Amine-Containing Vinyldisiloxanes in the Preparation of Elastomeric Polymers

Abstract

The present invention relates to amine-containing vinyldisiloxane compounds useful in the manufacture of elastomeric polymers that can be used in rubber products such as tires. The present invention further relates to processes for preparing elastomeric polymers in the presence of vinyldisiloxane compounds, elastomeric polymers obtained by such processes, unvulcanized and vulcanized polymer compositions comprising the elastomeric polymers, and articles comprising one or more components formed from the vulcanized polymer compositions, such as tires or components thereof.

Description

[Technical field]

[0001] The present invention relates to novel amine-containing vinyldisiloxane compounds that are useful as modifying monomers in the manufacture of elastomeric polymers that can be used in rubber products such as tires. The present invention further relates to a process for preparing elastomeric polymers in the presence of the vinyldisiloxane compounds, the elastomeric polymers obtained by the process, unvulcanized and vulcanized polymer compositions comprising the elastomeric polymers, and articles comprising one or more components formed from the vulcanized polymer compositions. [Background technology]

[0002] Amine-containing vinyl silanes are used in the rubber art as modifying monomers in the polymerization of diene monomers such as butadiene, optionally together with aromatic vinyl monomers such as styrene, to produce rubbers that can be suitably used in the manufacture of fuel-efficient rubbers.

[0003] One approach to obtain fuel-efficient tires consists in the production of tire compounds with reduced hysteresis loss. The hysteresis loss of crosslinked elastomeric polymer compositions is related to their tan δ value at 60°C (see: ISO 4664-1:2005; Rubber, Vulcanized or thermoplastic; Determination of dynamic properties-part 1: General guidance). In general, vulcanized elastomeric polymer compositions with relatively low tan δ values ​​at 60°C are preferred due to their low hysteresis loss. In the final tire product, this leads to lower rolling resistance and improved fuel economy. In contrast, it is generally accepted that a decrease in the tan δ value at 0°C corresponds to a decrease in the wet grip of the tire product, and that tires with lower rolling resistance can be obtained at the expense of a decrease in wet grip.

[0004] For example, in random solution styrene butadiene rubber (random SSBR), when the polystyrene unit concentration decreases relative to the total polybutadiene unit concentration, the glass transition temperature of the SSBR decreases, resulting in a decrease in tan δ at 60° C. and tan δ at 0° C. (corresponding to a decrease in tire rolling resistance and a decrease in wet grip performance). Therefore, to properly evaluate the performance of a rubber vulcanizate, tan δ at 60° C. and tan δ at 0° C. should be monitored along with the heat build-up of the tire.

[0005] US Pat. No. 8,304,488 relates to conjugated diene polymers obtained by polymerizing conjugated diene monomers and aminosilane-containing monomers, which can be used in rubber articles such as tires.

[0006] DE 102011109823 describes conjugated diene-based polymers containing diene-based, vinyl silane and vinyl amine monomer units for use in rubber compositions for tires.

[0007] The present invention is directed to providing modifying monomers useful for the preparation of elastomeric polymers, and corresponding elastomeric polymers and compositions containing same, which provide an improved performance balance of rolling resistance and wet grip properties combined with satisfactory processability in terms of Mooney viscosity (CML) and maintenance of mechanical properties (e.g. tensile strength (TS), elongation at break (EB), and abrasion resistance). Summary of the Invention

[0008] The present invention is based on the discovery that the above objects can be achieved by carrying out the polymerization of conjugated diene monomers in the presence of specific amine-containing vinyldisiloxane compounds.

[0009] Accordingly, in a first aspect, the present invention provides a vinyldisiloxane compound of formula 1: [ka] (In the formula, VS is a vinyldisiloxane moiety; X is an organic group bonded to a Si atom of the vinyldisiloxane moiety and having at least one tertiary amino group A; m is 1 or 2).

[0010] Vinyldisiloxane compounds of formula 1 include compounds represented by formula 2: [ka] (In the formula, R and R' are independently C 1-18 is selected from hydrocarbyl, R 1 is optionally substituted vinyl, wherein one or more optional substituents are selected from methyl, ethyl, and vinyl; X is independently selected from one of the following moieties (X-1 through X-5): [ka] R 2 is C 1-18 is hydrocarbylene, A is NR 3 R 4 and R 3 and R 4 are independently linear, branched, and cyclic C 1-8 Alkyl, C 6-12 Aryl, C7-C 15 Aralkyl, SiR″3, or linear, branched, and cyclic C 2-8 alkyl-O-SiR″3, each R″ is independently selected from 1-6 Alkyl, C 6-12 Aryl and C 7-18 alkylaryl; R 3 R is arranged to form a ring. 2 or R 4 and the ring may be further bonded to R 2 In addition to the nitrogen atom bonded to R, R may contain one or more selected from oxygen atoms, nitrogen atoms, and sulfur atoms. 3 and R 4are both SiR″3, the two R″ may be bonded to each other to form a ring together with the Si atom to which they are bonded; A' is NR 5 and R 5 is linear, branched, and cyclic C 1-8 Alkylene, C 6-12 Arylene, C7-C 15 AralkyleneSiR″3 or R 2 A or A' is a cyclic diaminediyl group such as piperazinyl; n is 1 or 2, m is 1 or 2, and m+n is 2 or 3.

[0011] In a second aspect, the present invention provides a process for the preparation of an elastomeric polymer, the process comprising polymerizing at least one conjugated diene monomer and, optionally, one or more aromatic vinyl monomers in the presence of one or more initiator compounds and one or more compounds of formula 1 as defined in the first aspect of the present invention. In a preferred embodiment of the second aspect of the present invention, the polymerization is carried out in the presence of one or more compounds of formula 2 as defined in the first aspect of the present invention.

[0012] In a third aspect, the present invention provides an elastomeric polymer obtainable by the process defined in the second aspect of the present invention.

[0013] In a fourth aspect, the present invention provides a non-vulcanized polymer composition comprising an elastomeric polymer of the third aspect of the present invention and one or more additives.

[0014] In a fifth aspect, the present invention provides a vulcanised polymer composition obtainable by vulcanising the polymer composition of the fourth aspect of the present invention and one or more vulcanising agents.

[0015] In a sixth aspect, the present invention provides a method for preparing a vulcanised polymer composition, the method comprising the step of vulcanising a polymer composition of the fourth aspect of the invention comprising one or more vulcanising agents.

[0016] In a seventh aspect, the present invention provides an article comprising at least one component formed from the vulcanized polymer composition of the fourth aspect of the invention.

[0017] The present invention is based on the discovery that certain amine-containing vinyldisiloxanes can be used as modifiers ("modifying monomers") to allow for the preparation of elastomeric polymers and compositions that exhibit beneficial properties, particularly when used in the manufacture of tires. In particular, it has been surprisingly found that vulcanized polymer compositions ("vulcanized rubber compounds") produced from the elastomeric polymers of the present invention exhibit an improved balance of low rolling resistance and high wet grip combined with good processing and mechanical properties. The beneficial properties have been found especially when using vulcanized polymer compositions of the present invention that contain silica or carbon black as fillers.

[0018] Aminosilanes as modifiers are known to result in the formation of covalent Si-O-Si bonds between the modified polymer and, for example, silica as a filler. However, it has been observed that aminosilane-modified polymer compositions have poor processing properties and unfavorable mechanical properties.

[0019] Without being bound by theory, the inventors speculate that due to the presence of both amine groups and disiloxane structures, the amine-containing vinyldisiloxanes of the present invention can further generate non-covalent bonds in the form of coordinate bonds, resulting in more favorable interactions with fillers such as silica or carbon black in polymer compositions. The elastomeric polymers of the present invention modified with one or more amine-containing vinyldisiloxane compounds of the present invention provide an improved balance of performance in terms of rolling resistance and wet grip, as well as satisfactory processability and satisfactory or improved mechanical properties.

[0020] As a result, the present invention addresses the requirements set forth herein and allows them to be met by a modifying monomer not previously contemplated in the art, namely, an amine-containing vinyldisiloxane. [Brief description of the drawings]

[0021] [Figure 1] 1 shows the molecular weight distribution of polymer example A (Ex. A) and comparative polymer example A (CEx. A) as measured by size exclusion chromatography (SEC). [Diagram 2] 1 shows the molecular weight distributions of Polymer Example K (Ex.K), Polymer Example L (Ex.L), Polymer Comparative Example K (CEx.K), and Polymer Reference Example L (REx.L) as determined by size exclusion chromatography (SEC). [Diagram 3] 1 shows the molecular weight distributions of SP / LP blends A, B, C, and D as measured by size exclusion chromatography (SEC). [Figure 4] FIG. 2 is a monomer incorporation plot showing the conversion of butadiene (Bd) and modifying monomer S13 as a function of time for Polymer Example A (Ex. A) as measured by gas chromatography (GC). [Diagram 5] 1 is a monomer incorporation plot showing the conversion of butadiene (Bd), styrene, and modifying monomer C2 as a function of time for Comparative Polymer Example K (CEx.K) as measured by gas chromatography (GC). [Figure 6] FIG. 1 is a monomer incorporation plot showing butadiene (Bd) and styrene conversion as a function of time for Polymer Reference Example L (REx.L) as measured by gas chromatography (GC). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] Amine-containing vinyldisiloxane compounds The amine-containing vinyldisiloxane compound according to the first aspect of the present invention is characterized by having in combination both a siloxy group bonded to a silicon atom of the vinylsilane portion (representing a vinyldisiloxane) and an organic group bonded to a Si atom of the vinyldisiloxane portion and having at least one tertiary amino group.

[0023] Specifically, the vinyldisiloxane compound of the first aspect of the present invention corresponds to Formula 1: [ka]

[0024] In formula 1, VS represents a vinyldisiloxane moiety. According to the present invention, the vinyldisiloxane moiety is characterized by containing Si-O-Si units and at least one vinyl group.

[0025] The vinyldisiloxane compound of the first aspect of the present invention may have one organic moiety bonded to the Si atom of the vinyldisiloxane and having at least one tertiary amino group (i.e., m in Formula 1 represents 1), or may have two organic moieties bonded to each Si atom of the vinyldisiloxane and each having at least one tertiary amino group (i.e., m in Formula 1 represents 2). In the present invention, a tertiary amino group refers to a nitrogen-containing group in which the nitrogen has three organic substituents.

[0026] In a preferred embodiment, the vinyldisiloxane compound corresponds to Formula 2: [ka] (Wherein R and R′ are independently C 1-18 R is selected from hydrocarbyl; 1 is an optionally substituted vinyl, where one or more optional substituents are selected from methyl, ethyl, and vinyl; X is independently selected from one of the following moieties (X-1 through X-5): [ka] R 2 is C 1-18 is hydrocarbylene, A is NR 3 R 4 and R 3 and R 4 are independently linear, branched, and cyclic C 1-8Alkyl, C 6-12 Aryl, C 7-15 Aralkyl, SiR″3, or linear, branched, and cyclic C 2-8 alkyl-O-SiR″3, each R″ is independently selected from 1-6 Alkyl, C 6-12 Aryl and C 7-18 alkylaryl; R 3 R is arranged to form a ring. 2 or R 4 and the ring may be bonded to R 2 In addition to the nitrogen atom bonded to R, R may contain one or more selected from oxygen atoms, nitrogen atoms, and sulfur atoms. 3 and R 4 When both are SiR″3, the two R″ may be bonded to each other to form a ring together with the Si atom to which they are bonded; A′ is NR 5 and R 5 is linear, branched, and cyclic C 1-8 Alkylene, C 6-12 Arylene, C7-C 15 Aralkylene, SiR″3, or R 2 A' is a cyclic diaminediyl group such as piperazinyl; n is 1 or 2, m is 1 or 2, and m+n is 2 or 3).

[0027] In a preferred embodiment, R in formula 2 2 is linear or branched C 1~8 Alkylene, C 6~12 Arylene, or C7~C 15 More preferably, R 2 are independently phenylene or linear C 1-8 Alkylene, preferably a straight chain C 3-6 It is preferably alkylene, and more preferably C3 alkylene.

[0028] In another preferred embodiment, R and R' in formula 2 are independently selected from methyl, ethyl, n-propyl, i-propyl, t-butyl, phenyl and benzyl.1 is an optionally substituted vinyl, where one or more optional substituents are selected from methyl, ethyl, and vinyl. X is independently selected from one of the moieties X-1 to X-5. R in Formula 2 2 is C 1-18 Hydrocarbylene, preferably linear or branched C 1-8 Alkylene, C 6-12 Arylene, or C7-C 15 Aralkylene, more preferably R 2 are independently phenylene or straight-chain C 1-8 Alkylene, preferably a straight chain C 3-6 A is preferably C alkylene, more preferably C alkylene. 3 R 4 and R 3 and R 4 are independently linear, branched, and cyclic C 1-8 Alkyl, C 6-12 Aryl, C 7-15 Aralkyl, SiR″3, or linear, branched, and cyclic C 2-8 alkyl-O-SiR″3, each R″ is independently selected from 1-6 Alkyl, C 6-12 Aryl and C 7-18 alkylaryl; R 3 R 2 or R 4 and the ring may be bonded to R 2 In addition to the nitrogen atom bonded to R, R may contain one or more selected from oxygen atoms, nitrogen atoms, and sulfur atoms. 3 and R 4 When both are SiR″3, the two R″ may be bonded to each other to form a ring together with the Si atom to which they are attached. A′ is NR 5 and R 5 is linear, branched, and cyclic C 1-8 Alkylene, C 6-12 Arylene, C7-C 15In formula 2, n is 1 or 2, m is 1 or 2, and m+n is 2 or 3.

[0029] In the present invention, the vinyl group is represented by the group C(R a R b )=C(R c )-defined as R a , R b , and R c is independently selected from hydrogen, methyl, ethyl, or vinyl. In one particularly preferred embodiment of any of the above vinyldisiloxane compounds, R 1 The vinyl group in R represents an unsubstituted vinyl, i.e., R a , R b and R c are all hydrogen, and R 1 corresponds to CH2=CH-. In another preferred embodiment, R 1 is a substituted vinyl, R a or R b is unsubstituted vinyl, and R c is hydrogen and R 1 corresponds to 1,3-butadienyl. More preferably, R 1 is unsubstituted vinyl.

[0030] In any of the above vinyldisiloxane compounds, the amine moiety A may be represented by a cyclic amine, including, for example, the following: [ka] Preferably, A is [ka] It is expressed as R * is C 1-6 Alkyl, C 6-12 Aryl and C 7-18 Alkylaryl, SiR″3, or linear, branched, and cyclic C 2-8alkyl-O-SiR"3, where R" is defined as above. More preferably, A is a piperazinyl moiety. [ka] It is expressed as:

[0031] Preferably, when A represents a piperazinyl moiety, R * is methyl, ethyl, butyl, phenyl, benzyl, or A is SiR″3 or C 2-8 The piperazinyl may be represented by a piperazinyl substituted with alkyl-O-SiR"3, where R" is independently selected from methyl, ethyl, n-propyl, i-propyl, t-butyl, phenyl, and benzyl.

[0032] In another embodiment, in A, R 3 and R 4 are independently linear, branched, and cyclic C 1-8 Alkyl, C 6-12 Aryl and C 7-15 Preferably, R is selected from the group consisting of aryl, arylalkyl ... 3 and R 4 is independently selected from methyl, ethyl, phenyl, and benzyl.

[0033] In any of the vinyldisiloxane compounds of the first aspect of the invention corresponding to formula 2, each R may be independently selected from methyl, ethyl, i-propyl, t-butyl, and phenyl. Preferably, the three R may be selected from the following combinations of substituents: (methyl, methyl, methyl), (ethyl, ethyl, ethyl), (i-propyl, i-propyl, i-propyl), (phenyl, phenyl, phenyl), (methyl, methyl, t-butyl), (methyl, methyl, i-propyl), (ethyl, ethyl, i-propyl), and (phenyl, phenyl, t-butyl). More preferably, R is selected from (ethyl, ethyl, ethyl), (i-propyl, i-propyl, i-propyl), and (methyl, methyl, t-butyl). When R″ is present, it may be equally selected from the substituents of R.

[0034] In any of the above vinyldisiloxane compounds corresponding to formula 2, n is 1 and m is 2, or n is 2 and m is 1, or n is 1 and m is 1; Preferably, n is 1 and m is 2 or 1.

[0035] As noted above, in one embodiment of the vinyldisiloxane compound of the first aspect of the present invention, X in Formula 2 corresponds to (X-1): [ka] (In the formula, R, R', R 1 , R 2 and A are defined as above. Preferably, R 1 is an unsubstituted vinyl group, or R 2 is C 1-8 Alkylene, preferably linear C 1-8 alkylene, such as methylene, ethylene, n-propylene, and n-butylene, or R 1 is an unsubstituted vinyl group, R 2 is C 1-8 Alkylene, preferably linear C 1-8 It represents alkylene, such as methylene, ethylene, n-propylene, and n-butylene. In another preferred embodiment, when n is 1 and m is 1, R' is selected from methyl, ethyl, n-propyl, i-propyl, t-butyl, phenyl, and benzyl, and is preferably methyl.

[0036] In another exemplary embodiment, R 1 is unsubstituted vinyl, R' is methyl, and R 2 is C 1-8 In this exemplary embodiment, A is selected from alkylene, preferably n-propylene, and each R is independently selected from methyl, ethyl, i-propyl, t-butyl, and phenyl. 3 R 4 It is expressed as R 3 and R 4forms a ring which may further contain heteroatoms selected from oxygen, nitrogen, and sulfur, preferably nitrogen. For example, R 3 and R 4 Piperazinyl [ka] The bonds form R * is preferably methyl, phenyl, benzyl, SiR″3, or linear, branched and cyclic C 2-8 Alkyl-O-SiR″3, C 2-8 The alkyl may preferably be a linear alkyl, and R″ is preferably selected from methyl, ethyl, n-propyl, i-propyl, t-butyl, and phenyl. In a preferred embodiment, R * is methyl, phenyl, or benzyl.

[0037] Or, R 3 and R 4 may each independently represent SiR″3, where R″ may preferably be selected from methyl, ethyl, n-propyl, i-propyl, t-butyl, and phenyl. In one embodiment, each R″ represents methyl. In another embodiment, R 3 and R 4 are both SiR″3, and the two R″ attached to different Si atoms together form a ring. For example, the two R″ can form an alkylene group such as ethylene, and the remaining R″ can each independently be C 1-6 It may be selected from alkyl, preferably methyl.

[0038] In any of the above vinyldisiloxane compounds corresponding to Formula 2, m is preferably 1 and n is preferably 1.

[0039] Also, in any of the above vinyldisiloxane compounds corresponding to formula 2, R 3 can also be combined with R to form a ring. 2In this case, A may be bonded to the Si atom via a cyclic ring structure, and preferably A is incorporated into the cyclic ring structure. For example, -R 2 -A is [ka] and R * is defined as above and may preferably be methyl; y is 1 or more, preferably 1 or 2, and more preferably 2.

[0040] In another embodiment of the above vinyldisiloxane compound corresponding to formula 2, X is (X-1) and m is 2. In this embodiment, R 2 is preferably C 1-8 It may be an alkylene, for example, methylene, ethylene, n-propylene, or n-butylene, and more preferably n-propylene. 3 R 4 In A, which is represented by R 3 and R 4 is independently 1-8 alkyl, preferably methyl and / or benzyl. Alternatively, R 3 and R 4 may be attached to form a ring together with the nitrogen atom to which it is attached to represent a pyrrolidine or piperidine moiety.

[0041] In one embodiment of the vinyldisiloxane compound where X is (X-1) and m is 2, R 3 and R 4 Each set may be different or the same.

[0042] In another embodiment of any of the vinyldisiloxane compounds described above, X in formula 2 can correspond to (X-2), and the compound can be represented by the formula: [ka] (In the formula, each R 2are each independently selected from the above definitions, and A is as defined in (X-1). 2 At least one of the following is C 1-8 It is selected from alkylene, preferably methylene, ethylene, and n-propylene.

[0043] In another embodiment, X in formula 2 can correspond to (X-3), and the compound has the formula: [ka] (In the formula, each R 2 are each independently selected from the above definitions, and A is as defined in (X-1). 2 At least one of the following is C 1-8 It is selected from alkylene, preferably methylene, ethylene, and n-propylene.

[0044] In a further embodiment, X in formula 2 may correspond to (X-4) and the compound is represented by the formula: [ka]

[0045] In this embodiment, R 2 are each preferably linear or branched C 1-8 Preferably, A' represents a cyclic diaminediyl structure, such as piperazinyl as shown above. As a non-limiting example, a compound of formula 2 in which X represents (X-4) can be: [ka] (Wherein, R′ and R 3 is defined as above).

[0046] In another embodiment, X in formula 2 can correspond to (X-5). That is, the vinyldisiloxane compound can have a structure where X is represented by the following structure: [ka] (In the formula, R, R 1 , R 2 , R', and n are defined as above).

[0047] In the present invention, X preferably corresponds to (X-1) as defined above.

[0048] Preparation of amine-containing vinyldisiloxane compounds The synthesis of the amine-containing vinyldisiloxanes of the present invention constitutes part of the common general knowledge of the person skilled in the art. For example, a chlorovinyldisiloxane precursor can be reacted with a Grignard reagent prepared from a halogenated derivative of the amine-containing moiety X defined in formula 1. [ka]

[0049] The conversion of chlorovinyldisiloxanes can be carried out in a manner similar to the reactions disclosed for chlorovinylalkylsilanes with Grignard reagents, for example, as described in: RA Benkeser et al. J. Org. Chem. 1979, 44, pp. 1370-1376; or J. Kazmierczak at al. J. of Catalysis 2018, 367, pp. 95-103.

[0050] Chlorovinyldisiloxanes can be prepared from the corresponding dichlorovinylsilane (when m=1) or trichlorovinylsilane (when m=2) and silanol R3SiOH in the presence of a base such as triethylamine (TEA). A second approach to alkylamine-containing vinylsilanes is described in US20100317852A1 (Shin Etsu). Here, allylamine is converted to chlorosilane in the presence of a transition metal catalyst such as a Pt complex. However, for the vinyldisiloxanes of the present invention, this approach needs to be slightly adjusted.

[0051] polymerization The process for preparing an elastomeric polymer according to the second aspect of the present invention comprises polymerizing at least one conjugated diene monomer and optionally one or more aromatic vinyl monomers in the presence of an initiator compound and one or more of the modifying monomers of the present invention.

[0052] The elastomeric polymers can generally be prepared by anionic polymerization, radical polymerization, or transition metal catalyzed polymerization, but are preferably prepared by anionic polymerization. Two or more vinyldisiloxane compounds of formula 1 can be used in combination as the modifying monomer(s). The polymerization can be carried out in a solvent and can be carried out using one or more of chain end modifiers, coupling agents including modified coupling agents, randomizing compounds, and polymerization promoter compounds.

[0053] In addition to the specific disclosure below, generally applicable instructions regarding polymerization techniques including polymerization initiator compounds, polar coordination compounds and accelerators (for increasing / varying initiator reactivity, for randomly placing aromatic vinyl monomers, and / or for randomly placing and / or varying the concentration of 1,2-polybutadiene or 1,2-polyisoprene or 3,4-polyisoprene units incorporated into the polymer); the amount of each compound, the monomer(s); and suitable process conditions are described in WO2009 / 148932, the contents of which are incorporated herein by reference in their entirety.

[0054] a) Conjugated diene (conjugated diene monomer) Examples of conjugated diene monomers useful in the present invention include 1,3-butadiene, 2-(C 1-5-alkyl)-1,3-butadiene, such as isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 2-methyl-2,4-pentadiene, cyclopentadiene, 2,4-hexadiene, 1,3-cyclooctadiene, β-myrcene, terpinene, α-farnesene. A mixture of two or more conjugated dienes may be used. Preferred conjugated dienes include 1,3-butadiene and isoprene. In a preferred embodiment, the conjugated diene is 1,3-butadiene. The conjugated dienes may be used in an amount of up to 99.99% by weight, preferably 30 to 99.99% by weight, based on the total weight of the monomers used in the polymerization reaction.

[0055] b) Aromatic vinyl monomers Any vinyl aromatic monomer is a compound that has only one vinyl group attached to an aromatic group. Examples of vinyl aromatic monomers are styrene, C 1-4 Alkyl-substituted styrenes, such as 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, α-methylstyrene, 2,4-diisopropylstyrene, and 4-tert-butylstyrene, stilbene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethylether, N,N-dimethylaminoethylstyrene, tert-butoxystyrene, and vinylpyridine. Two or more aromatic vinyl monomers may be used in combination. A preferred aromatic monovinyl monomer is styrene. The aromatic vinyl monomer(s) may be used in an amount of up to 70% by weight, in particular 40-70% by weight or 0-40% by weight, for example 15-40% by weight or 2-15% by weight, based on the total weight of the monomers used in the polymerization reaction, depending on the application.

[0056] In a preferred embodiment, the conjugated diene is 1,3-butadiene and the aromatic vinyl monomer is styrene.

[0057] c) Other monomers Comonomers other than the vinyldisiloxane monomers of Formula 1, the conjugated diene monomers and the aromatic vinyl monomers that may be used in preparing the elastomeric polymers of the present invention include acrylic monomers such as acrylonitrile, acrylates such as acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, and methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate.

[0058] Comonomers also include aromatic divinyl compounds having two or more vinyl groups attached to an aromatic group, such as 1,2-divinylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene (which may be used as an isomeric mixture of 1,2- / 1,3- / 1,4-divinylbenzene, referred to herein as "DVB"). They may be used in a total amount of 1% by weight or less (based on the total molar weight of the monomers used to make the polymer). In one preferred embodiment, 1,2-divinylbenzene is used in combination with styrene and butadiene or isoprene. Further monomers include, for example, vinylaminosilanes as described in WO2015 / 055252, WO2016 / 131590, WO2017 / 216344, and WO2019 / 020752, or monomers as described in WO2008108377A or WO2019216645A1, the contents of which are incorporated herein by reference in their entirety.

[0059] d) Initiator Compound The polymerization process of the present invention is carried out in the presence of an initiator compound, and two or more initiator compounds may be used in combination. The initiator compound may be a monovalent or polyvalent (divalent, trivalent, etc.) initiator compound, including a dianionic initiator. Suitable initiator compounds include alkali metals, organic alkali metal compounds, complexes of alkali metals with polar compounds, oligomers containing alkali metals, and Lewis acid-base complexes. Exemplary alkali metals include lithium, sodium, potassium, rubidium, and cesium. Exemplary organic alkali metal compounds include ethyl lithium, n-butyl lithium, s-butyl lithium, t-octyl lithium, isopropyl lithium, phenyl lithium, cyclohexyl lithium, 2-butyl lithium, 4-phenylbutyl lithium, t-butyldimethylsilyloxypropyl lithium, dialkylaminopropyl lithium, N-morpholinopropyl lithium, lithium diisopropylamide, lithium piperidide, lithium pyrrolidide, dilithiated diphenylethylene compounds, multilithiated trivinylbenzene compounds, sodium biphenylide, sodium naphthalenide, and potassium naphthalenide. Exemplary complexes between alkali metals and polar compounds include lithium-tetramethylethylenediamine complex, lithium-tetrahydrofuran complex, lithium-ditetrahydrofuranpropane complex, and their sodium and potassium analogs. More preferably, the initiator compound is a mono- or di-lithium alkyl, alkylaryl or aryl compound. Further useful initiators include the aminosilane polymerization initiators described in WO2014 / 040640 (incorporated herein in its entirety by reference) and the polymerization initiators described in WO2015 / 010710 (incorporated herein in its entirety by reference). The total amount of initiator(s), in particular organolithium initiator(s), will be adjusted depending on the monomer and the target molecular weight. The total amount is usually 0.05-5 mmol, preferably 0.2-3 mmol, per 100 grams of monomer.

[0060] e) Solvent The polymerization is usually carried out as a solution polymerization, where the polymer formed is substantially soluble in the reaction mixture, or as a suspension / slurry polymerization, where the polymer formed is substantially insoluble in the reaction medium. The terms "solution polymerization" and "suspension polymerization" or "slurry polymerization" are used in their conventional sense in the art of polymerization. More preferably, the polymer is obtained by solution polymerization. As the polymerization solvent, a hydrocarbon solvent that does not quench the initiator, catalyst, or active polymer chains is conventionally used. A combination of two or more solvents may be used. Exemplary hydrocarbon solvents include aliphatic and aromatic solvents. Specific examples include propane (including possible structural isomers), butane, pentane, hexane, heptane, butene, propene, pentene, hexane, octane, benzene, toluene, ethylbenzene, and xylene.

[0061] f) Chain End Modifiers In the polymerization reaction of the present invention, one or more chain end modifiers may be used to react with the ends of the polymer chains in the polymers of the present invention to further control the polymer properties. In general, silane sulfide omega chain end modifiers such as those disclosed in WO2007 / 047943, WO2009 / 148932, US6,229,036, and US2013 / 0131263 (each of which is incorporated herein by reference in its entirety) can be used for this purpose. Other chain end modifiers suitable for use in the present invention include those disclosed in WO2014 / 040640 and WO2015 / 010710, as well as the silane sulfide modifiers described in WO2014 / 040639, each of which is incorporated herein by reference in its entirety.

[0062] The chain end modifying agent may be added intermittently (at regular or irregular intervals) or continuously during the polymerization, but is preferably added when the polymerization conversion is greater than 80%, more preferably when the conversion is greater than 90%. Preferably, a substantial amount of the polymer chain ends are not terminated prior to reaction with the chain end modifying agent, i.e., living polymer chain ends are present and available to react with the modifying agent.

[0063] Other chain end modifiers suitable for use in the present invention include those disclosed in WO2014 / 040639, WO2020179705A1, JP2020015881A, and WO2019225824A1, the contents of each of which are incorporated herein in their entirety.

[0064] g) Coupling Agent Additionally, coupling agents ("coupling agents") can be used as optional components in the process of the present invention to control polymer molecular weight and polymer properties. Coupling agents will reduce the number of free chain ends of the elastomeric polymer and / or reduce the polymer solution viscosity, compared to a non-coupled essentially linear polymer of the same molecular weight. Coupling agents such as tin tetrachloride, tetrachlorosilane, tetraethoxysilane, tetramethoxysilane, hexachlorodisilane (HCDS), etc., functionalize the polymer chain ends and can react with components of the elastomeric composition, such as fillers or unsaturated moieties of the polymer. Exemplary coupling agents are described in US 3,281,383, US 3,244,664, and US 3,692,874 (e.g., tetrachlorosilane); US 3,978,103, US 4,048,206, US 4,474,908, and US 6,777,569 (blocked mercaptosilanes); US 3,078,254 (polyhalogen-substituted hydrocarbons, e.g., 1,3,5-tri(bromomethyl)benzene); US 4,616,069 (tin compounds and organic amino or amine compounds); and US 2005 / 0124740. In general, the chain end modifier is added before, during, or after the addition of the coupling agent, and the modification reaction is preferably carried out after the addition of the coupling agent. The total amount of coupling agent used affects the Mooney viscosity of the coupled polymer and typically ranges from 0.001 to 4.5 milliequivalents per 100 grams of elastomeric polymer, for example, from 0.01 to about 1.5 milliequivalents per 100 grams of polymer.

[0065] Further exemplary coupling agents are disclosed in DE102019117685A1, EP3666800A1, WO2016133154A, and JP2014055264A, the contents of each of which are incorporated herein in their entirety.

[0066] h) Randomizer Compounds Randomizing compounds (also known as polar coordination compounds), which are conventionally known in the art, may be optionally added to the monomer mixture or polymerization reaction to adjust the microstructure (i.e., the content of vinyl bonds) of the conjugated diene portion of the polymer, or to adjust the composition distribution of aromatic vinyl monomers and vinyl bonds in the polymer chain. A combination of two or more randomizing compounds may be used. The randomizing compounds useful in the present invention are generally exemplified by Lewis base compounds. Lewis bases suitable for use in the present invention include, for example, ether compounds, such as diethyl ether, di-n-butyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, (C1-C8 alkyl) tetrahydrofuryl ethers (e.g., methyl tetrahydrofuryl ether, ethyl tetrahydrofuryl ether, propyl tetrahydrofuryl ether, butyl tetrahydrofuryl ether, hexyl tetrahydrofuryl ether, and octyl tetrahydrofuryl ether), tetrahydrofuran, 2,2-(bis(2-phenylpropanediol), 2,2-dimethylphenyl ether, ... Examples of suitable randomized compounds include bis(tetrahydrofuryl)propane (DTHFP), bis(tetrahydrofurfuryl)formal, methyl ether of tetrahydrofurfuryl alcohol, ethyl ether of tetrahydrofurfuryl alcohol, butyl ether of tetrahydrofurfuryl alcohol, α-methoxytetrahydrofuran, dimethoxybenzene, and dimethoxyethane, as well as tertiary amines such as triethylamine, pyridine, N,N,N',N'-tetramethylethylenediamine (TMEDA), dipiperidinoethane, methyl ether of N,N-diethylethanolamine, ethyl ether of N,N-diethylethanolamine, N,N-diethylethanolamine, and dimethyl N,N-tetrahydrofurfurylamine. Examples of suitable randomized compounds are described in WO2009 / 148932, which is incorporated herein by reference in its entirety.The randomizing compound will typically be added in a molar ratio of randomizing compound to initiator compound of from 0.012:1 to 10:1, preferably from 0.1:1 to 8:1, and more preferably from 0.25:1 to about 6:1.

[0067] i) Accelerator Compounds The polymerization may optionally include an accelerator compound that increases the reactivity of the initiator (thus increasing the rate of polymerization) or that provides random placement or single chains of the aromatic vinyl monomer incorporated into the polymer, thereby affecting the distribution of the aromatic vinyl monomer in the living anionic elastomeric copolymer. Examples of accelerators include sodium alkoxides or phenoxides and potassium alkoxides or phenoxides, preferably potassium alkoxides or phenoxides, such as potassium isopropoxide, potassium t-butoxide, potassium t-amyl oxide, potassium n-heptyl oxide, potassium benzyl oxide, potassium phenoxide; potassium salts of carboxylic acids, such as isovaleric acid, caprylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, benzoic acid, phthalic acid, and 2-ethylhexanoic acid; potassium salts of organic sulfonic acids, such as dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, and octadecylbenzenesulfonic acid; and potassium salts of organic phosphoric acids, such as diethyl phosphite, diisopropyl phosphite, diphenyl phosphite, dibutyl phosphite, and dilauryl phosphite. Such accelerator compounds can be added in a total amount of 0.005-0.5 mol per 1.0 gram atom equivalent of initiator. If less than 0.005 mol is added, sufficient effect is usually not obtained. On the other hand, if the amount of accelerator compound is more than about 0.5 mol, the productivity and efficiency of the chain end modification reaction can be significantly reduced.

[0068] j) Administration The vinyl disiloxane of the present invention can be used in an amount of 0.2 equivalents per equivalent of initiator compound(s) up to 50% by weight based on the total amount of the resulting elastomeric polymer. When the polymer of the present invention is used in a tire application, such as a rubber compound for a tire tread or tire sidewall, the vinyl disiloxane of the present invention is preferably used in an amount of 0.5 equivalents per equivalent of initiator compound(s) up to 20% by weight, more preferably up to 10% by weight, and even more preferably up to 1% by weight, based on the elastomeric polymer. The remaining amount of the elastomeric polymer is derived from the conjugated diene monomer and any aromatic vinyl monomer, as well as any further optional components, such as chain end modifiers, coupling agents, and randomizers.

[0069] The mode of addition ("dosing") of the vinyldisiloxane of the present invention during polymerization to the conjugated diene monomer and any aromatic vinyl monomer, initiator compound, and other components influences the structure of the resulting polymer. Thus, statistical and block copolymers can be prepared having blocks of vinyldisiloxane polymer and blocks of other monomers in the desired ratio and order. Without intending to be limiting to the generally available dosing options, the following dosing options are mentioned by way of example for the process for preparing the elastomeric polymer of the present invention:

[0070] (1) Continuously (stepwise) adding the vinyldisiloxane compound of the present invention to a mixture comprising conjugated diene monomer, optionally an aromatic vinyl monomer, and an initiator compound as the polymerization proceeds, resulting in the provision of a statistical copolymer. (2) Dosing the vinyldisiloxane compound of the present invention before adding the main amount of initiator a) with the main amount of comonomer (tapered structure) or b) without other comonomer which can be added after conversion of the vinyldisiloxane to produce block structures. After the monomer is quantitatively or nearly quantitatively converted, a second addition of vinyldisiloxane can be performed to produce block structures at the polymer ends. (3) before adding the main amount of initiator, dosing the vinyldisiloxane compound of the present invention a) with the main amount of comonomer (tapered structure) or b) without other comonomers, which can be added after quantitative or near quantitative conversion of vinyldisiloxane to produce block structure. Furthermore, dosing the vinyldisiloxane compound of formula 1 multiple times (n times) in various proportions can be carried out at a predetermined conversion degree of the total monomer to produce n tapered or block structural elements in the polymer chain. For example, 67% of the vinyldisiloxane can be provided before adding the main amount of initiator, and 33% of the vinyldisiloxane can be added after 50% conversion of the total monomer. Dosing of vinyldisiloxane can also be carried out by providing 20% ​​of the vinyldisiloxane before adding the main amount of initiator, and adding 80% of the vinyldisiloxane after 50% conversion of the total monomer.

[0071] As another example, 67% of the vinyldisiloxane can be provided prior to addition of the main amount of initiator, and 33% of the vinyldisiloxane can be added 10-15 minutes prior to adding a coupling agent (defined above) and / or a chain end modifier (defined above) to terminate the polymerization.

[0072] (4) The step of administering the vinyldisiloxane compound of the present invention multiple times (n times) in various proportions can be carried out at a predetermined conversion of the total monomer to produce n (tapered or block) structural elements in the polymer chain. For example, 50% of the vinyldisiloxane can be provided before adding the main amount of initiator, and 50% of the vinyldisiloxane can be added after 50% conversion of the total monomer and before adding a coupling agent and / or a chain end modifier to stop the polymerization. As another example, 33% of the vinyldisiloxane can be provided before adding the main amount of initiator, and 33% of the vinyldisiloxane can be added after 50% conversion of the total monomer, and 33% of the vinyldisiloxane can be added 10 to 15 minutes before adding a coupling agent and / or a chain end modifier to stop the polymerization.

[0073] (5) Dosing the vinyldisiloxane compound of the present invention in an amount of 50% only after the main amount of initiator has been added, e.g., after 50% conversion of the comonomer (50% of the vinyldisiloxane can be added 10-15 minutes prior to adding the coupling agent and / or chain end modifier to stop the polymerization).

[0074] Elastomeric Polymers The elastomeric polymer according to the third aspect of the invention is obtainable by the process of the second aspect of the invention, i.e. a process comprising polymerizing at least one conjugated diene monomer and optionally one or more aromatic vinyl monomers in the presence of one or more initiator compounds and one or more compounds according to the first aspect of the invention. The elastomeric polymer of the invention may be a statistical, block or tapered copolymer, or an alpha or alpha,omega modified polymer in which the vinyldisiloxane compound of the invention is incorporated into the polymer chain by a vinyl functionality. The elastomeric polymer may be linear or branched.

[0075] For example, the elastomeric polymer may include the following repeat units in the polymer chain: [ka] where R, R', and X, and m and n are defined above for formula 2.

[0076] In a preferred embodiment, the elastomeric polymer of the present invention is an SSBR (solution styrene butadiene rubber) with a preferred vinyl content (vinyl content = content of 1,2-butadiene fraction based on the BR fraction of the polymer or copolymer) of 5 to 80 wt%, preferably 10 to 75 wt%, for example 10 to 30 wt%, 30 to 50 wt%, or 50 to 70 wt%, and a styrene content (depending on the specific application) of 40 to 70 wt%, or 15 to 40 wt%, or 2 to 15 wt%; a PBR (polybutadiene rubber) with a vinyl content of less than 15 wt%, or 15 to 40 wt%, or 40 to 80 wt%; a PIR (polyisoprene rubber); an SSIR (solution styrene isoprene rubber); or an SSIBR (solution styrene isoprene butadiene rubber); more preferably an SSBR or a PBR; even more preferably the elastomeric polymer is an SSBR, each modified by the incorporation of a vinyldisiloxane monomer according to the present invention. In the case of SSBR, the elastomeric polymer is characterized by a glass transition temperature (Tg, measured by DSC) of −90 to 0° C., preferably −85 to −5° C., more preferably −80 to −15° C. Preferred embodiments for passenger or truck tire applications include −80 to −60° C., −60 to −40° C., and −40 to −15° C.

[0077] In a preferred embodiment, the polymers of the invention have a peak molecular weight (measured by GPC) prior to coupling and chain end modification of 800 to 10,000 g / mol, or 10,000 to 50,000 g / mol, or 50,000 to 120,000 g / mol, or 120,000 to 250,000 g / mol, or 250,000 to 400,000 g / mol, or 400,000 to 800,000 g / mol.

[0078] In this embodiment, the double bonds of the conjugated diene polymer obtained by the above-mentioned production method can be further hydrogenated in an inert solvent to convert all or part of them into saturated hydrocarbons. This hydrogenation improves heat resistance and weather resistance and prevents deterioration of the product during processing at high temperatures. Therefore, excellent performance can be exhibited in various applications including automotive applications.

[0079] The hydrogenation rate of the unsaturated double bond based on the conjugated diene compound (also simply referred to as "hydrogenation rate") is not particularly limited and can be arbitrarily selected according to the purpose. When used as a vulcanized rubber, it is preferable that the double bond of the conjugated diene portion partially remains. From this viewpoint, the hydrogenation rate of the conjugated diene portion in the polymer is preferably 3.0% or more and 95% or less, more preferably 10.0% or more and 90% or less, and even more preferably 20% or more and 85% or less. The hydrogenation rate of the aromatic double bond based on the aromatic vinyl compound in the copolymer of the conjugated diene compound and the aromatic vinyl compound is not particularly limited. However, the hydrogenation rate of the aromatic double bond based on the aromatic vinyl compound in the copolymer of the conjugated diene compound and the aromatic vinyl compound is preferably 50% or less, more preferably 30% or less, and even more preferably 20% or less. The hydrogenation rate can be measured using a nuclear magnetic resonance apparatus (NMR).

[0080] The hydrogenation method is not particularly limited, and known methods can be used. An example of a method suitable for hydrogenation is a method of blowing hydrogen gas into a polymer solution in the presence of a catalyst. Examples of catalysts include homogeneous catalysts, such as catalysts containing noble gold supported on a porous inorganic material; and heterogeneous catalysts, such as catalysts derived from the reaction of solubilized salts of nickel, cobalt, etc. with organoaluminum, as well as catalysts containing metallocenes such as titanocene. Among them, titanocene catalysts are preferred from the viewpoint of being able to select particularly mild hydrogenation conditions. Hydrogenation of aromatic groups can be carried out by using a noble metal supported catalyst.

[0081] Specific examples of hydrogenation catalysts include, but are not limited to, (1) supported heterogeneous hydrogenation catalysts containing metals such as Ni, Pt, Pd, and Ru supported on carbon, silica, alumina, diatomaceous earth, etc.; (2) so-called Ziegler-type hydrogenation catalysts containing transition metal salts such as organic acid salts or acetylacetone salts of Ni, Co, Fe, Cr, etc., and reducing agents such as organoaluminum; and (3) so-called organometallic complexes such as organometallic compounds of Ti, Ru, Rh, Zr, etc. Further examples of hydrogenation catalysts include the hydrogenation catalysts described below: Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-37970, Japanese Patent Publication No. 1-53851, Japanese Patent Publication No. 2-9041, and Japanese Patent Publication No. 8-109219. Preferred examples of hydrogenation catalysts include a reaction mixture of a titanocene compound and a reducing organometallic compound.

[0082] Non-vulcanized polymer composition The unvulcanized (uncured) polymer composition of the fourth aspect of the present invention comprises an elastomeric polymer of the present invention and one or more additives. For example, the one or more additives may be extender oils, stabilizers, and polymer oils (M measured by GPC). p (real number)=800-50,000 g / mol) (not a polymer of the present invention). Such further polymers include those conventionally referred to in the art as oligomers. The liquid polymer or polymer oil or oligomer is, for example, a homopolymer or copolymer of styrene, isoprene, butadiene or farnesene.

[0083] In one embodiment, the polymer composition comprises one or more fillers. In another embodiment, the polymer composition further comprises one or more vulcanizing agents. In a preferred embodiment, the polymer composition comprises one or more fillers and one or more vulcanizing agents.

[0084] In one embodiment, the non-vulcanized polymer composition is obtained by conventional post-treatment of the reaction mixture obtained from the polymerization process, which means removing the solvent using steam stripping or vacuum evaporation techniques.

[0085] In another embodiment, the non-vulcanized polymer composition of the present invention is preferably obtained as a result of a further mechanical mixing process comprising a post-treatment reaction mixture (comprising the polymer of the present invention) in the form of a rubber bale (i.e., the product of a conventional compounding process with an internal mixer and / or a two-roll mill) and at least one filler.

[0086] The following components are usually added to non-vulcanized compositions used in tires: extenders, stabilizers, fillers, polymer oils (M measured by GPC). p (Actual) = 800-50,000 g / mol) of further polymers.

[0087] a) Extension oil In one embodiment, the polymer composition of the present invention comprises the elastomeric polymer of the present invention in combination with one or more oils, particularly mineral oils or extending oils derived from natural (non-fossil) sources (e.g., sunflower oil, rapeseed oil, soybean oil, tall oil, or castor oil). For representative examples and classifications of oils, see, for example, WO2009 / 148932 and US2005 / 0159513, each of which is incorporated herein by reference in its entirety.

[0088] Such oils include, for example, conventionally known extender oils, such as aromatic, naphthenic, and paraffinic extender oils, such as MES (mild extract solvates), TDAE (treated distillate aromatic extract), rubber to liquid (RTL) oil, biomass to liquid (BTL) oil, factice, extender resin, or liquid polymers (e.g., liquid BR) having an average molecular weight (measured by GPC according to BS ISO11344:2004) of 800 to 50,000 g / mol. When mineral oil is used as the extender oil, it is preferably one or more selected from DAE (distillate aromatic extract), RAE (residual aromatic extract), TDAE, MES, and naphthenic oil. The above-mentioned oils contain different concentrations of polycyclic aromatic compounds, paraffins, naphthenes, and aromatics, and have different glass transition temperatures. The above types of oils are characterized in: "Kautschuk, Gummi, Kunststoffe", vol. 52, pages 799-805. In some embodiments, MES, RAE, and TDAE are preferred extending oils for rubber.

[0089] One or more oils can be added to the polymer before or after the end of the polymerization process. When the extending oil is added to the polymer solution, the timing of addition is preferably after the modification of the polymer or after the termination of the polymerization, for example, after the addition of a modifier or a polymerization terminator. After the addition of the extending oil, the oil-extended polymer composition can be obtained by separating the polymerization solvent from the polymer by direct drying or steam stripping, and drying the rubber using a vacuum dryer, hot air dryer, roller, etc.

[0090] The polymer composition may contain one or more oils in a total amount of 0 to 70 phr, preferably 0.1 to 60 phr, more preferably 0.1 to 50 phr. Liquid polymers, when used as extending oils in the polymer composition of the present invention, are not taken into account when calculating the composition of the polymer matrix.

[0091] In another embodiment, the oil is preferably added to the "solvent-free" polymer in a mechanical mixer along with at least one filler and at least one additional polymer.

[0092] b) Stabilizers To prevent degradation of the elastomeric polymer by molecular oxygen, one or more stabilizers (also called "antioxidants") can optionally be added to the polymer before or after the completion of the polymerization process. Antioxidants based on sterically hindered phenols, such as 2,6-di-tert-butyl-4-methylphenol, 6,6'-methylenebis(2-tert-butyl-4-methylphenol), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, isotridecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, Typically used antioxidants include tetrakis[methylene-3-(3,5-di-tert-butylphenol), 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenylacrylate, and 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, as well as thioester-based antioxidants such as 4,6-bis(octylthiomethyl)-o-cresol and pentaerythrityl tetrakis(3-laurylthiopropionate). Other stabilizers are phosphite-based (e.g., tris[4-(1,1-dimethylpropyl)phenyl]phosphite, bis[2,4-bis(2-methylbutan-2-yl)phenyl][4-(2-methylbutan-2-yl)phenyl]phosphite, bis[4-(2-methylbutan-2-yl)phenyl][2,4-bis(2-methylbutan-2-yl)phenyl]phosphite, tris[2,4-bis(2-methylbutan-2-yl)phenyl]phosphite, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate).Further examples of suitable stabilizers can be found in: F. Rothemeyer, F. Sommer, Kautschuk Technologie, 2. nd ed., (Hanser Verlag, 2006) pages 340-344, and the references cited therein.

[0093] c) Further polymers Apart from the inventive polymer, extending oil(s), filler(s) etc., the inventive polymer composition may further contain further polymers, in particular further elastomeric polymers. The further polymers can be added in the form of a solution to the solution of the inventive polymer before post-treatment of the polymer blend or can be added during the mechanical mixing process, for example in a Brabender mixer.

[0094] The further (elastomeric) polymers referred to herein are elastomeric polymers that are not in accordance with the polymers of the present invention, i.e. do not contain repeat units derived from the vinyldisiloxane compounds of the present invention. Such further polymers include those conventionally referred to in the art as oligomers.

[0095] d) Filler The polymer composition of the present invention may optionally comprise one or more extender oils as defined above, and may further comprise one or more fillers. One or more fillers can be added to the polymer before or after the end of the polymerization process. Examples of suitable fillers include carbon black (including conductive carbon black), carbon nanotubes (CNTs) (including individual CNTs, hollow carbon fibers (HCFs), and modified CNTs with one or more functional groups (e.g., hydroxyl groups, carboxyl groups, and carbonyl groups), graphite, graphene (including individual graphene platelets), silica, carbon-silica dual-phase fillers, clays (including layered silicates, exfoliated nanoclays, and organoclays), calcium carbonate, magnesium carbonate, magnesium oxide, titanium dioxide, rubber gel, lignin, amorphous fillers, such as glass particle-based fillers, starch-based fillers, and combinations thereof. Further examples of suitable fillers are described in WO2009 / 148932, which is fully incorporated herein by reference.

[0096] In the polymer composition of the present invention, the one or more fillers are preferably selected from carbon black, carbon nanotubes, graphite, graphene, silica, carbon-silica dual-phase fillers, clay, calcium carbonate, magnesium carbonate, lignin, glass particle-based fillers, and starch-based fillers, preferably the filler is carbon black or silica, or a combination thereof. More preferably, the filler is silica.

[0097] Any type of carbon black conventionally known to those skilled in the art may be used as the carbon black. In one embodiment, the carbon black has an iodine value according to ASTM D1510 of 20-250mg / g, preferably 30-180mg / g, more preferably 40-180mg / g, even more preferably 40-130mg / g, and a DBP value according to ASTM D2414 of 80-200ml / 100g, preferably 100-200ml / 100g, more preferably 115-200ml / 100g (DBP value determines the specific absorption capacity of carbon black or any glossy filler according to dibutyl phthalate).

[0098] Any type of silica known to those skilled in the art and suitable as a filler for tire rubber blends may be used. In particular, silica having a nitrogen surface area (BET surface area, according to DIN ISO 9277 and DIN 66132) of 35 to 350 m 2 / g, preferably 35 to 260 m 2 / g, more preferably 100 to 260 m 2 / g, more preferably 130 to 235 m 2 / g, and the CTAB surface area (according to ASTM D3765) is 30 to 400 m 2 / g, preferably 30 to 250m 2 / g, more preferably 100 to 250m 2 / g, more preferably 125 to 230 m 2 Highly dispersed precipitated silicas with a molecular weight of 0.01 to 0.01 g are used. Such silicas, for example in rubber blends for tire treads, provide particularly beneficial physical properties of the vulcanizate. In addition, the blending process may provide the advantage of reducing the time required for blending while maintaining the product properties, thereby improving productivity. Useful silicas include those of the Ultrasil® VN3 (trademark of Evonik Industries) type, and the so-called HD silicas of the highly dispersed type (e.g. Zeosil® 1165MP from Rhodia).

[0099] e) Vulcanizing agents and vulcanization accelerators The polymer compositions of the present invention may optionally further comprise one or more vulcanizing agents. Any vulcanizing agent conventionally used in the manufacture of rubber products may be used in the present invention, and combinations of two or more vulcanizing agents may be used.

[0100] Sulfur, sulfur-containing compounds acting as sulfur donors such as dithiols, sulfur accelerator systems, and peroxides are the most common vulcanizing agents. Examples of sulfur-containing compounds acting as sulfur donors include dithiodimorpholine (DTDM), tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), and dipentamethylenethiuram tetrasulfide (DPTT). Examples of sulfur accelerators include amine derivatives, guanidine derivatives, aldehyde-amine condensation products, thiazoles, xanthogenates, thiuram sulfides, dithiocarbamates, and thiophosphates. Preferably, one or more sulfonamide accelerators are used, selected from N-cyclohexyl 2-benzothiazole sulfenamide (CBS), N,N-dicyclohexyl benzothiazole 2-sulfenamide (DCBS), benzothiazyl 2-sulfene morpholide (MBS), and N-tert-butyl 2-benzothiazyl sulfenamide (TBBS).Additional crosslinking systems, such as those available under the trade names Vulkuren® (1,6-bis(N,N-dibenzylthiocarbamoyldithio)-hexane; Lanxess), Duralink®, or Perkalink® (1,3-bis(citraconimidomethyl)benzene; Lanxess) or disclosed in WO2010 / 049261, can be added to the polymer composition. Examples of peroxides include di-tert-butyl peroxide, di-(tert-butylperoxytrimethylcyclohexane), di-(tert-butylperoxyisopropyl)benzene, dichlorobenzoyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, dimethyl-di(tert-butylperoxy)hexane, dimethyl-di(tert-butylperoxy)hexyne, and butyl-di(tert-butylperoxy)valerate (Rubber Handbook, SGF, The Swedish Institution of Rubber Technolgy 2000).

[0101] If necessary, a sulfenamide type, guanidine type, or thiuram type vulcanization accelerator can be used in combination with the vulcanizing agent.

[0102] Furthermore, the polymer composition of the present invention may contain conventional additives and vulcanization aids in the proportions conventionally used. Such additives include: a) Antiaging agents, such as N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (6PPD), N,N'-diphenyl-p-phenylenediamine (DPPD), N,N'-ditolyl-p-phenylenediamine (DTPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ). b) activators, such as zinc oxide and fatty acids (e.g., stearic acid); c) wax, d) resins, in particular adhesive resins; e) chewing additives, such as 2,2'-dibenzamidodiphenyl disulfide (DBD), and f) Processing additives, such as zinc soaps and fatty acid esters and their derivatives.

[0103] Zinc oxide (zinc white) is preferably used as a component of the sulfur accelerator system.

[0104] The vulcanizing agent is typically added to the polymer composition in a total amount of 0.5 to 10 parts by weight, or in some embodiments, 1 to 6 parts by weight, per 100 parts by weight of polymer. Examples of vulcanization accelerators and their amounts (relative to the polymer) are described in WO2009 / 148932, which is incorporated herein by reference in its entirety.

[0105] Vulcanized polymer composition The vulcanized polymer composition of the fifth aspect of the invention is obtained by vulcanizing the polymer composition of the invention containing one or more vulcanizing agents. The method of producing the vulcanized polymer composition of the sixth aspect of the invention comprises the step of vulcanizing the polymer composition of the invention under conditions and with machines conventionally known in the art.

[0106] Goods The vulcanized polymer composition of the present invention exhibits low rolling resistance and improved wet grip performance, as well as favorable mechanical properties, and can be favorably used, for example, in a variety of different SBR / BR grades having different microstructures, and is therefore highly suitable for use in, for example, the manufacture of tires or tire components (e.g., tire treads, sidewalls, and tire carcasses), as well as other industrial products (including, for example, belts, hoses, vibration dampers, and footwear components). Thus, the article of the seventh aspect of the present invention comprises at least one component formed from the vulcanized polymer composition of the present invention. The article may include, for example, a tire (including portions thereof, for example, tire treads, tire sidewalls, and tire carcasses), a belt, a gasket, a seal, a hose, a vibration damper, a footwear component (e.g., a sole), a golf ball, or a hose. Preferably, the article is a tire (including summer, winter, all-weather passenger or truck tires) or a part thereof, and more preferably, the article is a tire.

[0107] Definitions and Abbreviations The chemical definitions of substituents or specific moieties, as well as abbreviations used herein, generally correspond to their meanings known in the art.

[0108] For example, an alkyl group, as used herein, unless specifically stated otherwise, whether by itself or in conjunction with other groups such as alkylaryl, includes straight chain (linear) alkyl groups, such as methyl (Me), ethyl (Et), n-propyl (n-Pr), n-butyl (n-Bu), n-pentyl, n-hexyl, octyl, and the like; branched alkyl groups, such as isopropyl (i-Pr), tert-butyl (t-Bu), and the like; and cyclic alkyl groups, such as cyclohexyl (Cy).

[0109] Aryl groups as used herein include phenyl, biphenyl, and other benzenoid compounds. Aryl groups preferably contain only one aromatic ring, and most preferably contain a C6 aromatic ring.

[0110] As used herein, alkylaryl refers to the combination of one or more aryl groups bonded to one or more alkyl groups, for example, alkyl-aryl, aryl-alkyl, alkyl-aryl-alkyl, and aryl-alkyl-aryl.Alkylaryl preferably contains only one aromatic ring, and most preferably contains a C6 aromatic ring.For example, one of the preferred alkylaryl groups is benzyl (Bn). EXAMPLES

[0111] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

[0112] 1) Preparation and characterization of amine-containing vinyldisiloxane modified monomers a) Synthesis of halogen amine precursors Preparation Example 1 [ka] 1-Bromo-3-chloropropane (78.7 g, 500 mmol) was dissolved in dioxane (750 ml). Sodium bicarbonate (42.0 g, 500 mmol, 1.0 equiv) was added followed by 1-methylpiperazine (100 g, 1000 mmol, 2.0 equiv). The reaction mixture was stirred at 50° C. for 16 hours. The solids were filtered off, the solvent was removed under reduced pressure and the residue was fractionally distilled to give Preparation Example 1 (52.3 g, 296 mmol, 59%) as a colorless oil. Purity 94% (GC), C8H 17 ClN2, M w = 176.69 g / mol.

[0113] bp = 81-83°C (1.1 mbar). 1 H NMR (400 MHz, 20℃, CDCl3): δ = 3.59 (t, J = 6.6 Hz, 2 H), 2.49 (t, J = 7.0 Hz, 2 H), 2.52-2.39 (m, br, 8 H), 2.29 (s, 3 H), 1.95 (pent, J = 6.9 Hz, 2 H) ppm.13 C NMR (101 MHz, 20℃, CDCl3): δ = 55.40 (CH2), 55.13 (2 CH2), 53.21 (2 CH2), 46.04 (CH3), 43.20 (CH2), 29.89 (CH2) ppm. GC-MS (EI, 70 eV): m / z (%) = 176 (M + , 43), 132 (7), 113 (Me-Pip-Me + , 100), 106 (8), 98 (25), 85 (14), 70 (85). IR (ATR): λ -1 = 2938 (m), 2877 (w), 2793 (s), 2684 (w), 1458 (m), 1448 (m), 1373 (m), 1356 (m), 1296 (m), 1283 (s), 1181 (m), 1162 (s), 1124 (m), 1088 (m), 1013 (vs), 814 (m), 787 (m), 758 (m), 723 (m), 653 (s) cm -1 .

[0114] Preparation Example 2 [ka] 1-Bromo-3-chloropropane (34.5 g, 219 mmol) was added to a solution of triethylamine (26.6 g, 263 mmol, 1.2 equiv) and 1-ethylpiperazine (25.0 g, 219 mmol, 1.0 equiv) in DCM (220 ml). The reaction mixture was stirred at 25° C. for 16 h. Hexane (200 ml) was added and the solid was filtered off using Celite. The solvent was removed under reduced pressure and the residue was fractionated to give Preparation Example 2 (26.9 g, 141 mmol, 64%) as a colorless oil. Purity 95% (GC), C9H 19 ClN2, M w = 190.72 g / mol.

[0115] bp = 82-84 °C (0.4 mbar). Spectroscopic data were from the following publication to date: (JS Adav et al. Synth Commun. 2003, 33, pp. 2483-2486. DOI: 10.1081 / SCC-120021838).

[0116] Preparation Example 3 [ka] Chloropropylamine hydrochloride (20.0 g, 154 mmol, 1.0 equiv.) was dissolved in DCM (310 ml). Triethylamine (54.5 g, 538 mmol, 3.5 equiv.) and chlorotrimethylsilane (41.8 g, 385 mmol, 2.5 equiv.) were then added. The reaction mixture was stirred at 25° C. for 16 hours. Cyclohexane (300 ml) was added and the precipitate was filtered off. The solvent was removed under reduced pressure and the residue was vacuum distilled to give Preparation Example 3 (30.0 g, 126 mmol, 82%) as a colorless oil. Purity 96% (GC), C9H 24 ClNSi2, M w = 237.92 g / mol.

[0117] bp = 67-69°C (0.6 mbar). 1 H NMR (400 MHz, 20℃, CDCl3): δ = 3.47 (t, J = 6.4 Hz, 2 H), 2.94-2.89 (m, 2 H), 1.86-1.78 (m, 2 H), 0.10 (s, 18 H) ppm. 13 C NMR (101 MHz, 20℃, CDCl3): δ =43.13 (CH2), 42.85 (CH2), 37.66 (CH2), 2.05 (6 CH3) ppm. GC-MS (EI, 70 eV): m / z (%) = 237 (M + , 2), 194 (30), 174 (100), 114 (8), 100 (11), 86 (66).

[0118] Preparation Example 4 [ka] Morpholine (17.4 g, 200 mmol, 1.0 equiv) was dissolved in DCM (80 ml). Triethylamine (25.3 g, 250 mmol, 1.25 equiv) and 1-bromo-3-chloropropane (39.4 g, 250 mmol, 1.25 equiv) were then added. The reaction mixture was stirred at reflux for 2 and 16 hours at 25° C. Cyclohexane (100 ml) was added and the precipitate was filtered off. The solvent was removed under reduced pressure and the residue was distilled in vacuum to give Preparation Example 4 (27.3 g, 166 mmol, 83%) as a colorless liquid. C7H 14 ClNO, M w = 163.65 g / mol.

[0119] bp=70~73℃(0.2mbar). GC-MS(EI, 70 eV): m / z (%) = 186 (M + , 0.01),100 (CH2=NC4H8O + , 100), 70 (0.1). IR (ATR): λ -1 = 2958 (m), 2851 (m), 2795 (m), 1455 (m), 1413 (m), 1355 (m), 1281 (m), 1259 (m), 1150 (m), 1112 (s), 1071 (m), 1033 (m), 1017 (m), 928 (w), 905 (m), 866 (s), 797 (m), 639 (m) cm -1 .

[0120] Preparation Example 5 [ka] Benzylmethylamine (10.0 g, 82.5 mmol, 1.0 equiv) was dissolved in DCM (80 ml). Triethylamine (9.19 g, 91.1 mmol, 1.1 equiv) and 1-bromo-3-chloropropane (13.0 g, 82.5 mmol, 1.0 equiv) were then added. The reaction mixture was stirred at 25° C. for 16 h. Water (100 ml) was added and the pH was adjusted to pH=10. The aqueous phase was then extracted with MTBE (3×100 ml). The combined organic phase was dried over MgSO4, filtered, the solvent was removed under reduced pressure and the residue was distilled in vacuum to give Preparation Example 5 (9.97 g, 50.4 mmol, 65%) as a colorless oil. Purity 92% (GC), C 11 H 16 ClN, M w = 197.71 g / mol.

[0121] bp: 85-90°C (1.1 mbar). 1 H NMR (400 MHz, 20℃, CDCl3): δ = 7.32-7.29 (m, 4 H), 7.26-7.23 (m, 1 H), 3.60 (t, J = 6.8 Hz, 2 H), 3,48 (s, 2), 2.51 (t, J = 6.8 Hz, 2 H), 2.10 (s, 3 H), 1.96 (pent, J = 6.8 Hz, 2 H) ppm. 13 C NMR (101 MHz, 20℃, CDCl3): δ = 139.05 (C), 128.87 (2 CH), 128.20 (2 CH), 126.94 (CH), 62.42 (CH2), 54.31 (CH2), 43.15 (CH2), 42.10 (CH3), 30.54 (CH2), 17.15 (CH3) ppm. GC-MS (EI, 70 eV): m / z (%) = 197 (M + , 5), 134 (85), 120 (4), 91 (C7H7 + ,100). IR (ATR): λ -1= 3062 (w), 3027 (w), 2949 (w, br), 2791 (m, br), 1452 (m), 1025 (m), 733 (s), 693 (s), 653 (m) cm -1 .

[0122] Preparation Example 6 [ka] Phenylpiperazine (13.0 g, 80.0 mmol, 1.0 equiv) was dissolved in THF (80 ml). Triethylamine (9.31 g, 92.0 mmol, 1.15 equiv) and 1-bromo-3-chloropropane (12.6 g, 80 mmol, 1.0 equiv) were then added. The reaction mixture was stirred at 25° C. for 16 h and at 50° C. for 2 days. Water (80 ml) was added and the pH was adjusted to pH=10. The aqueous phase was then extracted with MTBE (3×80 ml). The combined organic phase was dried over MgSO4, filtered, the solvent was removed under reduced pressure and the residue was distilled in vacuum to give Preparation Example 6 (9.71 g, 40.7 mmol, 51%) as a colorless oil. Purity 97% (GC), C 13 H 19 ClN2, M w = 238.76 g / mol.

[0123] bp: 143-146°C (0.7 mbar). 1 H NMR (400 MHz, 20℃, CDCl3): δ = 7.29-7.24 (m, 2 H), 6.94-6.92 (m, 2 H), 6.85 (t, J = 7.2 Hz, 1 H), 3.63 (t, J = 6.6 Hz, 2 H), 3.21-3.18 (m, 4 H), 2.62-2.59 (m, 4 H), 2.55 (t, J = 7.0 Hz, 2 H), 1.99 (pent, J = 6.8 Hz, 2 H) ppm. 13C NMR (101 MHz, 20℃, CDCl3): δ = 151.29 (C), 129.09 (2 CH), 119.68 (CH), 116.03 (2 CH), 55.43 (CH2), 53.27 (2 CH2), 49.14 (2 CH2), 48.18 (CH2), 29.88 (CH2) ppm. GC-MS (EI, 70 eV): m / z (%) = 238 (M + , 60), 175 (Me-Pip-Ph + , 100), 160 (6), 147 (12), 132 (34), 105 (35).

[0124] Preparation Example 7 [ka] Pyrrolidine (7.11 g, 100 mmol, 0.7 equiv) was slowly added to a solution of triethylamine (13.7 g, 136 mmol, 0.95 equiv) and 1-bromo-3-chloropropane (22.5 g, 143 mmol, 1.0 equiv) in DCM (40 ml). The reaction mixture was refluxed for 3 days. Cyclohexane (50 ml) was added and the solid was filtered off multiple times. The solvent was removed under reduced pressure and the residue was vacuum distilled to give Preparation Example 7 (3.83 g, 22.0 mmol, 22%) as a colorless oil. Purity 95% (GC), C7H 14 ClN, M w = 147.65 g / mol.

[0125] bp: 25-29°C (0.023 mbar). 1 H NMR (400 MHz, 20℃, CDCl3): δ = 3.33 (t, J = 6.6 Hz, 2 H), 2.33 (t, J = 6.8 Hz, 2 H), 2.24-2.20 (m, 4 H), 1.66 (pent, J = 6.7 Hz, 2 H), 1.56-1.50 (m, 4 H) ppm. 13C NMR (101 MHz, 20℃, CDCl3): δ = 54.12 (2 CH2), 53.03 (CH2), 43.19 (CH2), 32.26 (CH2), 23.87 (2 CH2) ppm. GC-MS (EI, 70 eV): m / z (%) = 147 (M + , 6), 110 (2), 84 (C5H 10 N + , 100), 70 (4).

[0126] Preparation Example 8 [ka] Chloroethylamine hydrochloride (17.4 g, 150 mmol, 1.0 equiv) was dissolved in DCM (300 ml). Triethylamine (50.1 g, 495 mmol, 3.3 equiv) and 1,2-bis(chlorodimethylsilyl)ethane (35.9 g, 150 mmol, 1.0 equiv) were then added. The reaction mixture was stirred at 25° C. for 16 hours. The mixture was filtered, the solvent removed under reduced pressure, and the residue was fractionally distilled to give Preparation Example 8 (28.0 g, 126 mmol, 84%) as a colorless liquid. Purity 95% (GC), C8H 20 ClNiSi2, M w = 221.88 g / mol.

[0127] Bp: 39-41°C (0.01 mbar). 1 H NMR (400 MHz, 20℃, CDCl3): δ = 3.19 (t, J = 8.4 Hz, 2 H), 3.00 (t, J = 8.0 Hz, 2 H), 0.67 (s, 4 H), -0.04 (s, 12 H) ppm. 13 C NMR (101 MHz, 20℃, CDCl3): δ = 45.65 (CH2), 45.08 (CH2), 8.14 (2 CH2), -0.14 (4 CH3) ppm. GC-MS (EI, 70 eV): m / z (%) = 206 (M +, 13), 172 (100), 150 (5), 137 (5), 117 (4), 100 (5), 85 (4).

[0128] Preparation Example 9 [ka] Chloropropylamine hydrochloride (10.0 g, 76.9 mmol) was suspended in DCM (154 ml) at 25° C. Triethylamine (25.7 g, 254 mmol, 3.3 eq) and 1,2-bis(chlorodimethylsilyl)ethane (18.4 g, 76.9 mmol, 1 eq, dissolved in 40 ml DCM) were added and the resulting solution was stirred at 25° C. for 16 hours. Cyclohexane (100 ml) was then added and the precipitate was filtered off. All volatiles were removed under reduced pressure and the residue was distilled in vacuum. Preparation Example 9 was obtained as a colorless liquid (17.5 g, 74.2 mmol, 96%). C9H 22 ClNSi2, M w = 235.90 g / mol.

[0129] Bp:97~100℃(0.3mbar). GC-MS (EI, 70 eV): m / z (%) = 235 (M + , 4), 220 (M + -CH3, 2), 192 (31), 172 (100), 145 (5), 117 (5), 100 (5), 85 (5), 73 (10), 59 (15). Preparation Example 10 [ka]

[0130] 1,4-Dibromobenzene (100 mmol, 23.6 g, 1.0 equiv.) was dissolved in THF (80 ml). Next, Pd(dppf)Cl2 (360 mg, 0.005 equiv.) and 1-chloro-3-(N-ethylpiperazinyl)propane were added. *A Grignard solution of (80 mmol, 0.8 equiv., 1M in THF) was added at 25° C. The reaction mixture was stirred for 2 h. Water (100 ml) was then added and the aqueous phase was extracted with MTBE (3×100 ml). The organic phase was extracted with dilute aqueous HCl and the pH adjusted (pH=10) aqueous phase was extracted with MTBE (3×100 ml), dried over MgSO4 and filtered. The solvent was removed under reduced pressure to give Preparation Example 10 (19.1 g, 61.4 mmol, 61%) as a yellow oil. C 15 H 23 BrN2, M w = 311.27 g / mol.

[0131] 1 H NMR (400 MHz, 20℃, CDCl3): δ = 7.37 (d, J = 8.4 Hz, 2 H), 7.05 (d, J = 8.4 Hz, 2 H), 2.58 (t, J = 7.8 Hz, 3 H), 2.48 (s, br, 6 H), 2.40 (q, J = 7.2 Hz, 2 H), 2.36-2.33 (m, 3 H), 1.78 (pent, J = 7.6 Hz, 2 H), 1.08 (t, J = 7.2 Hz, 3 H) ppm. 13 C NMR (101 MHz, 20℃, CDCl3): δ = 141.04 (C), 131.24 (2 CH), 130.10 (2 CH), 119.36 (C), 57.74 (CH2), 53.16 (2 CH2), 52.79 (2 CH2), 52.26 (CH2), 33.02 (CH2), 28.41 (CH2), 11.94 (CH3) ppm. GC-MS (EI, 70 eV): m / z (%) = 310 (M + , 19), 295 (M + -CH3, 3), 267 (2), 254 (3), 240 (4), 168 (6), 141 (28), 127 (100), 99 (11), 84 (26).

[0132] *The Grignard solution of 1-chloro-3-(N-ethylpiperazinyl)propane used in Preparation Example 10 was prepared in the same manner as described in section b) below.

[0133] Preparation Example 11 [ka] 4-Bromoaniline (15.0 g, 87.2 mmol) was dissolved in DCM (300 ml). Then, triethylamine (18.5 g, 183 mmol, 2.1 eq) and 1,2-bis(chlorodimethylsilyl)ethane (20.9 g, 87.2 mmol, 1.0 eq, dissolved in 30 ml of DCM) were added and the mixture was stirred at 25° C. for 16 hours. Then, cyclohexane (200 ml) was added and the precipitate was filtered off. All volatiles were removed under reduced pressure and the residue was distilled in vacuum. Preparation Example 11 was obtained as a yellow liquid (26.7 g, 84.9 mmol, 97%). C 12 H 20 BrNSi2, M w = 314.37 g / mol.

[0134] bp: 90-95 °C (0.03 mbar). 1 H NMR (400 MHz, 20°C, C6D6): δ = 7.21-7.18 (m, 2 H), 6.64-6.61 (m, 2 H), 0.76 (s, 4 H), 0.08 (s, 12 H) ppm. 13 C NMR (101 MHz, 20°C, C6D6): δ = 146.61 (C), 132.36 (2 CH), 126.03 (2 CH), 114.17 (C), 8.54 (2 CH2), -0.14 (4 CH3) ppm. 29 Si{H} ​​NMR (79.5 MHz, 20°C, C6D6): δ = 13.04 (2 Si) ppm.

[0135] b) Synthesis of Grignard Reagents [ka] Magnesium turnings (1.3 equiv.) were placed in a nitrogen flushed flask and dried under vacuum at elevated temperature for 5-10 min. The flask was backfilled with nitrogen and then cooled under nitrogen. THF (1 ml per mmol of alkyl chloride or alkyl bromide, respectively) and 1,2-dibromoethane were added for activation, followed by dropwise addition of the alkyl chloride of one of Preparation Examples 1-9 or the alkyl bromide of Preparation Examples 10 or 11. The reaction mixture was then refluxed for a further 2 h and stirred at reflux or at 25 °C depending on the conversion for a further time to give the Grignard reagent Alk-MgX. * obtained.

[0136] c) Synthesis of chlorosilane precursors Preparation Example 12 [ka] Dichloromethylvinylsilane (28.2 g, 200 mmol) was dissolved in DCM (200 ml) at 25° C. Triethylamine (22.3 g, 220 mmol, 1.1 equiv.) was added. Then TBSOH (26.5 g, 200 mmol, 1.0 equiv.) was added dropwise at 25° C. The reaction mixture was stirred at 25° C. for 2.5 h. Then cyclohexane (100 ml) was added and the precipitate was filtered off. All volatiles were removed under reduced pressure and the residue was distilled under vacuum. Preparation Example 12 was obtained as a colorless liquid (34.2 g, 144 mmol, 72%). Purity 98% (GC). Bp: 103-105° C. (50 mbar). C9H 21 ClOSi2, M W = 236.89 g / mol.

[0137] The material was carried on directly to the next transformation.

[0138] Preparation Example 13 [ka] Dichloromethylvinylsilane (5.78 g, 41.0 mmol) was dissolved in DCM (40 ml) at 25° C. Triethylamine (4.56 g, 45.1 mmol, 1.1 equiv) was added. TIPSOH (7.15 g, 41.0 mmol, 1.0 equiv) was then added dropwise at 25° C. The reaction mixture was stirred at 25° C. for 16 h. Cyclohexane (50 ml) was then added and the precipitate was filtered off. All volatiles were removed under reduced pressure and the residue was distilled in vacuum. Preparation Example 13 was obtained as a colorless liquid (9.95 g, 35.7 mmol, 87%). Purity 99% (GC). Bp: 66-72° C. (0.83 mbar). C 12 H 27 ClOSi2, M W = 278.97 g / mol.

[0139] GC-MS (EI, 70 eV): m / z (%) = 263 (M + -CH3, 0.2), 235 (M + -C3H7, 100), 207 (46), 193 (22), 179 (54), 165 (50), 153 (19), 139 (18), 123 (9), 105 (10).

[0140] The material was carried on directly to the next transformation.

[0141] Preparation Example 14 [ka] Dichloromethylvinylsilane (6.02 g, 45.5 mmol) was dissolved in DCM (45 ml) at 25° C. Triethylamine (5.06 g, 50.0 mmol, 1.1 equiv) was added. TESOH (6.02 g, 45.5 mmol, 1.0 equiv) was then added dropwise at 25° C. The reaction mixture was stirred at 25° C. for 16 hours. Cyclohexane (50 ml) was then added and the precipitate was filtered off. All volatiles were removed under reduced pressure and the residue was distilled under vacuum. Preparation Example 14 was obtained as a colorless liquid (6.63 g, 28.0 mmol, 62%). Purity 96% (GC). C9H 21 ClOSi2, M W=236.89g / mol

[0142] Bp:40~44℃(0.6mbar). GC-MS (EI, 70 eV): m / z (%) = 221 (M + -CH3, 0.2), 207 (M + -C2H5, 100), 179 (45), 151 (41), 125 (17), 107 (7).

[0143] The material was carried on directly to the next transformation.

[0144] Preparation Example 15 [ka] Trichlorovinylsilane (61.0 g, 378 mmol) was dissolved in DCM (300 ml) at 25° C. Triethylamine (38.2 g, 378 mmol, 1.0 equiv.) was added. Then TBSOH (50.0 g, 378 mmol, 1.0 equiv.) dissolved in DCM (200 ml) was added dropwise at 0° C. The reaction mixture was stirred at 25° C. for 16 hours. Then cyclohexane (100 ml) was added and the precipitate was filtered off. All volatiles were removed under reduced pressure and the residue was distilled in vacuum. Preparation Example 15 was obtained as a colorless liquid (77.3 g, 300 mmol, 80%). Purity 99% (GC). C8H 18 Cl2OSi2, M W = 257.30 g / mol.

[0145] Bp: 33-35 °C (0.2 mbar). 1 H NMR (400 MHz, 20°C, CDCl3): δ = 6.19 (dd, J = 7.6 Hz, J = 10.4 Hz, 1 H), 6.15-6.09 (m, 2 H), 0.92 (s, 9 H), 0.17 (s, 6 H) ppm. 13C NMR (101 MHz, 20°C, CDCl3): δ = 137.31 (CH2), 131.82 (CH3), 25.36 (3 CH3), 17.97 (C), -3.39 (2 CH3) ppm. 29 Si{H} ​​NMR (79.5 MHz, 20°C, CDCl3): δ = 18.70 (1 Si), -34.89 (1 Si) ppm.

[0146] d) Synthesis of Modified Monomer Modified body S1 [ka] Chloro-tert-butyldimethylsiloxymethylvinylsilane (Preparation Example 12, 48.0 g, 203 mmol, 1.0 eq.) was dissolved in THF (50 ml). A Grignard solution of Preparation Example 1 in THF (243 mmol, 1.2 eq., 243 ml) was added dropwise at 25° C. The reaction mixture was stirred for 18 h. After filtration, MTBE (50 ml) was added and the organic phase was washed with water (50 ml). The aqueous phase was extracted with MTBE (3×50 ml). The combined organic phases were dried over MgSO4, the solids were filtered off and all volatiles were removed under reduced pressure. Modification S1 (37.7 g, 110 mmol, 54%) was obtained as a pale yellow oil. C 17 H 38 N2OSi2,M w = 342.67 g / mol.

[0147] 11H NMR (400 MHz, 20 °C, CDCl3): δ = 6.06 (dd, J = 20.0 Hz, J = 14.8 Hz, 1 H), 5.91 (dd, J = 14.8 Hz, J = 4.0 Hz, 1 H), 5.69 (dd, J = 20.4 Hz, J = 4.4 Hz, 1 H), 2.56 - 2.34 (m, br, 8 H), 2.33 - 2.29 (m, 2 H), 2.26 (s, 3 H), 1.53 - 1.45 (m, 2 H), 0.83 (s, 9 H), 0.55 - 0.51 (m, 2 H), 0.10 (s, 3 H), -0.01 (s, 6 H) ppm. 13 13C NMR (101 MHz, 20 °C, CDCl3): δ = 138.42 (CH, vinyl), 132.04 (CH2, vinyl), 62.03 (CH2), 55.09 (2 CH3), 53.11 (2 CH2), 46.01 (CH3), 25.64 (3 CH3), 20.36 (CH2), 18.01 (C), 14.75 (CH2), -1.48 (CH3), -2.89 (2 CH3) ppm. GC-MS (EI, 70 eV): m / z (%) = 342 (M + , 12), 327 (M + -CH3, 5), 315 (1), 285 (6), 133 (5), 113 (CH3-C2N2H7-CH3 + , 100). IR (ATR): λ -1 = 3049 (w), 2931 (m), 2857 (m), 2793 (m), 1460 (m), 1252 (m), 1174 (m), 1052 (s), 1005 (s), 954 (m), 834 (s), 776 (vs), 686 (m) cm -1 .

[0148] Modified substance S2

Chemical formula

[0149] 1 H NMR (400 MHz, 20℃, CDCl3): δ = 6.01-5.92 (m, 2 H), 5.77 (dd, J = 16.0 Hz, J = 8.4 Hz, 1 H), 2.61-2.36 (m, br, 8 H), 2.35-2.31 (m, 2 H), 2.20 (s, 3 H), 1.55-1.51 (m, 2 H), 0.87 (s, 18 H), 0.55-0.51 (m, 2 H), 0.05 (s, 12 H) ppm. 13 C NMR (101 MHz, 20 °C, CDCl3): δ = 136.55 (CH, vinyl), 132.96 (CH2, vinyl), 62.06 (CH2), 55.18 (2 CH2), 53.14 (2 CH2), 46.10 (CH3), 25.71 (6 CH3), 20.10 (CH2), 18.11 (2 C), 13.86 (CH2), -2.85 (4 CH3) ppm. GC-MS (EI, 70 eV): m / z (%) = 458 (M + , 30), 443 (M + -CH3, 10), 401 (15), 388 (5), 205 (6), 191 (8), 113 (CH2=Pip-CH3 + , 100), 98 (6), 70 (22). IR (ATR): λ -1= 3053 (w), 2952 (m), 2930 (m), 2857 (m), 2794 (m), 1461 (m), 1284 (m), 1252 (m), 1046 (s), 1004 (s), 957 (m), 831 (vs), 777 (vs), 717 (m), 677 (m) cm -1 .

[0150] Modified body S3 [ka] Chloro-tert-butyldimethylsiloxymethylvinylsilane (Preparation Example 12, 13.0 g, 55.0 mmol, 1.0 equiv.) was dissolved in THF (50 ml). A Grignard solution of Preparation Example 6 in THF (55.0 mmol, 1.0 equiv., 55 ml) was added dropwise at 25° C. The reaction mixture was stirred for 3 days. Water (50 ml) was added and the aqueous phase was extracted with MTBE (3×50 ml). The combined organic phases were dried over MgSO4, the solids were filtered off and all volatiles were removed under reduced pressure. Modification S3 (18.9 g, 46.6 mmol, 85%) was obtained as a brown solid. C 22 H 40 N2OSi2,M W = 404.75 g / mol.

[0151] 1H NMR (400 MHz, 20℃, CDCl3): δ = 7.27-7.23 (m, 2 H), 6.93-6.91 (m, 2 H), 6.86-6.83 (m, 1 H), 6.10 (dd, J = 20.0 Hz, J = 14.8 Hz, 1 H), 5.96 (dd, J = 14.8 Hz, J = 4.0 Hz, 1 H), 5.74 (dd, J = 20.0 Hz, J = 4.4 Hz, 1 H), 3.23 (t, J = 5.2 Hz, 4 H), 2.63 (t, J = 5.0 Hz, 4 H), 2.44-2.40 (m, 2 H), 1.63-1.55 (m, 2 H), 0.87 (s, 9 H), 0.62-0.57 (m, 2 H), 0.15 (s, 3 H), 0.03 (s, 6 H) ppm. 13 C NMR (101 MHz, 20℃, CDCl3): δ = 151.22 (C, Ar), 138.34 (CH,ビニル), 132.18 (CH2,ビニル), 129.04 (2 CH), 119.67 (CH), 116.02 (2 CH), 61.91 (CH2), 53.10 (2 CH2), 48.94 (2 CH2), 25.66 (3 CH3), 20.23 (CH2), 18.02 (C), 14.73 (CH2), -1.44 (CH3), -2.86 (2 CH3) ppm. 29 Si{H} ​​NMR (79.5 MHz, 20℃, CDCl3): δ = 10.53 (1 Si), -4.98 (1 Si) ppm. GC-MS (EI, 70 eV): m / z (%) = 403 (M + , 0.8), 388 (M + -CH3, 0.5), 246 (0.8), 230 (2), 201 (2), 174 (CH2-Pip-Bn + ,100), 159 (7), 133 (7), 73 (14). IR (ATR): λ -1= 3050 (w), 2952 (m), 2929 (m), 2882 (w), 2856 (w), 2816 (w), 2772 (w), 1600 (m), 1501 (m), 1304 (w), 1252 (m), 1233 (m), 1056 (s), 1004 (m), 954 (m), 953 (m), 834 (s), 777 (vs), 689 (s) cm -1 .

[0152] Modified body S4 [ka] Chloro-tert-butyldimethylsiloxymethylvinylsilane (Preparation Example 12, 10.7 g, 45.0 mmol, 1.0 equiv.) was dissolved in THF (50 ml). A THF Grignard solution of 1-benzyl-4-(3-chloropropyl)piperazine (CAS: 23145-99-5, available, for example, from Chemieliva Pharmaceuticals) (45.0 mmol, 1.0 equiv., 45 ml) was added dropwise at 25° C. The reaction mixture was stirred for 3 days. Water (50 ml) was added and the aqueous phase was extracted with MTBE (3×50 ml). The combined organic phases were dried over MgSO4, the solids were filtered off and all volatiles were removed under reduced pressure. Modification S4 (14.5 g, 34.6 mmol, 77%) was obtained as a brown oil that solidified after some time at 25° C. 23 H 42 N2OSi2,M W = 418.77 g / mol.

[0153] 1H NMR (400 MHz, 20℃, CDCl3): δ = 7.31-7.23 (m, 5 H), 6.08 (dd, J = 20.0 Hz, J = 14.8 Hz, 1 H), 5.94 (dd, J = 14.8 Hz, J = 4.0 Hz, 1 H), 5.72 (dd, J = 20.4 Hz, J = 4.0 Hz, 1 H), 3.52 (s, 2 H), 2.62-2.42 (s, br, 8 H), 2.39-2.35 (m, 2 H), 1.58-1.49 (m, 2 H), 0.85 (s, 9 H), 0.57-0.53 (m, 2 H), 0.12 (s, 3 H), 0.01 (s, 6 H) ppm. 13 C NMR (101 MHz, 20℃, CDCl3): δ = 138.39 (CH,ビニル), 137.96 (C, Ar), 132.15 (CH2,ビニル), 129.23 (2 CH), 128.19 (2 CH), 127.03 (CH), 63.01 (2 CH2), 61.95 (CH2), 53.06 (2 CH2), 52.80 (CH2), 25.66 (3 CH3), 20.21 (CH2), 18.04 (C), 14.76 (CH2), -1.55 (CH3), -2.86 (2 CH3) ppm. 29 Si{H} ​​NMR (79.5 MHz, 20℃, CDCl3): δ = 10.46 (1 Si), -5.01 (1 Si) ppm. GC-MS (EI, 70 eV): m / z (%) = 418 (M + , 10), 403 (M + -CH3, 5), 361 (5), 327 (1), 244 (3), 189 (C 12 H 17 N2 + , 100), 161 (3), 133 (4), 119 (4), 91 (C7H7 + , 22). IR (ATR): λ -1= 3028 (w), 2952 (m), 2930 (m), 2806 (m), 1460 (m), 1406 (w), 1252 (m), 1057 (s), 1006 (s), 954 (m), 833 (s), 777 (vs), 736 (s), 697(s)cm -1 .

[0154] Modified S5 [ka] Chloro-tert-butyldimethylsiloxymethylvinylsilane (Preparation Example 12, 25 g, 106 mmol, 1.0 equiv.) was dissolved in THF (50 ml). A Grignard solution of Preparation Example 3 in THF (127 mmol, 1.2 equiv., 127 ml) was added dropwise at 25° C. The reaction mixture was stirred at 60° C. for 16 hours. The solid was filtered off and all volatiles were removed under reduced pressure. Modification S5 (33.6 g, 83.1 mmol, 79%) was obtained as a colorless liquid after vacuum distillation. C 18 H 45 NOSi4, M W = 403.90 g / mol.

[0155] bp = 85-95°C (0.2 mbar). 1 H NMR (400 MHz, 20℃, C6D6): δ = 6.17 (dd, J = 20.4 Hz, J = 14.8 Hz, 1 H), 5.93 (dd, J = 14.9 Hz, J = 4.0 Hz, 1 H), 5.77 (dd, J = 20.4 Hz, J = 4.0 Hz, ppm. 13C NMR (101 MHz, 20 °C, C6D6): δ = 138.69 (CH,vinyl), 132.40 (CH2,vinyl), 49.62 (CH2), 29.45 (CH2), 25.90 (3 CH3), 18.34 (C), 14.86 (CH2), 2.31 (6 CH3), -1.24 (CH3), -2.61 (2 CH3) ppm. 29 Si{H} ​​NMR (79.5 MHz, 20℃, CDCl3): δ = 10.43 (1 Si), 4.46 (2 Si), -4.99 (1 Si) ppm. GC-MS (EI, 70 eV): m / z (%) = 403 (M + , 0.8), 388 (M + -CH3, 0.5), 246 (0.8), 230 (2), 201 (2), 174 (100), 159 (7), 133 (7), 73 (14). IR (ATR): λ -1 = 3051 (w), 2954 (m), 2931 (m), 2895 (w), 2858 (w), 1595 (w), 1406 (w), 1250 (s), 1184 (m), 1065 (s), 1005 (m), 955 (m), 907 (s), 875 (m), 833 (vs), 777 (s), 678 (m) cm -1 .

[0156] Modified body S6 [ka] Chloro-tert-butyldimethylsiloxymethylvinylsilane (Preparation Example 12, 15.0 g, 63.8 mmol, 1.0 equiv.) was dissolved in THF (30 ml). A Grignard solution of Preparation Example 11 in THF (76.5 mmol, 1.2 equiv., 76.5 ml) was added dropwise at 25° C. The reaction mixture was stirred at 50° C. for 16 h. Cyclohexane was added (50 ml). The solid was filtered off and all volatiles were removed under reduced pressure. Modification S6 (18.6 g, 42.7 mmol, 67%) was obtained as a brown oil after vacuum distillation. C 21 H41 NOSi4。

[0157] 1 H NMR (400 MHz, 20℃, C6D6): δ = 7.58 (d, J = 8.4 Hz, 2 H), 7.04 (d, J = 8.4 Hz, 2 H), 6.33 (dd, J = 20.0 Hz, J = 14.8 Hz, 6.0 Hz, J = 10.0). Hz, J = 3.6 Hz, 1 H), 5.88 (dd, J = 20.4 Hz, J = 4.0 Hz, 1 H), 0.95 (s, 9 H), 0.79 (s, 4 H), 0.20 (s, 12 H), 0.17 (s, 3 H). 13 C NMR (101 MHz, 20℃, C6D6): δ = 149.40 (C, Ar), 138.72 (CH,ビニル), 135.13 (2 CH, Ar), 133.22 (CH2,ビニル), 128.4 (C, 22.9), Ar CH, Ar), 25.97 (3 CH3), 18.42 (C), 8.74 (2 CH2), 0.07 (4 CH3), -0.58 (CH3), -2.62 (CH3), -2.68 (CH3) ppm. 29 Si{H} ​​NMR (79.5 MHz, 20℃, C6D6): δ = 12.61 (2 Si), 11.14 (1 Si), -14.08 (1 Si) ppm. GC-MS (EI, 70 eV): m / z (%) = 435 (M + , 83), 420 (M + -CH3, 5), 378 (65), 350 (4), 304 (17), 290 (100), 278 (23), 262 (5), 230 (40), 218 (10), 192 (5), 181 (37), 168 (10), 147 (2), 35 (35). IR (ATR): λ -1= 3013 (w), 2955 (m), 2928 (w), 2856 (w), 1593 (m), 1502 (m), 1405 (w), 1251 (m), 1117 (m), 1051 (m, br), 1005 (m), 955 (m), 922 (m), 834 (m), 777 (vs), 687 (m), 627 (m) cm -1 .

[0158] Modified S7 [ka] Chloro-tert-butyldimethylsiloxymethylvinylsilane (Preparation Example 12, 9.11 g, 38.5 mmol, 1.0 eq.) was dissolved in THF (20 ml). A Grignard solution of 4-chloro-1-methylpiperidine (CAS 5570-77-4, e.g. available from abcr GmbH, Karlsruhe) (50 mmol, 1.3 eq., 50 ml) in THF was added dropwise at 25° C. The reaction mixture was stirred at 25° C. for 16 h. Water (50 ml) was added and the aqueous phase was extracted with MTBE (2×50 ml). The combined organic phases were dried over MgSO4, the solids were filtered off and all volatiles were removed under reduced pressure. Modification S7 (7.81 g, 26.1 mmol, 68%) was obtained after vacuum distillation as a yellow oil. C 15 H 33 NOSi2, M W = 299.61 g / mol.

[0159] 11H NMR (400 MHz, 20 °C, C6D6): δ = 6.12 (dd, J = 20.4 Hz, J = 15.2 Hz, 1 H), 5.95 (dd, J = 14.8 Hz, J = 4.0 Hz, 1 H), 5.76 (dd, J = 20.4 Hz, J = 4.0 Hz, 1 H), 2.84 - 2.81 (m, 2 H), 2.16 (s, 3 H), 1.78 - 1.70 (m, 2 H), 1.67 - 1.60 (m, 4 H), 0.95 (s, 9 H), 0.59 - 0.51 (m, 1 H), 0.14 (s, 3 H), 0.00 (s, 6 H) ppm. 13 13C NMR (101 MHz, 20 °C, C6D6): δ = 137.60 (CH, vinyl), 132.89 (CH2, vinyl), 57.73 (2 CH2), 47.21 (CH3), 26.70 (CH2), 26.65 (CH2), 25.96 (3 CH3), 24.65 (CH), 18.36 (C), -2.61 (2 CH3), -3.36 (CH3) ppm. GC-MS (EI, 70 eV): m / z (%) = 299 (M + , 19), 284 (M + -CH3, 58), 270 (6), 256 (2), 242 (33), 188 (8), 161 (14), 147 (20), 133 (29), 119 (13), 96 (C5H7NCH3 + , 100), 73 (12). IR (ATR): λ -1 = 3050 (w), 2954 (m), 2929 (m), 2777 (w), 2675 (w), 1463 (w), 1376 (w), 1252 (m), 1202 (w), 1142 (w), 1050 (s), 1005 (s), 954 (m), 888 (m), 834 (s), 776 (vs), 685 (m) cm -1 .

[0160] Modified substance S8 [Chemical formula] Chlorotriisopropylsiloxymethylvinylsilane (Preparation Example 13, 9.39 g, 35.6 mmol, 1.0 equiv.) was dissolved in THF (10 ml). Grignard solution of Preparation Example 1 in THF (39 mmol, 1.1 equiv., 40 ml) was added dropwise at 25° C. The reaction mixture was stirred at 25° C. for 16 h. Water (50 ml) was added and the aqueous phase was extracted with MTBE (2×50 ml). The combined organic phases were dried over MgSO4, the solids were filtered off and all volatiles were removed under reduced pressure. Modified S8 (6.65 g, 25.6 mmol, 72%) was obtained as a brown solid after vacuum distillation. C 20 H 44 N2OSi2,M W = 384.76 g / mol.

[0161] 1 H NMR (400 MHz, 20℃, C6D6): δ = 6.23 (dd, J = 20.4 Hz, J = 15.2 Hz, 1 H), 5.96 (dd, J = 14.8 Hz, J = 3.6 Hz, 1 H), 5.80 (dd, J = 20.0 Hz, J = 3.6 Hz, 1 H), 2.46 (s, br, 4 H), 2.36 (s, br, 4 H), 2.31-2.28 (m, 2 H), 2.11 (s, 3 H), 1.63 (pent, J = 6.4 Hz, 2 H), 1.09 (d, J = 6.4 Hz, 18 H), 1.02 (hept, J = 6.4 Hz, 3 H), 0.76-0.71 (m, 2 H), 0.26 (s, 3 H) ppm. 13 C NMR (101 MHz, 20 °C, C6D6): δ = 138.67 (CH, vinyl), 131.98 (CH2, vinyl), 61.54 (CH2), 54.94 (2 CH2), 52.84 (2 CH2), 45.56 (CH3), 20.71 (CH2), 17.81 (6 CH3), 14.82 (CH2), 12.78 (3 CH), -1.51 (CH3) ppm. GC-MS (EI, 70 eV): m / z (%) = 384 (M+ , 31), 341 (M + -C3H7, 38), 314 (4), 284 (2), 157 (5), 145 (8), 131 (8), 113 (C6H 13 N2 + , 100). IR (ATR): λ -1 = 3049 (w), 2940 (m), 2865 (m), 2794 (w), 1461 (m), 1253 (m), 1082 (s), 1055 (vs), 1010 (s), 862 (m), 806 (m), 788 (m), 676 (s) cm -1 .

[0162] Modified S9 [ka] Chlorotriethylsiloxymethylvinylsilane (Preparation Example 14, 6.61 g, 27.9 mmol, 1.0 equiv.) was dissolved in THF (10 ml). A Grignard solution of Preparation Example 1 in THF (31 mmol, 1.1 equiv., 31 ml) was added dropwise at 25° C. The reaction mixture was stirred at 25° C. for 16 h. Water (30 ml) was added and the aqueous phase was extracted with MTBE (3×30 ml). The combined organic phases were dried over MgSO4, the solids were filtered off and all volatiles were removed under reduced pressure. Modification S9 (9.13 g, 24.8 mmol, 89%) was obtained after vacuum distillation as an orange oil. C 17 H 38 N2OSi2,M w = 342.67 g / mol.

[0163] 1H NMR (400 MHz, 20℃, CDCl3): δ = 6.09 (dd, J = 20.4 Hz, J = 15.2 Hz, 1 H), 5.94 (dd, J = 14.8 Hz, J = 4.4 Hz, 1 H), 5.72 (dd, J = 20.4 Hz, J = 4.0 Hz, 1 H), 2.55-2.36 (m, br, 8 H), 2.35-2.31 (m, 2H), 2.28 (s, 3 H), 1.56-1.47 (m, 2 H), 0.92 (t, J = 8.0 Hz, 9 H), 0.58-0.54 (m, 2 H), 0.51 (q, J = 8.0 Hz, 6 H), 0.13 (s, 3 H) ppm. 13 C NMR (101 MHz, 20℃, CDCl3): δ = 138.56 (CH,ビニル), 131.97 (CH2,ビニル), 62.08 (CH2), 55.15 (2 CH2), 53.17 (2 CH2), 46.06 (CH3), 20.42 (CH2), 14.84 (CH2), 6.74 (3 CH3), 6.28 (3 CH2), -1.45 (CH3) ppm. 29 Si{H} NMR (79.5 MHz, 20℃, CDCl3): δ = 10.10 (1 Si), -5.41 (1 Si) ppm. GC-MS (EI, 70 eV): m / z (%) = 342 (M + , 11), 313 (M + -CH3, 14), 145 (4), 113 (C6H 13 N2 + , 100), 70 (17). IR (ATR): λ -1 = 3050 (w), 2952 (m), 2937 (m), 2875 (m), 2793 (m), 2765 (w), 1594 (w), 1458 (m), 1406 (w), 1296 (m), 1252 (m), 1174 (m), 1120 (m), 1060 (s), 1008 (s), 954 (m), 807 (m), 790 (m), 740 (s), 725 (vs), 671 (m) cm-1 .

[0164] Modified S10 [ka] Dichloro-tert-butyldimethylsiloxyvinylsilane (Preparation Example 15, 12.3 g, 47.6 mmol, 1.0 equiv.) was dissolved in THF (25 ml). A Grignard solution of 3-chloro-N,N-dimethylpropan-1-amine (100 mmol, 2.1 equiv., 100 ml) in THF was added dropwise at 25° C. The reaction mixture was stirred at 25° C. for 1 h. Water (100 ml) was added and the aqueous phase was extracted with MTBE (3×50 ml). The combined organic phases were dried over MgSO4, the solids were filtered off and all volatiles were removed under reduced pressure. Modification S10 (14.4 g, 40.0 mmol, 61%) was obtained as a colorless oil after vacuum distillation.

[0165] bp = 129-131°C (0.02 mbar). 1 H NMR (400 MHz, 20℃, C6D6): δ = 6.16 (dd, J = 20.4 Hz, J = 15.2 Hz, 1 H), 5.96 (dd, J = 15.2 Hz, J = 4.0 Hz, 1 H), 5.82 (dd, J = 20.4 Hz, J = 4.0 Hz, 1 H), 2.22 (t, J = 7.2 Hz, 4 H), 2.13 (s, 12 H), 1.66-1.58 (m, 4 H), 0.96 (s, 9 H), 0.76-0.72 (m, 4 H), 0.11 (s, 6 H) ppm. 13 C NMR (101 MHz, 20°C, C6D6): δ = 138.00 (CH,vinyl), 132.70 (CH2,vinyl), 63.33 (2 CH2), 45.58 (4 CH3), 25.99 (3 CH3), 21.85 (2 CH2), 18.42 (C), 13.41(2 CH2), -2.54 (2 CH3) ppm GC-MS (EI, 70 eV): m / z (%) = 358 (M + , 0.4), 343 (M+ -CH3, 3), 314 (25), 301 (M + -C4H9, 14), 274 (65), 230 (5), 145 (7), 119 (5), 103 (4), 84 (10), 58 (C3H8N + , 100). IR (ATR): λ -1 = 3050 (w), 2930 (m), 2856 (m), 2814 (m), 2763 (m), 1463 (m), 1405 (m), 1252 (m), 1181 (m), 1059 (s), 1041 (s), 1005 (m), 953 (m), 833 (s), 777 (vs), 676 (m) cm -1 .

[0166] Modified body S11 [ka] Dichloro-tert-butyldimethylsiloxyvinylsilane (Preparation Example 15, 3.44 g, 20.0 mmol, 1.0 equiv.) was dissolved in THF (13 ml). A Grignard solution of Preparation Example 7 in THF (46.0 mmol, 2.3 equiv., 46 ml) was added dropwise at 25° C. The reaction mixture was stirred at 25° C. for 16 h. Cyclohexane (50 ml) was added and the solid was filtered off. All volatiles were removed under reduced pressure. Modification S11 (4.15 g, 10.1 mmol, 51%) was obtained as a colorless oil. C 22 H 46 N2OSi2,M w = 410.79 g / mol.

[0167] 1H NMR (400 MHz, 20℃, CDCl3): δ = 6.19 (dd, J = 20.0 Hz, J = 14.8 Hz, 1 H), 5.97 (dd, J = 15.0 Hz, J = 4.0 Hz, 1 H), 5.84 (dd, J = 20.4 Hz, J = 4.4 Hz, 1 H), 2.48-2.43 (m, 12 H), 1.75-1.67 (m, 4 H), 1.65-1.58 (m, 8 H), 0.96 (s, 9 H), 0.82-0.78 (m, 4 H), 0.12 (s, 6 H) ppm. 13 C NMR (101 MHz, 20℃, CDCl3): δ = 138.03 (CH,ビニル), 132.72 (CH2,ビニル), 59.95 (2 CH2), 54.30 (4 CH2), 26.02 (3 CH3), 23.93 (4 CH2), 23.14 (2 CH2), 18.43 (C), 13.70(2 CH2), -2.51 (2 CH3) ppm. 29 Si{H} NMR (79.5 MHz, 20℃, CDCl3): δ = 10.01 (1 Si), -4.52 (1 Si) ppm. GC-MS (EI, 70 eV): m / z (%) = 409 (M + , 0.1), 395 (M + -CH3, 4), 383 (2), 353 (7), 340 (16), 326 (4), 300 (60), 298 (57), 270 (3), 242 (2), 110 (9), 84 (C5H 10 N + , 100). IR (ATR): λ -1 = 3049 (w), 2954 (m), 2928 (m), 2780 (m), 2736 (w), 1594(w), 1461 (m), 1405 (m), 1351 (m), 1251 (m), 1139 (m), 1065 (s), 1005 (s), 953 (m), 833 (s), 776 (vs), 676 (m) cm -1 .

[0168] Modified S12 [ka] Dichloro-tert-butyldimethylsiloxyvinylsilane (Preparation Example 15, 9.00 g, 35.0 mmol, 1.0 equiv.) was dissolved in THF (30 ml). Grignard solution of Preparation Example 5 in THF (75 mmol, 2.14 equiv., 75 ml) was added dropwise at 25° C. The reaction mixture was stirred at 25° C. for 1 h. Water (50 ml) was added and the aqueous phase was extracted with MTBE (3×50 ml). The combined organic phases were dried over MgSO4, the solids were filtered off and all volatiles were removed under reduced pressure. Modification S12 (16.4 g, 32.2 mmol, 92%) was obtained as a yellow oil. C 30 H 50 N2OSi2,M w = 510.91 g / mol.

[0169] 1 H NMR (400 MHz, 20℃, CDCl3): δ = 7.34-7.24 (m, 10 H), 6.06-5.95 (m, 2 H), 5.73 (dd, J = 19.6 Hz, J = 4.8 Hz, 1 H), 3.52 (s, 4 H), 2.41-2.37 (m, 4 H), 2.21 (s, 6 H), 1.61-1.52 (m, 4 H), 0.87 (s, 9 H), 0.60-0.56 (m, 4 H), 0.03 (s, 6 H) ppm. 13 C NMR (101 MHz, 20 °C, CDCl3): δ = 138.42 (2 C, Ar), 137.18 (CH, vinyl), 132.73 (CH2, vinyl), 129.17 (4 CH, Ar), 128.20 (4 CH, Ar), 127.03 (2 CH, Ar), 62.04 (2 CH2), 60.60 (2 CH2), 41.94 (2 CH3), 25.71 (3 CH3), 20.60 (2 CH2), 18.11 (C), 12.98 (2 CH2), -2.77 (2 CH3) ppm. 29Si{H} ​​NMR (79.5 MHz, 20℃, CDCl3): δ = 10.37 (1 Si), -5.28 (1 Si) ppm. GC-MS (EI, 70 eV): m / z (%) = 510 (M + , 0.5), 495 (M + -CH3, 2), 453 (2), 419 (8), 390 (5), 350 (18), 287 (5), 200 (3), 134 (C9H 12 N + , 100), 91 (C7H7 + , 72). IR (ATR): λ -1 = 3062 (w), 3028 (w), 2951 (m), 2928 (m), 2856 (m), 2785 (m), 1454 (m), 1252 (m), 1182 (w), 1053 (s, br), 1005 (s), 955 (s), 833 (s), 777 (s), 697 (vs) cm -1 .

[0170] Modified body S13 [ka] Dichloro-tert-butyldimethylsiloxyvinylsilane (Preparation Example 15, 28.1 g, 109 mmol, 1.0 equiv.) was dissolved in THF (75 ml). A Grignard solution of Preparation Example 1 in THF (230 mmol, 2.11 equiv., 230 ml) was added dropwise at 25° C. The reaction mixture was stirred at 25° C. for 16 h. Water (100 ml) was added and the aqueous phase was extracted with MTBE (3×100 ml). The combined organic phases were dried over MgSO4, the solids were filtered off and all volatiles were removed under reduced pressure. Modification S13 (38.2 g, 81 mmol, 74%) was obtained as a yellow oil. C 24 H 52 N4OSi2,M W = 468.88 g / mol.

[0171] 11H NMR (400 MHz, 20 °C, CDCl3): δ = 6.03 (dd, J = 19.6 Hz, J = 14.2 Hz, 1 H), 5.94 (dd, J = 15.2 Hz, J = 4.4 Hz, 1 H), 5.71 (dd, J = 19.6 Hz, J = 4.8 Hz, 1 H), 2.58 - 2.31 (m, 16 H), 2.32 - 2.28 (m, 4 H), 2.26 (s, 6 H), 1.53 - 1.44 (m, 4 H), 0.83 (s, 9 H), 0.57 - 0.53 (m, 4 H), 0.00 (s, 6 H) ppm. 13 13C NMR (101 MHz, 20 °C, CDCl3): δ = 137.16 (CH, vinyl), 132.69 (CH2, vinyl), 62.14 (2 CH2), 55.12 (4 CH2), 53.16 (4 CH2), 46.05 (2 CH3), 25.69 (3 CH3), 20.31 (2 CH2), 18.09 (C), 13.13 (2 CH2), -2.78 (2 CH3) ppm. GC-MS (EI, 70 eV): m / z (%) = 468 (M + , 59), 453 (M + -CH3, 16), 438 (5), 424 (21), 396 (16), 329 (16), 270 (10), 145 (6), 113 (CH3-NC4H7N-CH3 + , 100), 98 (22), 70 (55). IR (ATR): λ -1 = 3049 (w), 2933 (m), 2876 (m), 2792 (s), 1458 (m), 1283 (m), 1252 (m), 1174 (m), 1163 (m), 1052 (s), 1011 (s), 833 (s), 776 (vs), 675 (m) cm -1 .

[0172] Modified product S14

Chemical formula

[0173] 1 H NMR (400 MHz, 20℃, CDCl3): δ = 6.06 (dd, J = 19.6 Hz, J = 15.2 Hz, 1 H), 5.97 (dd, J = 15.2 Hz, J = 4.8 Hz, 1 H), 5.74 (dd, J = 19.6 Hz, J = 4.8 Hz, 1 H), 3.72-3.70 (m, 8 H), 2.43-2.40 (m, 8H), 2.33-2.29 (m, 4 H), 1.56-1.47 (m, 4 H), 0.86 (s, 9 H), 0.61-0.57 (m, 4 H), 0.03 (s, 6 H) ppm. 13 C NMR (101 MHz, 20 °C, CDCl3): δ = 137.09 (CH,vinyl), 132.79 (CH2,vinyl), 66.96 (4 CH2), 62.52 (2 CH2), 53.71 (4 CH2), 25.69 (3 CH3), 20.05 (2 CH2), 18.11 (C), 13.06 (2 CH2), -2.77 (2 CH3) ppm. 29 Si{H} ​​NMR (79.5 MHz, 20℃, CDCl3): δ = 10.40 (1 Si), -5.44 (1 Si) ppm. GC-MS (EI, 70 eV): m / z (%) = 442 (M + , 46), 427 (M +-CH3, 5), 412(17), 385(-C4H9, 10), 316(30), 314(30), 286(25), 230(4), 184(4), 145(11), 100(100). -1 = 3049 (w), 2953 (m), 2928 (m), 2855 (m), 2804 (m), 1462 (m), 1359 (w), 1252 (m), 1118 (s), 1056 (s), 1004 (s), 868 (m), 833 (s), 777 (vs), 675 (m) cm -1 .

[0174] e) Preparation of Reference Compounds Reference compound C1 [ka] Chlorodimethylvinylsilane (11.2 g, 92.4 mmol, 1.0 equiv.) was added dropwise to a solution of tertbutyldimethylsilanol (12.2 g, 92.4 mmol, 1.0 equiv.) and triethylamine (10.3 g, 102 mmol, 1.1 equiv.) in cyclohexane (100 ml) at room temperature. The mixture was stirred at room temperature for 18 h. After filtration, the solvent was removed under reduced pressure and distilled at 15 mbar to give the vinylsilane compound of reference compound C1 (14.6 g, 67.4 mmol, 73%) as a colorless liquid. 10 H 24 OSi2, M w = 216.47 g / mol.

[0175] bp=49-51°C (15mbar). 1 H NMR (400 MHz, 20℃, C6D6): δ = 6.17 (dd, J = 20.3 Hz, J = 14.8 Hz, 1 H), 5.89 (dd, J = 14.9 Hz, J = 4.0 Hz, 1 H), 5.75 (dd, J = 20.3 Hz, J = 4.0 Hz, 1 H), 0.94 (s, 9 H), 0.17 (s, 6 H), 0.06 (s, 6 H) ppm. 13C NMR (101 MHz, 20 °C, C6D6): δ = 139.75 (CH, vinyl), 131.79 (CH2, vinyl), 25.89 (3 CH3), 18.28 (C), 0.55 (2 CH3), -2.71 (2 CH3) ppm. GC-MS (EI, 70 eV): m / z (%) = 216 (M + , 0.1), 201 (M + -CH3, 3), 159 (M + -tertBu, 100), 131 (11), 145 (100), 73 (12).

[0176] Reference compound C2 [ka] A mixture of divinylbenzene isomers in ethylstyrene (122 g, 750 mmol, 1.0 equiv, 63%) was dissolved in cyclohexane (375 ml). Pyrrolidine (750 mmol, 1.0 equiv) was added at 25° C. Then, TMEDA (4.36 g, 37.5 mmol, 0.05 equiv) and n-butyllithium hexane solution (15 ml, 37.5 mmol, 0.05 equiv) were added. The reaction mixture was stirred at 25° C. for 16 h. The reaction mixture was washed three times with water (400 ml). After drying over MgSO4, the solid was filtered off and the solvent was removed under reduced pressure. After vacuum distillation, an isomeric mixture of vinyl compounds of reference compound C2 (40.5 g, 201 mmol, 27%) was obtained as a colorless oil. 14 H 19 N, M W = 201.31 g / mol.

[0177] bp = 105-106°C (0.25 mbar).

[0178] Reference compound C3 [ka] Dichloromethylvinylsilane (4.23 g, 30 mmol, 1.0 equiv.) was dissolved in THF (30 ml). Grignard solution in THF (60 mmol, 2.0 equiv., 60 ml) was added dropwise at 25° C. The reaction mixture was stirred for 18 h. After filtration, cyclohexane (50 ml) was added and the organic phase was washed with water (50 ml, pH=14). The organic phase was dried over MgSO4, the solid was filtered off and all volatiles were removed under reduced pressure. Reference compound C3 (10.3 g, 27.0 mmol, 90%) was obtained as a pale yellow oil. C 21 H 44 N4Si, M W = 380.70 g / mol.

[0179] 1 H NMR (400 MHz, 20℃, CDCl3): δ = 6.10 (dd, J = 20.0 Hz, J = 14.8 Hz, 1 H), 5.96 (dd, J = 14.8 Hz, J = 4.0 Hz, 1 H), 5.67 (dd, J = 20.0 Hz, J = 4.0 Hz, 1 H), 2.70-2.35 (m, br, 16 H), 2.41 (q, J = 7.2 Hz, 4 H), 2.34-2.30 (m, 4 H), 1.53-1.43 (m, 4 H), 1.08 (t, J = 7.2 Hz, 6 H), 0.56-0.52 (m, 4 H), 0.05 (s, 3 H) ppm. 13 C NMR (101 MHz, 20 °C, CDCl3): δ = 137.61 (CH,vinyl), 132.26 (CH2,vinyl), 62.31 (2 CH2), 53.22 (4 CH2), 52.78 (4 CH2), 52.31 (2 CH2), 21.10 (2 CH2), 11.95 (2 CH3), 11.48 (2 CH2), -5.51 (CH3) ppm. 29 Si{H} ​​NMR (79.5 MHz, 20℃, CDCl3): δ = -4.90 (1 Si) ppm. GC-MS (EI, 70 eV): m / z (%) = 380 (M + , 51), 365 (M +-CH3, 10), 351 (3), 336 (2), 322 (12), 310 (5), 296 (13), 267 (2), 225 (13), 154 (9), 140 (8), 127 (C2H5-C4N2H7-CH3 + , 100), 112 (15), 98 (10), 84 (31). IR (ATR): λ -1 = 3045 (w), 2967 (m), 2934 (m), 2874 (m), 2805 (s), 2765 (m), 1449 (m), 1346 (m), 1304 (m), 1252 (m), 1170 (s), 1162 (s), 1119 (s), 1009 (s), 946 (m), 797 (s), 775 (s), 745 (s), 706 (m) cm -1 .

[0180] 2. Polymer Synthesis General Polymerization Procedure: Cyclohexane, butadiene, and styrene (amounts given in the table) were charged into an air-free 10 L reactor and the stirred mixture was heated to 40 °C. Then TMEDA (amounts given in the table) as well as the modified monomer (amount and type of the modified) were added and n-butyl lithium (n-BuLi) was added dropwise to react the impurities (titration) until the color of the reaction mixture became yellowish. The polymerization was then started immediately by charging the desired amount of initiator in cyclohexane, corresponding to the target molecular weight of the polymer. The start time of the initiator charge was used as the polymerization start time. In parallel, the temperature was increased by heating or cooling the reactor walls starting from the initiator charge up to the final polymerization temperature. The final temperature was maintained until complete conversion was detected. Then butadiene (1.7-2% of the amount given in the table) was charged. When indicated in the table, the chain end modifier dimethoxydimethylsilane (DMDM, amount) was added after 5 min. The reaction was stopped after 20 min by adding methanol. The polymer solution was then stabilized with Irganox 1520D and the polymer was recovered by steam stripping and dried to a residual volatile content of less than 0.6%. The complete data set of samples is presented in the table below.

[0181] Hereinafter, the polymers according to the invention are referred to as examples (abbreviated as "Ex"), the polymers not according to the invention are referred to as reference examples (abbreviated as "REx") since they were prepared in the absence of a modifying monomer, and the polymers not according to the invention are referred to as comparative examples (abbreviated as "CEx") since they were prepared in the presence of a modifying monomer not according to the invention. [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7] [Table 8]

[0182] Polymer characterization In the table below the polymer properties of the prepared polymers after steam stripping are shown. [Table 9] [Table 10] [Table 11] [Table 12] [Table 13] [Table 14] [Table 15] [Table 16]

[0183] Vulcanized polymer compositions (vulcanized rubber compounds) After post-treatment of the polymer, the samples were compounded in a two-step mixing process according to different mixing plans ("recipe") and the vulcanized polymer compositions (vulcanizates) were characterized. The corresponding mixing recipes (including further additives) are given in the table below with the amounts of compounding ingredients expressed in phr ("parts per hundred parts of rubber"). [Table 17]

[0184] In the following tables, performance data of vulcanized polymer compositions ("vulcanizates") are listed. It should be noted that only one series of vulcanized rubbers can be compared. Therefore, only items in one table can be compared with each other, except for Table 18 and Table 19, which were evaluated in one run and therefore can be compared with each other. [Table 18] [Table 19] The use of the materials of the present invention results in an improved balance of performance (as reflected by tan d(0°C) / tan d(60°C)) or improved (C8) mechanical properties (EB and TS) while keeping the balance of performance constant. The vinyl siloxanes of the present invention can be selected depending on the respective performance priorities of the cured rubber compound.

[0185] [Table 20] The performance balance of WG and RR for compound C10 was improved compared to comparative example C11. Furthermore, the absolute values ​​of the RR predictors tan d(60°C), RB, and HBU were significantly improved compared to commercial BUNA cis 132. A higher degree of polymer-filler interaction can be noted in the bound rubber value, which increased from 39.7% to 67.3%.

[0186] [Table 21] Significant performance advantages of the present technology can also be observed when carbon black is used as a filler: C13 has better RB values, HBU, RR predictor tan d(60°C), and improved performance balance compared to reference example C14.

[0187] [Table 22] Both vulcanizates (C15 and C16) show an improved WG / RR performance balance compared to Reference Example C17 and Comparative Example C18, respectively.

[0188] [Table 23] Compound C20 of the present invention exhibits improved WG / RR performance balance as reflected by a quotient of 1.839 versus 1.723 or 1.766 for the Reference and Comparative Examples, respectively. As the data in Table 23 show.

[0189] [Table 24] Depending on the choice of vinyldisiloxane, either the RR index, the WG / RR balance, or the mechanical properties reflected by EB and TS can be improved compared to the reference or comparative examples. C25 and C27 show improved RR and WG / RR balance, while C23 and C24 show improved levels of mechanical properties while holding other properties constant.

[0190] [Table 25] C30 shows an improvement in the WG / RR balance compared to the reference.

[0191] [Table 26] The modified polymer of the present invention and C36, which contains a DMDM ​​modified low molecular weight polymer component, show significant improvement compared to the state-of-the-art modified polymer and blend C (C36), which contains the same DMDM ​​modified low molecular weight polymer component. The RR predictor tan d(60°C) and the WG / RR balance are both improved. Other properties (RB, HBU) confirm this trend.

[0192] [Table 27] The first part of Table 27 (C38-40) shows the effect of different microstructures with the same Tg on the performance of the inventive technology. C39 (15ST / 30V) and C40 (8ST / 40V) have similar significant performance improvements in RR and WG / RR balance compared to the reference C38. The inventive modifications can be applied independently of the microstructure selected.

[0193] The inventive C43 is the best cured rubber compound in the series C41-C44. C42 was prepared by applying the most recent state-of-the-art (vinylsilane with aminoalkyl groups without disiloxane units). C42 shows improved performance over the reference compound, but is inferior in performance compared to the inventive example C43.

[0194] As demonstrated above, the modifying monomers according to the invention allow the preparation of vulcanized polymer compositions with excellent properties, in particular an improved performance balance (expressed in the balance between rolling resistance and wet grip performance combined with acceptable or improved processing and mechanical properties, such as DIN abrasion (wear resistance) and handling properties).

[0195] Test Method Molecular weight analysis was performed by size exclusion chromatography SEC / RI using a HEWLETT PACKARD HP1100. The eluent THF was degassed online. The solvent flow rate was 1.0 ml / min. 100 μL of polymer solution was injected per analysis. The analysis was performed at 40° C. Molecular weights were initially calculated based on polystyrene calibration and shown as polystyrene in the tables. The actual molecular weight (SSBR molecular weight) was determined by dividing by the ratio derived from an initial comparison between the SEC / RI and SEC / MALLS molecular weights. The value of the ratio depends on the composition of the polymer (styrene and butadiene content). A ratio of 1.52 was used for SSBR with 21% and 25% styrene. For the calculation of the TMEDA molar ratio, Mp (as SSBR) was used.

[0196] Gas chromatography (GC) was used to monitor the polymerization reaction and monomer conversion.

[0197] NMR spectroscopy was performed on a BRUKER Avance400 with a 5 mm BBO probe.

[0198] FTIR spectroscopy measured attenuated total reflectance was used to determine the vinyl and styrene content.

[0199] The glass transition temperature T was measured using the DSC Q2000 under the following conditions: g It was decided. Weight: about 10~12mg Sample container: Alu / S Temperature range: (-140...80)℃ Heating rate: 20K / min or 5K / min Cooling rate: free cooling Purge gas: 20ml Ar / min Coolant: Liquid nitrogen

[0200] Each sample was measured at least once. The measurement contained two heating runs. The second heating experiment was used to determine the glass transition temperature.

[0201] To evaluate the curing properties, the uncured rheological properties were measured according to ASTM D5289-95 using a rotorless shear rheometer (MDR 2000E). The specimens were heated at 160°C for t 95 In the rebound resilience (RB) test, the specimens were vulcanized at 160°C. 95+5 The samples were vulcanized up to 100° C. The tensile strength (TS) and modulus were measured on a Zwick Z010 according to ASTM D412. DIN abrasion was measured according to DIN 53516 (1987-06-01). Rebound resilience (ISO 4662) was measured at 0° C., RT (20° C.) and 60°. The dynamic properties in terms of tan δ and E′ at the specified temperatures were measured using a dynamic spectrometer Eplexor 150N / 500N manufactured by Gabo Qualimeter Testanlagen GmbH (Germany) (strain measurement mode, applying a compressive dynamic strain of 1% at a frequency of 2 Hz).

[0202] Shrinkage rate: The shrinkage ratio is obtained in the same manner as the method established by Asahi (EP3536720A1). The shrinkage ratio is obtained by measuring the elgram using gel chromatography equipped with a triple detector system equipped with a light scattering detector, a viscometer, and an RI detector. In particular, a GPC-light scattering measurement device equipped with a light scattering detector and a viscometer connected to one mixed bed column packed with polystyrene gel as a packing material is used to obtain absolute molecular weights and intrinsic viscosities corresponding to each absolute molecular weight, calculate the intrinsic viscosity of a linear polymer corresponding to the absolute molecular weight, and obtain the shrinkage ratio as the ratio of the intrinsic viscosities corresponding to each absolute molecular weight. In addition, the RI signal is detected as a concentration-specific value by the RI region. For example, the shrinkage ratio was obtained as follows. 50 μl of a sample dissolved in THF was injected into a GPC triple detector system (Viscotek TDAmax, Malvern Co.) equipped with a light scattering detector, a viscometer, and an RI detector. The absolute molecular weight was obtained from a light scattering detector, and the intrinsic viscosity [μ] related to the absolute molecular weight for each peak was obtained from a light scattering detector and a viscometer, and the intrinsic viscosity [μ]0 of a linear polymer relative to the absolute molecular weight M was calculated using Equation 1.

number

[0203] The shrinkage factor SF(g') is the average value of the ratio of the intrinsic viscosities.

number

[0204] The procedure for measuring the Staudinger index (intrinsic viscosity) is as follows. 1. Preparation of four different concentrations of synthetic rubber in toluene a. The concentrations are as follows: i.0.7g / dL ii. 0.6 g / dL iii. 0.5 g / dL iv.0.4g / dL b. Place the Erlenmeyer flask on an analytical balance (accurate to less than 0.1 mg) and zero the weight. c. Crush the polymer into particles, charge it to an Erlenmeyer flask, and record the weight. i. Approx. 0.28g ii. Approximately 0.24g iii. Approximately 0.20g iv.About 0.16g d. Add approximately 40 ml of toluene to the polymer pieces and record the resulting weight. e. Close the Erlenmeyer flask and leave it on the shaker for approximately 24 hours. 2. Measurement of the dynamic viscosity of polymer solutions using a capillary viscometer (Rheotest LK 2.2) a. Transfer the polymer solution to a measurement container → Check for complete solubility and insoluble fraction of polymer void measurement! b. Measurement at 25°C c. 10 measurement runs d. Take the average of the last five runs for evaluation. 3. Calculation of the reduced viscosity or "Staudinger function" according to equation 1.1.

number

Claims

1. Vinyldisiloxane compounds of Formula 2: 【Chemistry 1】 (In the formula, R and R' are independently selected from C 1-18 hydrocarbyl; R 1 is optionally substituted vinyl, wherein one or more optional substituents are selected from methyl, ethyl, and vinyl; X is independently selected from one of the following moieties (X-1 to X-5): 【Chemistry 2】 Preferably, X is (X-1), R 2 is C 1-18 hydrocarbylene; A is NR 3 R 4 ; R 3 and R 4 are independently selected from linear, branched, and cyclic C 1-8 alkyl, C 6-12 aryl, C 7-15 aralkyl, SiR″ 3 , or linear, branched, and cyclic C 2-8 alkyl-O—SiR″ 3 , where each R″ is independently selected from C 1-6 alkyl, C 6-12 aryl, and C 7-18 alkylaryl; R 3 may be bonded to R 2 or R 4 to form a ring, and the ring may contain one or more atoms selected from oxygen atoms, nitrogen atoms, and sulfur atoms in addition to the nitrogen atom bonded to R 2 , but when R 3 and R 4 are both SiR″ 3 , the two R″ may be bonded to each other to form a ring together with the Si atom to which they are bonded; A' is NR 5 , where R 5 is selected from linear, branched, and cyclic C 1-8 alkylene, C 6-12 arylene, C 7 -C 15 aralkylene, SiR" 3 or R 2 A, or A' is a cyclic diaminediyl group such as piperazinyl; n is 1 or 2; m is 1 or 2; m+n is 2 or 3).

2. R ２ is a linear or branched C １－８ Alkylene, C ６－１２ Arylene, or C ７ -C １５ The compound of claim 1 which is an aralkylene.

3. 2. The compound of claim 1, wherein R and R' are independently selected from methyl, ethyl, n-propyl, i-propyl, t-butyl, phenyl, and benzyl.

4. R １ The compound of claim 1, wherein is vinyl or 1,3-butadienyl, preferably vinyl.

5. A is the following part: 【Transformation 3】 Preferably, 【Chemistry 4】 and R ＊ But C １－６ Alkyl, C ６－１２ Aryl, and C ７－１８ Alkylaryl, SiR ３ , or linear, branched, and cyclic C ２－８ Alkyl-O-SiR ３ 2. The compound of claim 1 selected from:

6. A is, 【Transformation 5】 and R ＊ but preferably methyl, ethyl, butyl, phenyl, benzyl, or SiR″ ３ Or C ２－８ Alkyl-O-SiR ３ and R″ is independently selected from methyl, ethyl, n-propyl, i-propyl, t-butyl, phenyl, and benzyl.

7. R ３ and R ４ The compound of claim 1 , wherein is independently selected from methyl, ethyl, phenyl, and benzyl.

8. R ２ are independently phenylene or linear C １－８ Alkylene, preferably linear C ３－６ alkylene, more preferably C ３ The compound of claim 1 which is an alkylene.

9. 2. The compound according to claim 1, wherein R is (methyl, methyl, methyl), (ethyl, ethyl, ethyl), (i-propyl, i-propyl, i-propyl), (phenyl, phenyl, phenyl), (methyl, methyl, t-butyl), (methyl, methyl, i-propyl), (ethyl, ethyl, i-propyl) or (phenyl, phenyl, t-butyl), preferably (ethyl, ethyl, ethyl), (i-propyl, i-propyl, i-propyl) or (methyl, methyl, t-butyl).

10. n is 1 and m is 2, or n is 2 and m is 1, or n is 1 and m is 1; Preferably, n is 1 and m is 2 or 1.

11. 11. A process for preparing an elastomeric polymer, said process comprising polymerizing at least one conjugated diene monomer and optionally one or more aromatic vinyl monomers in the presence of one or more initiator compounds and one or more compounds as defined in any of claims 1 to 10.

12. 12. The process of claim 11, wherein the diene monomer is 1,3-butadiene and the aromatic vinyl monomer is styrene.

13. 12. The process of claim 11, wherein the polymerization is a solution polymerization.

14. An elastomeric polymer obtainable by the process of claim 11.

15. 15. The elastomeric polymer of claim 14, comprising the following repeating units: 【Transformation 6】

16. 15. An unvulcanized polymer composition comprising an elastomeric polymer as defined in claim 14 and one or more additives.

17. 17. The polymer composition of claim 16, wherein the one or more additives are selected from extending oils, stabilizers, and additional polymers.

18. 20. The polymer composition of claim 17, further comprising one or more fillers.

19. 19. The polymer composition of claim 18, wherein the one or more fillers are selected from carbon black, carbon nanotubes, graphite, graphene, silica, carbon-silica dual phase fillers, clay, calcium carbonate, magnesium carbonate, lignin, glass particle based fillers, and starch based fillers, preferably wherein the filler is silica.

20. 20. The polymer composition of claim 17, further comprising one or more vulcanizing agents.

21. 21. A vulcanized polymer composition obtainable by vulcanizing the polymer composition defined in claim 20.

22. 21. A method for producing a vulcanized polymer composition, said method comprising the step of vulcanizing a polymer composition as defined in claim 20.

23. 22. An article comprising at least one component formed from the vulcanized polymer composition defined in claim 21.

24. 24. The article of claim 23, which is a tire, tire tread, tire sidewall, tire carcass, belt, gasket, seal, hose, vibration damper, footwear component, golf ball, or hose, preferably a tire.

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