. Patent Application Publication No. 2016 / 0075809 A1. - ) group) can be obtained.

[0062] Functionalizing reagents according to formula (7): Reagents according to formula (7) include silalactone-based functionalizing reagents. 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 are each selected from H or a residue having 1 to 20 carbon atoms, preferably alkyl, cycloalkyl, aryl, alkaryl or aralkyl, A is preferably a divalent organic group having 1 to 26 carbon atoms and which may contain, in addition to hydrogen atoms, heteroatoms selected from O, N, S, and Si.

[0063] Preferably R 1 , R 2 are the same or different, H, (C1-C 24 )-Alkyl, (C1-C 24 )-alkoxy, (C3-C 24 )-Cycloalkyl, (C3-C24 )-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, which may optionally contain one or more heteroatoms selected from O, N, S or Si.

[0064] Preferably R 3 , R 4 are the same or different, and are H, (C1-C 24 )-Alkyl, (C3-C 24 )-cycloalkyl, (C 6- C 24 )-aryl, (C6-C 24 )-alkaryl, or (C6-C 24 )-aralkyl groups, optionally containing one or more heteroatoms selected from O, N, S, or Si.

[0065] In one embodiment of the present disclosure, A is: -Xn-(CY1H)m-(CY2Y3)o-(CY1H)p-, where 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, where R is H, or C1-C3 alkyl, or X is N(Si(alkyl)3), where each "alkyl" independently represents C1-C6 alkyl, -oxyalkyl, or alkoxy; Y1 is H or C1-C3 alkyl, Y2 is H or C1-C3 alkyl, and Y3 is H or C1-C3 alkyl, preferably at least one of Y2 and Y3 is H.

[0066] 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(アルキル)3)-CH2-;-N(Si(アルキル)3)-CH2CH2-;N(Si(アルキル)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- Examples include:

[0067] 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-silacyclonexan-6-one, 2-methyl-2-ethenyl-1-oxa -4-thia-2-silacyclohexane-6-one, 2,2,5-trimethyl-1-oxa-4-thia-2-silacyclohexane-6-one, 2,2-dimethyl-1-oxa-4-aza-2-silacyclohexane-6-one, 2,2,4-trimethyl-1-oxa-4-aza-2-silacyclohexane-6-one, 2,4-dimethyl-2-phenyl-1-oxa-4-aza-2-silacyclohexane-6-one, 2,2-dimethyl-4-trimethylsilyl-1-oxa-4-aza-2-silacyclohexane-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,Examples of the 2-methyl-2-(2-propen-1-yl)-1-oxa-2-silacyclopentan-5-one include 2,4-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, and 2,2-dimethyl-1-oxa-2-silacycloheptan-7-one.

[0068] Reagents according to formula (7) are described in US Patent Application Publication No. 2016 / 0075809, particularly in paragraphs

[0034] to

[0042] . Such reagents can be used alone or in addition to other functionalizing reagents, such as reagents according to formula (6), to provide silacarboxylate groups, such as those of the general formula -Si(R 1 )(R 2 )-C(R 3 )(R 4 )-A-COO - It is possible to form a group according to the formula:

[0069] Functionalizing reagent according to formula (8): Reagents according to formula (8) include oxa-silacycloalkanes. 1 , R 2 , R 3 , R 4 , and A are the same as those described in formula (7).

[0070] 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 -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 Patent Application Publication No. 2013 / 0281605 A1. By using a reagent according to formula (8), a compound of formula -S(R 1 )(R 2 )-C(R 3 )(R 4 )-A-OH can be obtained as a corresponding carbinol group.

[0071] Functionalizing reagents according to formula (9): Reagents according to formula (9) include bis(trialkylsilyl)peroxides. 1 , R 2 , and R 3 are selected from linear, branched or cyclic alkyl, which may be the same or different and may optionally contain heteroatoms selected from O, N, S, and Si, and combinations thereof. Preferably, they are selected from C1-C10 linear alkyl, and preferably they are all the same. Preferably, R 1 , R 2 , and R 3 At least one of them is methyl, and more preferably all of them are methyl.

[0072] Functionalizing reagents according to formula (10): Reagents according to formula (10) include cyclic ureas. In formula (10), R3 represents a divalent, saturated or unsaturated, linear or branched, preferably aliphatic, hydrocarbon group having 1 to 20 carbon atoms and which, in addition to C and H, may preferably contain one or more heteroatoms 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) where 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 aminoalkyl (NR) groups, R is a linear, branched, or cyclic alkyl or alkylaryl residue having 1 to 12 carbon atoms, and X 1 and X 2 can represent chemical bonds between to form carbon-carbon bonds to obtain unsaturation in the carbon chain. The o, p, q, and X groups can be used together so that the total number of carbon atoms is 20 or less. 1 , X 2 , and X 3 is selected.

[0073] In one embodiment of the present disclosure, R3 is selected from substituted alkylene, e.g., X 1 , X 2 , and X 3 is selected from substituted alkylenes corresponding to formula (11) in which at least one of is not H.

[0074] In one embodiment of the present disclosure, R3 is selected from unsubstituted alkylene, e.g., X1 , X 2 , and X 3 is selected from unsubstituted alkylene corresponding to formula (11) in which all of are H. In one preferred embodiment, R3 is -[(CH)2] n -, where n is an integer of 1 to 5, preferably 1 to 3, and more preferably 1 or 2.

[0075] In one embodiment of the present disclosure, R3 is selected from unsaturated substituted or unsubstituted alkylene, e.g., X 1 and X 2 and (IIa) form a carbon-carbon bond. Specific examples of unsaturated alkylene include, but are not limited to, -CH=CH- or -CH2-CH=CH-.

[0076] In formula (10), R1 and R2 are the same or different and represent a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, where the hydrocarbon group can contain, in addition to C atoms and H atoms, one or more heteroatoms, preferably selected from the group consisting of O, N, S, and Si. For example, R1 and R2 can be the same or different and can contain one or more heteroatoms, preferably selected independently from O, N, S, or Si, -(C1-C 20 )-alkyl group, -(C3-C 20 )-cycloalkyl group, -(C6-C 20 )-aryl group, -(C6-C 20 )-alkaryl group, or -(C6-C 20 Preferably, R1, R2 are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, trialkylsilyl having alkyl groups of 1 to 4 carbon atoms per alkyl group, phenyl, and phenyl independently substituted with one, two or three methyl, ethyl, propyl and / or butyl residues.

[0077] Preferred examples of substances according to formula (10) include 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, tetrahydro-1,3-dimethyl-2( Examples of suitable imidazolidinone include, but are not limited to, 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, and hexahydro-1,3-dimethyl-2H-1,3-diazepin-2-one. A particularly preferred example is 1,3-dimethyl-2-imidazolidinone, also known as DMI, i.e., R3 is -CH2-CH2- and / or both R1 and R2 are -CH3.

[0078] Reagents according to formula (10) are described, for example, in U.S. Pat. No. 4,894,409 and International Patent Applications WO 2021 / 009154 and WO 2021 / 009156.

[0079] Equation (12)((RO) x (R) y Si-R''-S-(R') and (13)(RO) x (R) y Functionalizing agents with Si-R''-N(-R')2: R independently represents an alkyl group preferably having 1 to 12 carbon atoms, R' represents an alkyl group or an alkylsilyl group preferably having 1 to 12 carbon atoms, and in the case of two R', both R' can be linked to form a ring structure. In formulas (12) and (13), x is 0, 1, 2, or 3, y is 3-x, and R'' is a spacer group preferably containing 1 to 20 carbon atoms.

[0080] The coupling agent can also be used to obtain a functional group, e.g. an omega-functional group, in which case no functionalizing agent needs to be added after step (ii) but a separate functionalizing reagent can be used, e.g. an alpha-functionalizing agent to form a functional group at the alpha position of the polymer.

[0081] If the polymerization reaction is not initiated by reaction with a coupling agent or by optional reaction with one or more omega functionalizing agents as described above, the polymerization reaction can be terminated, for example, by quenching. Quenching agents known in the art can be used. Typical quenching agents for terminating polymerization include alcohols, such as octanol.

[0082] The polymer can be post-treated and isolated as known in the art. Antioxidants known in the art, such as sterically hindered phenols, aromatic amines, phosphites, thioethers, etc., can be added to the reaction mixture. Preferably, they can be added before or during the post-treatment of the polymer of the present disclosure. Extender oils used in diene rubbers, such as TDAE (Treated Distillate Aromatic Extract), MES (Mild Extraction Solvates), RAE (Residual Aromatic Extract), TRAE (Treated Residual Aromatic Extract), naphthenic oils, and heavy naphthenic oils, can be added to the reaction mixture before or during the post-treatment to obtain oil-extended rubber. The solvent can be removed by conventional methods such as distillation, stripping with steam, or by using vacuum or reduced pressure, at high temperature if necessary. Typically, the solvent is recycled. The polymer crumb may be further dried on a mill, or processed on a mill, for example to form a sheet, or compressed, for example, into a bale.

[0083] Alpha Functionalization: The aforementioned functionalizing reagents can react 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 the addition of an omega functionalizing reagent, an "alpha functionalizing agent" can be added at the start of the polymerization, for example as a functionalizing initiator. Typically, this results in an alpha functionalized polymer, i.e., a polymer with a polar group at the beginning of the chain. Examples of alpha functionalizing agents are described in EP 2847264 A1 and EP 2847242 A1. To prepare an alpha functionalized polymer, the polymer can be prepared as described above, except that one or more alpha functionalizing agents are used. The alpha functionalizing agent is used before step (ii), and typically the functionalizing agent is used at the start of the polymerization reaction, i.e., in step (i), preferably at the beginning of step (i). Typically, the alpha functionalizing agent includes an aliphatic compound that contains, in addition to carbon and hydrogen atoms, heteroatoms selected from Si, O, S, and N, and combinations thereof. Typical alpha functionalizing agents have a molecular weight of up to 5,000 g / mol or less than 2,000 g / mol.

[0084] Alpha functionalizing agents include functional initiators having a functional group or a precursor thereof, e.g., a protected group that can be hydrolyzed or otherwise deprotected, such as during post-processing or compounding to produce a rubber compound. Functional initiators include, for example, salts of organic anions, such as tertiary amines or salts of organic anions of cyclic amines in which the nitrogen atom forms part of an aliphatic ring structure. An example of a tertiary amine containing functional initiator is: [ka] where R3 and R4 are the same or different and have 1 to 20 carbon atoms, and are preferably organic residues selected from linear or branched alkyl, silyl-substituted alkyl, and silyl, and R3 and R4 can be linked to form a ring structure. R2 is preferably a negatively charged linear or branched C1- to C20-alkyl group or a silyl-substituted alkyl group. Further examples include, but are not limited to, linear or cyclic amide initiators, such as salts of aliphatic amines having 4, 5, 6, or 7 carbon atoms and at least one nitrogen atom having a negative charge. The ring may be unsubstituted or substituted one or more times, preferably by C1- to C20-alkyl substituents. Specific examples of cyclic amide initiators include: [ka] These include, but are not limited to:

[0085] Functional initiators also include the active reaction product of one or more initiators and one or more functionalized monomers. The functionalized monomers have at least one functional group or a precursor thereof. The functionalized monomers may be used in equimolar amounts or in excess relative to the initiator, or the initiator may be used in molar excess relative to the functionalized monomer. Examples of functionalized monomers include, but are not limited to, dienes, aliphatic and aromatic vinyls functionalized to one or more functional groups, such as trialkylamino groups, aminosilane groups, or alkoxy groups that can be hydrolyzed to hydroxy groups, or thioalkyl groups that can be hydrolyzed to thiol groups. Specific examples of functionalized aromatic vinyl compounds include, but are not limited to, trialkylaminostyrenes, such as (R1)(R2)N(R3) x -Ph-CH=CH2, where x is 1, 2, 3, 4, or 5, preferably 1, 2, or 3; R 1、R2 and R3 preferably each independently represent a C1-C20 alkyl group or an alkylsilyl group. R1 and R2 can be linked to form a ring. Further examples of functionalized aromatic vinyls include: [ka] where R 1 and R 2 represents a functional group containing at least two selected from the group consisting of carbon, hydrogen, and silicon. Examples include hydrocarbon-based functional groups (functional groups containing carbon and hydrogen) such as methyl and ethyl groups that can be used as phenol protecting groups, and silicon-based functional groups (functional groups containing carbon, hydrogen, and silicon) such as trimethylsilyl and triethoxysilyl groups. Among these, preferred are hydrocarbon-based functional groups, preferably alkyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2. Preferably, R 1 or R 2 At least one of the groups is branched. Examples of recent publications related to alpha functionalization include US Patent Publication No. 2021230416 A1 and EP Patent Publication No. 3733718 A1.

[0086] Mixtures of different functionalized initiators or mixtures of functionalized and non-functionalized initiators can also be used.

[0087] Instead of using functionalizing monomers to prepare functionalized initiators, they can also be used during the polymerization, for example during, after, before, during or after step (i). They can be used in addition to or as an alternative to functionalizing initiators or other functionalizing agents. They can be used, for example, to obtain in-chain functionalized polymers or to produce polymers with side chains carrying functional groups. Suitable functionalizing monomers include aromatic monomers, such as amino-substituted styrenes, and aliphatic monomers, such as vinyl silanes. They can be used during, after, and before, during or after step (ii), or a combination thereof. They can be added continuously or at intervals, for example to form blocks of functionalized monomer units.

[0088] Rubber Compound The polymers according to the present disclosure can be used to make 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 can further include one or more curatives. The curatives can crosslink (cure) the diene polymers and are also referred to herein as "crosslinking agents" or "vulcanizing agents." Suitable curatives include, but are not limited to, sulfur, sulfur-based compounds, and organic or inorganic peroxides.

[0089] In a preferred embodiment of the present disclosure, the curing agent comprises sulfur. Instead of one curing agent, a combination of one or more curing agents can be used, or a combination of one or more curing agents and one or more curing accelerators or curing catalysts can 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 curing accelerators include, but are not limited to, amine derivatives, guanidine derivatives, aldehyde amine condensation products, thiazoles, thiuram sulfides, dithiocarbamates, and thiophospahtes. In another embodiment of the present disclosure, the curing agent includes peroxides. 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. If necessary, a sulfenamide-type, guanidine-type, or thiuram-type vulcanizing accelerator can be used together with the vulcanizing agent. When added, the vulcanizing agent is typically present in an amount of 0.5 to 10 parts by weight, preferably 1 to 6 parts by weight, per 100 parts by weight of rubber.

[0090] The rubber compound is suitable for manufacturing tires or tire components such as sidewalls or tire treads. The tire or tire components include the rubber compound, which is typically in a vulcanized form.

[0091] 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 form, the rubber composition comprises 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.

[0092] Preferably, the filler has a viscosity of preferably 5 to 1,000, preferably 20 to 400 m 2 Examples of suitable fillers include silica-containing particles having a BET surface area (nitrogen absorption) of 1000 nm / g. Such fillers can be obtained, for example, by precipitation from a solution of silicates or by flame hydrolysis of silicon halides. The silica-containing filler particles can have a particle size of 10 to 400 nm. The silica-containing filler can also contain oxides of Al, Mg, Ca, Ba, Zn, Zr, or Ti. Another example of a silicon oxide-based filler is aluminum silicate, preferably 20 to 400 m. 2 Examples of fillers include alkaline earth metal silicates such as magnesium silicate or calcium silicate having a BET surface area of ​​100 / g and a primary particle size of 10 to 400 nm, natural silicates such as kaolin, and other natural silicates such as 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).

[0093] Polar fillers, such as silica-containing fillers, can be modified to increase their hydrophobicity. Suitable modifiers include silanes or silane-based compounds. Typical examples of such modifiers include, but are not limited to, those represented by the general formula (7): (R 1 R 2 R 3 O)3Si-R 4 -X (7) In particular, compounds corresponding to the formula: 1 , R2 , R 3 are each independently an alkyl group, preferably R 1 , R 2 , R 3 are 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.

[0094] Instead of, or in addition to, silica modified as described above, such modification can be carried out in situ, for example during compounding or during the manufacturing process of the tire or a component thereof, for example by adding a modifier, preferably a silane or a silane modifier, for example according to formula (7), during the manufacture of the rubber compound.

[0095] 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. Additional 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 having 3 to 8 carbon atoms and salts of acrylic or methacrylic acid such as zinc acrylate, zinc diacrylate, zinc methacrylate, zinc dimethacrylate, and mixtures thereof.

[0096] In another embodiment, the rubber compound comprises one or more carbon-based fillers, such as one or more carbon blacks. The carbon blacks can be produced, for example, by the lamp black process, the furnace black process, or the gas black process. Preferably, the carbon back has a thickness of 20 to 200 mm. 2 / g BET surface area (nitrogen adsorption). Suitable examples include, but are not limited to, SAF, ISAF, HAF, FEF, and GPF black.

[0097] Further examples of suitable fillers include carbon-silica dual phase fillers, lignin or lignin-based materials, starch or starch-based materials, and combinations thereof.

[0098] In a preferred embodiment, the filler comprises one or more silicon oxides, carbon black, or a combination thereof.

[0099] Typical amounts of filler include 5 to 200 parts per 100 parts of rubber, such as 10 to 150 parts by weight, or 10 to 95 parts by weight per 100 parts by weight of rubber.

[0100] The rubber compound may further include 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 can be used in an amount ranging from 0.5 to 95% by weight, preferably 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 using catalysts based on Ni, Co, T, I or Nd, polybutadiene rubber with a vinyl content of up to 80% and mixtures thereof are of particular interest for the production of automobile tires.

[0101] The rubber compound may also include one or more rubber additives, which are components that can improve the processing characteristics of the rubber composition, that can serve to crosslink the rubber composition, that can improve the physical properties of the vulcanizates made from the rubber, that can improve the interaction between the rubber and the filler, or that can serve to 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 (Mild Extraction Solvates), RAE (Residual Aromatic Extract), TRAE (Treated Residual Aromatic Extract), naphthenic oils, and heavy naphthenic oils, and activators.

[0102] The total amount of rubber additives may 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.

[0103] The rubber composition can be prepared using conventional processing equipment for the manufacture and processing of (vulcanizable) rubber compounds, including rollers, kneaders, internal mixers, or mixing extruders. The rubber composition can be manufactured in a one-stage or multi-stage process, with 2-3 mixing stages being preferred. The crosslinking agent, e.g. sulfur, and accelerators can be added in a separate mixing stage, 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.

[0104] Purpose The rubber composition according to the present disclosure can be used to make rubber vulcanizates, especially tires, especially tire treads. The rubber vulcanizates can be obtained by providing a vulcanizable composition according to the present disclosure and carrying out at least one curing reaction thereon. The vulcanizable and / or vulcanized rubber composition can be molded before, during, or after the curing reaction. The molding can be carried out by process steps including molding, extrusion, and combinations thereof.

[0105] The (vulcanizable) rubber compositions obtained herein are also suitable for the production of molded articles, such as cable sheaths, hoses, drive belts, conveyor belts, roll linings, shoe soles, sealing rings and damping elements.

[0106] Another aspect of the present disclosure relates to a molded article, particularly a tire component such as a tire tread, or a finished tire, comprising a vulcanized rubber composition obtained by vulcanization of the vulcanizable rubber composition according to the present disclosure.

[0107] 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.

[0108] Working Example method Gel permeation chromatography (GPC) at 35° C. (THF as the solvent and polystyrene calibration) was used to determine 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.

[0109] The Mooney viscosity was measured according to DIN ISO 289-1 (2018) under the measurement conditions ML(1+4) at 100 ° C. The Mooney stress relaxation (MSR) was determined from the same measurement according to ASTM D 1646-00.

[0110] The dynamic properties of the vulcanized compounds were determined in accordance with DIN 53513-1990 on an Eplexor 500 N from Gabo-Testanlagen GmbH, Ahlden, Germany, at 10 Hz in the temperature range from -100 °C to +100 °C and a heating rate of 1 K / min (sample: l * w * t=60mm * 10mm * 2 mm strip; free length between sample holders 30 mm). With this method the following properties can 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 tyre under driving conditions. A decrease in tan δ(60°C) reduces the rolling resistance of the tyre. tan δ(0°C) is a measure of the wet grip of the material. An increase in tan δ(0°C) increases the wet grip.

[0111] Elastic properties were 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, without static prestrain in the shear direction, on cylindrical specimens (each of the two specimens was 20 x 6 mm and precompressed to a thickness of 5 mm), with an oscillation of about 0 and a measurement frequency of 10 Hz in the strain range of 0.1 to 40%. This method was used to determine the following properties: G'(0.5%): Dynamic modulus at 0.5% amplitude sweep, G'(15%): Dynamic modulus at 15% amplitude sweep, G'(0.5%)-G'(15%): Difference of 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. The difference G'(0.5%)-G'(15%) is an indication of the Payne effect of the mixture. The smaller this value, the better the dispersion of the filler in the mixture and the better the rubber-filler interaction. tan δ(max) is another measure of hysteresis loss from the tire under driving conditions. A decrease in tan δ(max) reduces the rolling resistance of the tire.

[0112] The rebound resilience was determined at 60° C. in accordance with DIN 53512. An increase in rebound indicates a decrease in rolling resistance.

[0113] polymer Example 1 (for comparison) An inert 20 L reactor was charged with 8500 g hexane, 1500 g 1,3-butadiene, and 10 mmol n-butyllithium (as a 23 wt % solution in hexane) and stirred at 70° C. for 45 minutes. The polymer solution was quenched with 10 mmol n-octanol, stabilized with 4.5 g Irganox® 1520 (2,4-bis(octylthiomethyl)-6-methylphenol), precipitated in ethanol, and dried in a vacuum oven at 65° C. This reference example shows a general procedure for the preparation of diene polymers. Copolymers of one or more conjugated dienes and one or more vinyl aromatic monomers, such as styrene, can be prepared in the same manner.

[0114] Example 1A (for comparison) An inert 20 L reactor was charged with 8500 g hexane, 1500 g 1,3-butadiene, and 16 mmol n-butyllithium (as a 23 wt % solution in hexane) and stirred at 70° C. for 45 min. 2.56 mmol SiCl4 was added and stirred for 30 min. The polymer solution was quenched with 16 mmol n-octanol and stabilized with 7.5 g Irganox® 1520 (2,4-bis(octylthiomethyl)-6-methylphenol). The solvent was removed by steam distillation and the polymer was dried in a vacuum oven at 65° C. The Knee viscosity (ML(1+4) at 100° C.) was measured to be 83 MU.

[0115] Example 2 (for comparison) An inert 20 L reactor was charged with 8500 g hexane, 1500 g 1,3-butadiene, and 14.25 mmol n-butyllithium (as a 23 wt % solution in hexane) and stirred at 70° C. for 45 minutes. 7.125 mmol 2.2-bis(2-tetrahydrofuryl)-propane was added to the living polymer solution and stirred for 5 minutes. 1.924 mmol SiCl4 was added and stirred for 5 minutes. 8.55 mmol octamethylcyclotetrasiloxane was added and stirred for 15 minutes. 8.55 mmol 2,2-dimethyl-1-oxa-4-thia-2-silacyclohexan-6-one was added and stirred for 20 minutes. The solution was quenched with 14.25 mmol n-octanol and stabilized with 7.5 g Irganox® 1520 (2,4-bis(octylthiomethyl)-6-methylphenol). 2 phr of stearic acid was added. The solvent was removed by steam distillation. The polymer was dried in a vacuum oven at 65°C.

[0116] Example 3 (for comparison) Example 1 was repeated except that 16 mmol of n-BuLi was used and the reaction was stirred for 45 minutes, after which 8 mmol of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane was added to the solution and the solution was stirred for an additional 20 minutes.

[0117] Example 4 An inert 20 L reactor was charged with 8500 g hexane, 1500 g 1,3-butadiene, and 16 mmol n-butyllithium (as a 23 wt % solution in hexane) and stirred at 70° C. for 45 minutes. 8 mmol 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane was added and stirred for 20 minutes. 8 mmol 2,2-dimethyl-1-oxa-4-thia-2-silacyclohexan-6-one was added and stirred for an additional 20 minutes. The solution was quenched with 16 mmol n-octanol and stabilized with 7.5 g Irganox® 1520 (2,4-bis(octylthiomethyl)-6-methylphenol). The polymer was isolated as described above.

[0118] Example 5 An inert 20 L reactor was charged with 8500 g hexane, 1500 g 1,3-butadiene, and 15.7 mmol n-butyllithium (as a 23 wt % solution in hexane) and stirred at 70° C. for 45 minutes. To the polymer solution was added 15.7 mmol 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane and the solution was stirred for 20 minutes. 15.7 mmol 2,2,4-trimethyl-1-oxa-4-aza-2-silacyclohexane was added and the reaction mixture was stirred for an additional 20 minutes. The polymer solution was quenched, stabilized, and the polymer was isolated as previously described.

[0119] Example 6 An inert 20 L reactor was charged with 8500 g hexane, 1500 g 1,3-butadiene, and 14.25 mmol n-butyllithium (as a 23 wt % solution in hexane) and stirred at 70° C. for 60 minutes. 7.125 mmol 2,2-bis(2-tetrahydrofuryl)-propane was added to the living polymer solution and stirred for 5 minutes. 14.25 mmol 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane was added and stirred for 15 minutes. 14.25 mmol 2,2-dimethyl-1-oxa-4-thia-2-silacyclohexan-6-one was added and the reaction mixture was stirred for an additional 20 minutes. The polymer solution was quenched with 14.25 mmol of n-octanol and stabilized with 7.5 g of Irganox® 1520 (2,4-bis(octylthiomethyl)-6-methylphenol). After adding 2 phr of stearic acid, the solvent was removed by steam distillation and the polymer was dried in a vacuum oven at 65° C.

[0120] Example 7 An inert 20 L reactor was charged with 8500 g hexane, 1500 g 1,3-butadiene, and 15 mmol n-butyllithium (as a 23 wt % solution in hexane) and stirred at 70° C. for 60 minutes. 7.5 mmol 2,2-bis(2-tetrahydrofuryl)-propane was added to the living polymer solution and the reaction mixture was stirred for 5 minutes. 0.525 mmol octavinyloctasilasesquioxane (POSS-octavinyl substituted, Sigma Aldrich) was added and the reaction mixture was stirred for 5 minutes. 11 mmol octamethylcyclotetrasiloxane was added and stirred for 15 minutes. 11 mmol 2,2-dimethyl-1-oxa-4-thia-2-silacyclohexan-6-one was added and the polymer solution was stirred for an additional 20 minutes. The polymer solution was quenched with 15 mmol of n-octanol and stabilized with 7.5 g of Irganox® 1520 (2,4-bis(octylthiomethyl)-6-methylphenol). Work-up was carried out as in Example 6.

[0121] Example 8 An inert 20 L reactor was charged with 8500 g hexane, 1500 g 1,3-butadiene, and 14.25 mmol n-butyllithium (as a 23 wt % solution in hexane) and stirred at 70° C. for 60 minutes. 7.125 mmol 2,2-bis(2-tetrahydrofuryl)-propane was added to the living polymer solution and stirred for 5 minutes. 1.14 mmol 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane was added and stirred for 5 minutes. 10.83 mmol octamethylcyclotetrasiloxane was added and stirred for 15 minutes. 10.83 mmol 2,2-dimethyl-1-oxa-4-thia-2-silacyclohexan-6-one was added and the reaction mixture was stirred for an additional 20 minutes. The polymer solution was quenched with 14.25 mmol of n-octanol and stabilized with 7.5 g of Irganox® 1520 (2,4-bis(octylthiomethyl)-6-methylphenol). After adding 2 phr of stearic acid, the solvent was removed by steam distillation and the polymer was dried in a vacuum oven at 65° C.

[0122] [Table 1]

[0123] Examples 3-8 show that unsaturated siloxanes can be used to prepare coupled polymers. Coupling is indicated by the degree of coupling and low MSR values. Polymers prepared using unsaturated siloxanes according to the present disclosure can be reacted with different functionalizing agents as shown by Examples 4-8.

[0124] Compound Research It is known that diene rubber functionalized with polar functional groups can improve the dispersion of fillers in tire compounds. In tire compounds, rubber and fillers are the main components, and a good dispersion of fillers in the rubber matrix can ultimately result in improved tire properties. Rubber compounds containing functionalized diene rubbers are typically more difficult to process than their non-functionalized counterparts. It has been found that the polymers obtained using the unsaturated siloxane-based coupling agent according to the present disclosure can also be used to manufacture tire components, and can also obtain compounds with improved filler interaction.

[0125] Examples 9 to 16 Rubber compositions (Examples 9-16) containing the diene rubbers obtained in Examples 1, 1A, 2, 3, 6, 7, and 8 were prepared in a 1.5 L kneader using the ingredients shown in Table 3 and the mixing protocol shown in Table 2. The resulting compositions were vulcanized at 160° C. for 30 minutes. The properties of the vulcanizates are summarized in Tables 3 and 3A.

[0126] [Table 2]

[0127] [Table 3]

[0128] The results show that the polymers obtained with the unsaturated siloxanes according to the invention (Examples 11-13) had improved compound Mooney viscosity than the reference polymers 1 and 2 (Comparative Examples 9 and 10), indicating better processability. Examples 11-13 showed excellent filler dispersion, as shown by the improved Payne effect index (smaller [G'(0.5%)-G'(15%)]) and improved rolling resistance index (rebound 60°C, max tan δ, and tan δ at 60°C) compared to the reference polymer. Wet grip performance (tan δ at 0°C) was similar to the reference polymer.

[0129] Example 14 (for comparison) A functionalized styrene-butadiene polymer was prepared without the use of coupling reagents according to the present disclosure by anionic polymerization in hexane using BuLi as initiator. The living polymer was first treated with OMTS and then with SL in equimolar amounts. The reaction was stopped by adding octanol and IRGANOX1520. The polymer was obtained by steam distillation and drying at 60°C under reduced pressure.

[0130] Example 15 A coupled and functionalized polymer was prepared by anionic polymerization in hexane using 9.55 mmol BuLi as initiator. The living polymer was treated with a coupling agent according to the present disclosure by adding 1.19 mmol 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane. The temperature of the reaction mixture was 60° C. and the mixture was allowed to react at 60° C. for 10 minutes. The coupled polymer was functionalized by treating the reaction mixture with 9.55 mmol 2,2-dimethyl-[1,4,2]oxathiasilinan-6-one and allowing the reaction to proceed at 60° C. for 10 minutes. The reaction was stopped and the polymer was isolated as previously described.

[0131] Example 16 The coupled and functionalized polymers were prepared by first forming a reactive initiator mixture. A moisture-free, nitrogen-flushed 20 L reactor was charged with 8500 g hexane, 1.70 g N,N-dimethylaminomethylstyrene, and 5.43 mmol DTHFP, heated to 35° C., and reacted with 10.56 mmol BuLi for 20 minutes to form a reactive initiator solution. Anionic polymerization was performed by adding a mixture of 1185 g butadiene and 315 g styrene, which was allowed to react for 60 minutes (T Max 58.4° C.). 1.32 mmol 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane was added to the living polymer solution and allowed to react for 10 minutes at 60° C. 10.56 mmol 2,2-dimethyl-[1,4,2]oxathiasilinan-6-one was added and allowed to react for 10 minutes at 60° C. The reaction was quenched and worked up as described above.

[0132] Polymers from Examples 14-16 were compounded using the mixing protocol in Table 2 and the ingredients in Table 3, except that 70 phr of polymer and 30 phr of NdBR (trade name CB24) were used. ZEOSIL 1165 MP was used instead of ULTRASIL 7000 GR. Polymer properties are shown in Tables 4 and 5.

[0133] [Table 4]

[0134] [Table 5]

[0135] The results shown in Table 5 show that the properties of styrene-butadiene copolymers are also improved by coupling with the coupling agent according to the present disclosure. The decrease in the value of G'(0.5%)-G'(15%) indicates that the rubber-filler interaction is improved. The rolling resistance indices (rebound and tan δ at 60°C) remained similar. The wet grip properties were improved as shown by the increase in tan δ at 0°C.

[0136] The polymers of Examples 14-16 were extruded through a Garvey die (70° C. and 50 rpm). The profile obtained with Comparative Polymer 14 was rough, while the profiles obtained with the polymers from Examples 15 and 16 were smooth.

[0137] Example 17 (for comparison) Functionalized styrene-butadiene coupled with a coupling agent not according to the present disclosure was prepared by anionic polymerization in hexane using BuLi as initiator. Octamethylcyclotetrasiloxane and tetrachlorosilane were added to this living polymer and allowed to react for 10 minutes at 70°C. 2,2-Dimethyl-[1,4,2]oxathiasilinan-6-one was added and allowed to react for 30 minutes. The reaction was stopped and worked up as described above.

[0138] Example 18 Styrene-butadiene copolymer was prepared by anionic polymerization in hexane using BuLi as initiator. 3.5 mmol of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane was added to the living polymer and allowed to react at 70°C for 10 min. 14 mmol of 2,2-dimethyl-[1,4,2]oxathiasilinan-6-one was added and allowed to react at 70°C for 10 min. The reaction was quenched and worked up as described above.

[0139] Example 19 A styrene-butadiene copolymer was prepared as in Example 18, except that 15 mmol of glutaric anhydride was used as the modifier.

[0140] Polymers from Examples 17-19 were formulated using the mixing protocol in Table 2 and the ingredients in Table 3. Properties are shown in Tables 6 and 7.

[0141] [Table 6]

[0142] [Table 7]

[0143] Comparison of Examples 18 and 19 with Comparative Example 17 shows the improvement depending on the type of end group.

[0144] Example 20 (for comparison) A styrene-butadiene copolymer was prepared using the coupling agent according to the present disclosure, but without the use of a functionalizing agent. The polymer was prepared using 15 mmol of BuLi as the initiator. 1.6 mmol of octavinyloctasilasesquioxane was added to the living polymer and reacted at 60° C. for 30 minutes. The reaction was quenched and worked up as described above.

[0145] Example 21 Example 20 was repeated. Octavinyloctasilasesquioxane was added and reacted at 60° C. for 30 minutes, followed by addition of 8 mmol of 2,2-dimethyl-[1,4,2]oxathiasilinan-6-one and reaction at 60° C. for 10 minutes. The reaction was stopped and worked up as described above.

[0146] The polymers from Examples 20 and 21 were compounded (mixing protocol in Table 2 and ingredients in Table 3, except used at 70 phr with NdBR(CB24) at 30 phr). Properties are shown in Tables 8 and 9.

[0147] [Table 8]

[0148] [Table 9]

[0149] The results shown in Table 9 show the positive effect of functionalizing the polymer by coupling with different unsaturated siloxane agents (Comparative Example 20 vs. Example 21). The decrease in the value of G'(0.5%)-G'(15%) indicates an improvement in the rubber-filler interaction. The rolling resistance index (rebound and tan δ at 60°C) was improved, as indicated by the increase in rebound and the decrease in tan δ at 60°C. The wet grip properties were improved, as indicated by the increase in tan δ at 0°C.

[0150] When the polymers of Examples 20 and 21 were extruded through a Garvey die (70° C. and 50 rpm), both gave smooth profiles.

[0151] Example 22 A moisture-free, nitrogen-flushed 20 L reactor was charged with 8500 g hexane, 7.44 mmol hexamethyleneimine, 7.44 mmol pyrrolidine, and 6.4 mmol DTHFP, heated to 33.5° C., and reacted with 18.6 mmol BuLi for 30 minutes to form a reactive initiator solution. A mixture of 1185 g butadiene and 315 g styrene was added and polymerized under adiabatic conditions for 60 minutes (T Max 60.2° C.). To this living polymer solution was added 2.33 mmol 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane and reacted at 60° C. for 10 minutes. 18.6 mmol 3-(diethylamino)propyltrimethoxysilane was added and reacted at 60° C. for 10 minutes. The reaction was carried out as previously described.

[0152] Example 23 The polymer was prepared as in Example 22, except that 18.6 mmol of tert-butyl-[3-[dimethoxy(methyl)silyl]propylsulfanyl]-dimethylsilane was added instead of 2,2-dimethyl-[1,4,2]oxathiasilinan-6-one.

[0153] The polymers of Examples 22 and 23 were compounded and compared to Comparative Example 14. The compounding was done as described in Tables 2 and 3, except that 70 phr of polymer and 30 phr of NdBR (trade name CB24) were used. The polymer data is shown in Table 10 and the compound data is shown in Table 11.

[0154] [Table 10]

[0155] [Table 11]

[0156] The test results in Table 11 are shown as index values ​​relative to the values ​​obtained in the Reference Example. A larger index value means that the respective property is improved over the Reference Example. The index values ​​of maximum tan δ and tan δ at 60°C were calculated as: [(value obtained in the Reference Example) / (value in the Example)]×100. The resilience at 60°C, tan δ at 0°C, and S300 were calculated as: [(value in the Example) / (value obtained in the Reference Example)]×100; * The increase in Mooney viscosity is calculated as: ML(1+4)(compound) at 100° C.-ML(1+4)(polymer) at 100° C. Smaller values ​​indicate better processability.

[0157] The values ​​for were unchanged in Example 21 and decreased in Example 22 compared to the reference (not shown in Table 11), and the Garvey profile was the same as the reference. However, the rolling resistance and wet grip indices showed an improvement of the polymer compared to the reference.

Claims

1. A method for producing a polydiene rubber, comprising the steps of: (i) polymerizing at least one aliphatic conjugated diene monomer, preferably having from 4 to 25 carbon atoms, to produce a polymer having a reactive polymer chain end; (ii) reacting at least a portion of the reactive polymer chain ends with a coupling agent containing from 2 to 20 unsaturated siloxane units, preferably from 3 to 15 units, more preferably from 3 to 10 units; (iii) using at least one functionalizing agent to introduce at least one functional group into said polymer, said functional group preferably having, in addition to C and H atoms, at least one heteroatom selected from Si, S, N, O, or a combination thereof; Including, The method, wherein (iii) is performed before, after, or during step (ii).

2. 2. The method of claim 1, wherein the unsaturated siloxane units comprise at least one alkenyl group, preferably selected from the group consisting of vinyl, allyl, n-butenyl, isobutenyl, n-pentenyl, isopentenyl, or combinations thereof.

3. The unsaturated siloxane unit of the coupling agent is represented by formula (1) 【Chemistry 1】 2. The method of claim 1, wherein R1 represents alkenyl, preferably selected from the group consisting of vinyl, allyl, n-butenyl, isobutenyl, n-pentenyl, isopentenyl, and each R2 independently represents H, OH, or an organic residue, preferably having 1 to 20 carbon atoms, and optionally having one or more heteroatoms selected from O, N, Si, S, and combinations thereof.

4. 4. The method of claim 3, wherein each R2 independently represents H, OH, alkenyl having 2 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, wherein the alkyl or alkenyl chain or both may be interrupted once or more than once by ether oxygen atoms, or a siloxane or polysiloxane having up to 10 silicon atoms, wherein the siloxane or polysiloxane has at least one silicone atom optionally bearing at least one aliphatic substituent selected from an alkyl or alkenyl group or a combination thereof, preferably at least one R2 is methyl, more preferably all residues R2 are either methyl or ethyl or a combination thereof.

5. The unsaturated siloxane unit of the coupling agent has formula (2): 【Chemistry 2】 wherein each R independently represents H, OH, or an organic residue, preferably having 1 to 20 carbon atoms, and optionally having one or more heteroatoms selected from O, N, Si, S, and combinations thereof.

6. 6. The method of claim 5, wherein R represents H, OH, alkenyl having 2 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, wherein the alkyl or alkenyl chain or both may be interrupted once or more than once by ether oxygen atoms, or a siloxane or polysiloxane having up to 10 silicon atoms, wherein the siloxane or polysiloxane may have at least one silicone atom optionally bearing at least one aliphatic substituent selected from an alkyl or alkenyl group or a combination thereof, preferably at least one R is methyl, more preferably all residues R are either methyl or ethyl or a combination thereof.

7. The method of any one of claims 1 to 6, wherein the coupling agent has at least one cyclic structure containing at least three of the unsaturated siloxane units.

8. The coupling agent is represented by formula (3) 【Chemistry 3】 where n is an integer from 1 to 5, preferably from 1 to 3, R1 and R2 are defined as claimed in claim 4 or 5, preferably R1 is vinyl and each R2 independently corresponds to C １ -C ７ The process according to any one of claims 1 to 7, wherein the alkyl is selected from the group consisting of methyl, ...

9. The coupling agent has the formula (4): 【Chemistry 4】 wherein Ra, Rb, Rc, Rd, Re, Rf, Rg, and Rh are each the same or different and each independently correspond to C １ -C １０ -Alkyl group, C ２ -C ６ -alkenyl group, or -O-Si-(R １’ R ２’ R ３’ ) groups, R1', R2', and R3' are each independently selected from C １ -C １０ -Alkyl group or C ２ -C ６ -alkenyl groups, preferably at least one of R1', R2' and R3' is a vinyl group unit, and said coupling agent is selected from at least two, preferably at least three C ２ -C ６ The method according to claim 1, wherein the alkyl group comprises an alkenyl group, preferably a vinyl group, and preferably all of Ra to Rh are vinyl.

10. The method according to any one of claims 1 to 9, wherein the coupling agent has a molecular weight of less than 5000 g / mol, preferably less than 2000 g / mol.

11. The method of any one of claims 1 to 10, wherein the conjugated diene monomer is 1,3 butadiene.

12. 12. The process according to any one of claims 1 to 11, wherein step (i) comprises copolymerising one or more copolymerisable vinyl aromatic comonomers, preferably selected from styrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, para-tertbutylstyrene, and combinations thereof.

13. The method includes adding a functionalizing agent after step (i) and before, during, or after step (ii), or a combination thereof, the functionalizing agent being preferably an anhydride, a carbamide, (R ３ Si—N—; (R ３ ) Si-; (R) ３ Si-S-; (R) ２ 13. The method according to any one of claims 1 to 12, wherein the R comprises at least one group selected from Si(-O-)-, Si(-O-)-, or a combination thereof, each R independently represents an alkyl or alkoxy having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and two residues R can be linked together to form a ring structure.

14. 14. The method according to any one of claims 1 to 13, wherein the method comprises using and adding in step (i) an alpha functionalizing agent, or in steps (i), (ii) or after step (iii) a functionalized comonomer, or the method comprises the use of both at least one functionalized comonomer and at least one alpha functionalizing agent.

15. A polydiene rubber obtainable by the process according to any one of claims 1 to 14.

16. A curable composition comprising the polydiene rubber of claim 15, further comprising at least one vulcanizing agent for curing said polydiene rubber, preferably comprising said vulcanizing agent in an amount of 0.5 to 10 parts by weight per 100 parts by weight of diene rubber.

17. 16. A composition comprising a cured polydiene rubber obtained by curing the curable composition of claim 15, the composition being preferably an article preferably selected from a tire or a tire tread.

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