JP6480490B2 - Silane sulfide modified elastomeric polymer - Google Patents

Description

  The present invention relates to silane sulfide modifier compounds and methods of making the same. The present invention further relates to a silane sulfide modified polymer compound obtained by reacting a living anionic elastomer polymer with a silane sulfide modifier. The silane sulfide modified polymeric compound may be provided in the form of a polymer composition, which polymer composition is vulcanized (crosslinked) by reaction with at least one vulcanizing agent, resulting in vulcanization A polymer composition may be obtained. Finally, the invention further provides an article comprising at least one component comprising (formed of) a component formed of a vulcanized polymer composition. The vulcanized polymer composition has relatively low hysteresis loss and many articles such as low heat generation, low rolling resistance, good wet grip and ice grip, abrasion resistance and tensile strength, and excellent processability And other desirable physical and chemical properties, such as tire treads, etc., which are well-balanced.

  In response to rising crude oil prices and domestic legislation, it is generally accepted that a reduction in carbon dioxide emissions by motor vehicles is required, which makes them "fuel efficient" for tire and rubber manufacturers. There is a need to manufacture tires. One common approach to obtain a fuel efficient tire is to produce a tire formulation with reduced hysteresis loss. The main cause of hysteresis in vulcanized elastomeric polymers is attributed to free polymer chain ends, ie, the portion between the last crosslink in the elastomeric polymer chain and the end of the polymer chain. The free end of this polymer does not participate in any efficient elastic recovery process and as a result, the energy transmitted to this part of the polymer is lost. This dissipated energy leads to a pronounced hysteresis under dynamic deformation. Another source of this hysteresis in the vulcanized elastomeric polymer is attributed to the poor distribution of filler particles in the vulcanized elastomeric polymer composition. The hysteresis loss of the crosslinked elastomeric polymer composition is related to its Tan δ value at 60 ° C. (ISO 4644-1: 2005; Rubber, Vulcanized or thermoplastic; Determination of dynamic properties-part 1: see General guidance). Generally, vulcanized elastomeric polymer compositions with relatively low Tan δ values at 60 ° C. are preferred as having low hysteresis loss. In the final tire product this translates into low rolling resistance and good fuel economy.

  In addition, there is also a need to maintain and improve tire grip performance, especially on wet or frozen roads. The wet and ice grip of the crosslinked elastomeric polymer composition tire is related to its Tan δ value at 0 ° C. and Tan δ value at −10 ° C. Low rolling resistance tires are obtained at the expense of degraded wet grip performance and vice versa are generally accepted. For example, in a random solution styrene-butadiene rubber (random SSBR), if the polystyrene unit concentration is reduced relative to the total polybutadiene unit concentration and the 1,2-polydiene unit concentration is kept constant, the tan delta at 60.degree. Both the tan delta at 0 ° C. is lowered, generally corresponding to the improvement of the rolling resistance and the deterioration of the wet grip performance of the tire. Similarly, in a random solution styrene-butadiene rubber (random SSBR), if the 1,2-polybutadiene unit concentration is reduced relative to the total polybutadiene unit concentration and the polystyrene unit concentration is kept constant, tan δ at 60 ° C. The tan delta at 0 ° C. decreases, generally corresponding to improved tire rolling resistance and wet grip performance degradation. Therefore, both rolling resistance, ie tan delta at 60 ° C., and wet grip, ie tan delta at 0 ° C., should be monitored when correctly evaluating the vulcanization performance of the rubber.

  One commonly accepted approach to reduce hysteresis loss is to reduce the number of free chain ends of the elastomeric polymer. Various methods have been described in the published literature, for example “cups such as tin tetrachloride to functionalize the polymer chain ends and react with components of the elastomeric composition, such as eg packings or unsaturated parts of the polymer. A method is described which comprises using a "ring agent". Examples of such methods are described in the following patents, in conjunction with other subject documents. U.S. Pat. Nos. 3,281,383, 3,244,664 and 3,692,874 (e.g. tetrachlorosilane), U.S. Pat. No. 3,978,103, U.S. Pat. No. 4,048 , 206, 4,474, 908, U.S. Patent 6,777,569 (blocked mercaptosilane) and U.S. Patent 3,078,254 (1,3,5-tri (bromomethyl) benzene And the like), U.S. Patent No. 4,616,069 (tin compounds and organic amino or amine compounds), and U.S. Patent Application No. 2005/0124740.

  The more frequent use of the “coupling agent” as a reactive agent for a living polymer is more than two polymer arms at a portion of the linear or non-linked polymer and at the attachment point, as compared to when not used Leading to the formation of a polymer blend comprising one or more moieties. The literature "Synthesis of end-functionalized polymers by means of living anionic polymerization", Journal of Macromolecular Chemistry and Physics, 197, (1996), 3135-3148 describes living polymers and silyl ethers as well as haloalkanes containing silyl thioether functionality and alkanes and silyl thioether functionalities. Describe the synthesis of "polystyrene-containing" and "polyisoprene-containing" living polymers with hydroxy (-OH) and mercapto (-SH) functional end caps, obtained by reacting Tertiary butyldimethylsilyl (TBDMS) groups are preferred as protecting groups for the -OH and -SH functions in the termination reaction. The reason is that the corresponding silyl ethers and thioethers are found to be stable and compatible with anionic living polymers.

  WO 2007/047943 describes the use of silane sulfide omega chain end modifiers. The silane sulfide compound is reacted with an anionically initiated living polymer to form a "chain end modified" polymer, which is subsequently mixed with a filler, vulcanizing agent, accelerator or extender oil to have low hysteresis loss A vulcanized elastomeric polymer composition is produced. To further control polymer molecular weight and polymer properties, coupling agents (or linking agents) can be used as an optional component in the process of preparation of elastomeric polymers. The modifier is preferably added before, after or during the addition of the coupling agent, and the modification reaction is preferably complete after the addition of the coupling agent. In some embodiments, more than one-third of the polymer chain ends are reacted with the coupling agent prior to the addition of the modifier.

  WO 2009/148932 describes elastomeric polymer compositions as reaction products of living anionic elastomeric polymers having two silane modifier compounds (A) and (B). It is reported that the silane modifier compound (A) reacts with at least two polymer chains to form a branched modified polymer, and the silane modifier compound (B) reacts with only one polymer chain to form chains It has been reported to form terminally modified polymer macromolecules. The resulting cured compositions containing branched modified and chain end modified polymer polymers have lower "Tan δ at 60 ° C." without adversely affecting other physical properties, particularly "Tan δ at 0 ° C." It is said that the value will be obtained as a result.

  WO 2007/047943 and WO 2009/148932 do not provide rheological information for fill-containing polymer compositions. However, it is reasonable to expect higher viscosities as a result of the improved polymer-filler association.

  Two types of fillers, silica and carbon black, are typically used in tire manufacture. The standard formulations very frequently contain both fillers in various proportions. Thus, modified polymers (branched modified polymer polymers and chain-end modified polymers) which exhibit low viscosity, in particular lower Mooney viscosity, in the (uncured) polymer composition and / or improved rolling resistance / grip balance properties of the cured composition It is preferred to have either or both of the polymers.

式中、
Ｍはケイ素またはスズであり、
ｘは１、２、および３から選択される整数であり、
ｙは０、１、および２から選択される整数であって、ｘ＋ｙ＝３であり、
ｓは２、３、および４から選択される整数であり、
ｔは０、１、および２から選択される整数であり、
ｕは０、１、および２から選択される整数であって、ｓ＋ｔ＋ｕ＝４であり、
Ｒ¹は独立して、（Ｃ₁−Ｃ₆）アルキルから選択され、
Ｒ²は独立して、（Ｃ₁−Ｃ₁₆）アルキル、（Ｃ₇−Ｃ₁₆）アルキルアリールおよび（Ｃ₇−Ｃ₁₆）アリールアルキルから選択され、
Ｒ³は少なくとも二価であり、独立して、（Ｃ₁−Ｃ₁₆）アルキル、（Ｃ₈−Ｃ₁₆）アルキルアリールアルキル、（Ｃ₇−Ｃ₁₆）アリールアルキルおよび（Ｃ₇−Ｃ₁₆）アルキルアリールから選択され、各基は第三級アミン基、シリル基、（Ｃ₇−Ｃ₁₈）アラルキル基および（Ｃ₆−Ｃ₁₈）アリール基の１つ以上の基で置換されてもよく、
Ｒ⁴は独立して、（Ｃ₁−Ｃ₁₆）アルキルおよび（Ｃ₇−Ｃ₁₆）アルキルアリールから選択され、
Ｘは独立して、塩化物、臭化物、および−ＯＲ⁵から選択され、式中、Ｒ⁵は（Ｃ₁−Ｃ₁₆）アルキルおよび（Ｃ₇−Ｃ₁₆）アリールアルキルから選択される。 The present invention provides a silane sulfide modifier represented by Formula 1 below:

During the ceremony
M is silicon or tin,
x is an integer selected from 1, 2 and 3 and
y is an integer selected from 0, 1, and 2 and x + y = 3,
s is an integer selected from 2, 3 and 4 and
t is an integer selected from 0, 1 and 2;
u is an integer selected from 0, 1 and 2 and s + t + u = 4,
R ¹ is independently selected from (C ₁ -C ₆ ) alkyl;
R ² is independently selected from (C ₁ -C ₁₆ ) alkyl, (C ₇ -C ₁₆ ) alkylaryl and (C ₇ -C ₁₆ ) arylalkyl;
R ³ is at least bivalent and is independently (C ₁ -C ₁₆ ) alkyl, (C ₈ -C ₁₆ ) alkylarylalkyl, (C ₇ -C ₁₆ ) arylalkyl and (C ₇ -C ₁₆ ) And each group may be substituted with one or more of a tertiary amine group, a silyl group, a (C ₇ -C ₁₈ ) aralkyl group and a (C ₆ -C ₁₈ ) aryl group,
R ⁴ is independently selected from (C ₁ -C ₁₆ ) alkyl and (C ₇ -C ₁₆ ) alkylaryl;
X is independently chloride, bromide, and is selected from -OR ^5, wherein, R ⁵ is selected from (C ₁ -C ₁₆₎ alkyl and (C ₇ -C ₁₆₎ arylalkyl.

（式中、Ｒ¹、Ｒ²、Ｒ³、ｘおよびｙは上に規定されるとおりである）、および
（ｉｂ）以下の式３ａおよび式３ｂから選択されるアミン化合物

（式中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰およびＲ¹¹はそれぞれ独立して、水素、（Ｃ₁−Ｃ₁₆）アルキル、（Ｃ₇−Ｃ₁₆）アルキルアリール、（Ｃ₇−Ｃ₁₆）アリールアルキルならびに（Ｃ₆−Ｃ₁₆）アリールから選択され、ｖは１〜１０から選択される整数である）を組み合わせるステップと、
（ｉｉ）ステップ（ｉ）の結果として得られる混合物を、以下の式４の化合物

（式中、Ｍはケイ素またはスズであり、ｕは２、３、および４から選択される整数であり、Ｒ⁴、Ｘおよびｔは上に規定されるとおりであり、ｔ＋ｕ＝４である）を溶媒中で反応させるステップと、
（ｉｉｉ）任意に、ステップ（ｉｉ）にて得られる式１のシランスルフィド変性剤を単離するステップと、を含む。 The invention further provides a method of producing the silane sulfide modifier of formula 1 as defined above,
(I)
(Ia) compounds of formula 2 below

(Wherein R ¹ , R ² , R ³ , x and y are as defined above), and (ib) an amine compound selected from Formula 3a and Formula 3b below

(Wherein, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently hydrogen, (C ₁ -C ₁₆ ) alkyl, (C ₇ -C ₁₆ ) alkyl aryl , (C ₇ -C ₁₆ ) arylalkyl and (C ₆ -C ₁₆ ) aryl, and v is an integer selected from 1 to 10,
(Ii) the resulting mixture of step (i) is a compound of formula 4

(Wherein, M is silicon or tin, u is an integer selected from 2, 3 and 4; R ⁴ , X and t are as defined above, and t + u = 4) Reacting in a solvent,
(Iii) optionally isolating the silane sulfide modifier of Formula 1 obtained in step (ii).

The present invention provides a further method of producing the silane sulfide modifier of formula 1 as defined above,
(I) reacting the compound of formula 2 as defined above with an alkali metal hydride in a solvent;
(Ii) reacting the resulting reaction product of step (i) with a compound of formula 4 as defined above in a solvent,
(Iii) optionally isolating the silane sulfide modifier of Formula 1 obtained in step (ii).

The present invention is also
a silane sulfide-modified polymer compound (also referred to as a silane sulfide-modified elastomer polymer compound) obtained by reacting i) a living anion elastomer polymer and a silane sulfide modifier represented by the formula 1 defined on ii) Provide).

  The present invention is further modified by at least one such silane sulfide modified polymeric compound as defined above, and a non-modified elastomeric polymer and a non-inventive modifier or coupling agent as described herein. The present invention provides a first polymer composition comprising one or more additional components selected from elastomeric polymers. The first polymer composition may also include additives such as stabilizers or softeners, including oils, as described herein. In general, the first polymer composition is obtained as a result of the polymerization treatment (reaction) used to provide the silane sulfide modified polymer compound of the present invention, and thus the modified polymer compound, and (i B) including one or more further components selected from the components which are added in or formed as a result of the polymerization treatment and which remain after solvent removal.

The present invention further provides a second polymer composition comprising at least
(I) a first polymer composition as defined above, and (ii) at least one filler.

The invention further provides a vulcanized polymer composition comprising the reaction product of at least the following 1) at least one vulcanizing agent, and 2) the first or second polymer composition as defined above.
The vulcanized polymer composition is produced by reacting the at least one vulcanizing agent with the first or second polymer composition as described herein.

  The invention further provides an article comprising at least one component formed from a vulcanized polymer composition as defined above.

The present invention provides a silane sulfide modifier of Formula 1 as defined above.
In a preferred embodiment, M is a silicon atom.
In a preferred embodiment, R ³ is divalent and (C ₁ -C ₁₆ ) alkyl.
In one embodiment, X is -OR ⁵ where R ⁵ is selected from (C ₁ -C ₁₆ ) alkyl.
In another embodiment, X is chloride or bromide.
In a preferred embodiment, R ² and R ⁴ are independently selected from (C ₁ -C ₁₆ ) alkyl.
In a preferred embodiment, R ¹ , R ² , R ⁴ and R ⁵ are independently selected from (C ₁ -C ₄ ) alkyl.
In one embodiment, s and t are each 2 and u is 0.
In another embodiment, s is 3, t is 1 and u is 0.
In one embodiment, x is 2 and y is 1.
In another embodiment, x is 1 and y is 2.

The invention further provides a method of producing a silane sulfide modifying agent of formula 1 as defined above, comprising: (i) a compound of formula 2 as defined above (ia); Combining the amine compound selected from Formula 3a and Formula 3b as defined in (iv) and (ii) reacting the resulting mixture of step (i) with the compound of Formula 4 defined above in a solvent And (iii) optionally isolating the silane sulfide modifier of Formula 1 obtained in step (ii).
In a preferred embodiment, R ³ is divalent and (C ₁ -C ₁₆ ) alkyl.
In one embodiment, X is -OR ⁵ where R ⁵ is selected from (C ₁ -C ₁₆ ) alkyl.
In another embodiment, X is chloride or bromide.
In a preferred embodiment, R ² and R ⁴ are independently selected from (C ₁ -C ₁₆ ) alkyl.
In a preferred embodiment, R ¹ , R ² , R ⁴ and R ⁵ are independently selected from (C ₁ -C ₄ ) alkyl.
In one embodiment, in Formula 1, s and t are each 2, u is 0, and in Formula 4, u and t are each 2.
In another embodiment, s is 3, t is 1 and u is 0.
In one embodiment, x is 2 and y is 1.
In another embodiment, x is 1 and y is 2.
In a preferred embodiment, v is selected from an integer of two.
In a preferred embodiment, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are independently selected from (C ₁ -C ₄ ) alkyl.

The present invention provides a further method of producing a silane sulfide modifying agent of formula 1 as defined above, wherein (i) reacting a compound of formula 2 as defined above with an alkali metal hydride in a solvent (Ii) reacting the resulting reaction product of step (i) with the compound of formula 4 as defined above in a solvent, and optionally (iii) obtained in step (ii) Isolating the silane sulfide modifier of Formula 1.
In a preferred embodiment, R ³ is divalent and (C ₁ -C ₁₆ ) alkyl.
In one embodiment, X is -OR ⁵ where R ⁵ is selected from (C ₁ -C ₁₆ ) alkyl.
In another embodiment, X is chloride or bromide.
In a preferred embodiment, R ² and R ⁴ are independently selected from (C ₁ -C ₁₆ ) alkyl.
In a preferred embodiment, R ¹ , R ² , R ⁴ and R ⁵ are independently selected from (C ₁ -C ₄ ) alkyl.
In one embodiment, in Formula 1, s and t are each 2, u is 0, and in Formula 4, u and t are each 2.
In another embodiment, s is 3, t is 1 and u is 0.
In one embodiment, x is 2 and y is 1.
In another embodiment, x is 1 and y is 2.
In a preferred embodiment, v is selected from an integer of two.
In a preferred embodiment, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are independently selected from (C ₁ -C ₄ ) alkyl.

  In the process according to the invention for producing silane sulfide modifiers of the formula 1, the latter compounds are also isolated from the reaction mixture in the corresponding step (iii) by conventional methods, for example filtration, evaporation of the solvent or distillation Good.

The present invention is also
Provided are i) a living anionic elastomeric polymer, and ii) a silane sulfide modified polymeric compound obtainable by reacting a silane sulfide modifier of formula 1 as defined in the general and preferred embodiments.
In the modification reaction, one or more living polymer chains are modified at the end (s) of the polymer chain by one silane sulfide modifier. The resulting modified macromolecular compound is not necessarily chain end modified. For example, reaction of two polymer chains with one silane sulfide modifier can result in a polymer-silane sulfide-polymer structure.

  The present invention further comprises an elastomeric polymer modified with at least one such silane sulfide modified polymeric compound as defined above and a non-modified elastomeric polymer and a non-inventive modifier or coupling agent as defined above. There is provided a first polymer composition comprising one or more further components selected.

The present invention further provides a second polymer composition comprising at least
(I) a first polymer composition as defined above, and (ii) at least one filler.

In a preferred embodiment, at least one filler is silica.
In another preferred embodiment, at least one filler is carbon black.
In one embodiment, the second polymer composition further comprises an oil.
In a further embodiment, the second polymer composition comprises a vulcanizing agent.

  In one embodiment, the second polymer composition is obtained as a result of a mechanical mixing process with the first polymer composition and at least one filler. The second polymer composition typically comprises components that are added to the (solvent-free) first polymer composition and remain in the composition after completion of the mechanical mixing process. Thus, the specific component contained in the second polymer composition comprises at least one filler and may need to include, but not include, alternative (solvent-free) modified or non-modified polymers, stabilizers and emollients But not limited to them.

The invention also provides a vulcanized polymer composition comprising the reaction product of at least the following 1) at least one vulcanizing agent, and 2) the first or second polymer composition as defined above.
In a preferred embodiment of the vulcanized polymer composition, component 2) is a second polymer composition as described herein.

The present invention also provides a method of producing a vulcanized polymer composition, which comprises at least reacting the following components:
1) at least one vulcanizing agent, and 2) a first or second polymer composition as defined above.
In a preferred embodiment of the method of producing a vulcanized polymer composition, component 2) is a second polymer composition as described herein.

  The vulcanized polymer composition is obtained as a result of a reactive polymer-polymer cross-linking treatment performed on a first or second polymer composition comprising at least one vulcanizing agent. Thus, reactive processing converts the essentially non-crosslinked elastomeric polymer composition into a crosslinked elastomeric polymer composition, ie, a vulcanized polymer composition.

  The present invention also provides an article comprising at least one component formed from a vulcanized polymer composition as defined above. In one embodiment, the article is a tire or a tire tread.

  The following embodiments apply to all applicable aspects and embodiments described herein.

  In one embodiment, the polymer portion of the silane sulfide modified polymer compound of the present invention is selected from the group consisting of a modified styrene-butadiene copolymer, a modified polybutadiene, a modified butadiene-isoprene copolymer, a modified polyisoprene and a modified butadiene-styrene-isoprene terpolymer It is selected.

  In one embodiment, the first or second polymer composition according to the present invention further comprises a styrene-butadiene copolymer, including but not limited to solution styrene-butadiene rubber (SSBR) and emulsion styrene-butadiene rubber (ESBR) Polybutadiene comprising a polybutadiene having a concentration of 1,4-cis-polybutadiene within the range of 90 to 99 percent, 30 to 70 percent, or 2 to 25 percent by weight, butadiene-isoprene copolymer, polyisoprene, butadiene-styrene An isoprene terpolymer, and at least one polymer selected from the group consisting of combinations thereof.

  The present invention includes within its scope any combination of two or more of the specific or preferred features defined herein, unless the combination is technically or logically excluded.

Polymerization The living anionic elastomeric polymer employed in the present invention is obtained by polymerizing one or more monomers, as is well known in the art. The polymerization initiator compound, 1,2-polybutadiene or 1,2-polyisoprene or 3,4-polyisoprene unit introduced into the polymer by randomly adjusting the aromatic vinyl compound by increasing the reactivity of the initiator General information on applicable polymerization techniques, including randomizer agents (also called polar coordinator compounds) and accelerators for random adjustment, amounts of each compound, monomer (s), and appropriate processing conditions Is described in WO 2009/148932, which is fully incorporated herein by reference. Solution polymerization is usually carried out at low pressure, preferably less than 10 MPa, preferably in a temperature range of 0 to 120 ° C. The polymerization is generally carried out under batch, continuous or semi-continuous polymerization conditions. The polymerization process is preferably carried out as a solution polymerization in which the polymer formed is substantially soluble in the reaction mixture, or as a suspension / slurry polymerization in which the polymer formed is substantially insoluble in the reaction medium To be done. Examples of preferred randomizer agents (also called polar coordinator compounds) and enhancers are listed in WO 2009/148932.

Initiation Compounds The use of ionic initiators such as conjugated dienes, trienes, monovinyl aliphatic and aromatic monomers, and lithium initiators to polymerize other monomers is well known (anionic solution polymerization). Such polymerization is due to the initiation of nucleophile reaction, in which the reaction of the monomers forms and increases the polymer structure, which proceeds according to the anionic polymerization mechanism. In these polymerizations, the active center is typically a carbon ion that has a partial or total charge negative. Through polymerization, the polymer structure is ionized or "living". Thus, the polymer structure has at least one reactive or "living" end. This is the context for describing the crosslinked elastomeric polymer prepared by the anionic solution polymerization technique of the term "living" as used herein. Thus, living anionic elastomeric polymers are prepared by anionic polymerization as described herein.

  The polymerization of the monomers described herein, in the case of the anionic living-type polymerization reaction, is an organometallic compound having at least one lithium, sodium or potassium atom and contains 1 to about 20 carbon atoms. It is typically initiated with anionic initiators, including but not limited to organometallic compounds. Preferably, the organometallic compound is selected from ethyllithium, propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, hexyllithium, 1,4-dilithio-n-butane, 1,3-di- It has at least one lithium atom such as (2-lithio-2-hexyl) benzene, preferably n-butyllithium and sec-butyllithium atoms. These organic lithium initiators may be used alone, or may be used as a mixture of two or more different types. The amount of organolithium initiator used varies based on the monomers to be polymerized and the target molecular weight of the polymer to be produced, but the amount is typically 0.05 to 5 mmol, preferably 0.2, per 100 grams of monomer. ~ 3 mmol.

A randomizer Lewis base is optionally added to the polymerization mixture to control the microstructure (content of vinyl bonds) of the conjugated diolefin portion of the homopolymer, copolymer or terpolymer of the diolefin type, or the inclusion of a conjugated diene monomer The compositional distribution of the aromatic vinyl compound in the copolymer or terpolymer may be adjusted and thus, for example, may act as a randomizer component. The Lewis base includes, for example, 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, methyltetrahydrofuryl ether, ethyltetrahydrofuryl Ether compounds such as alkyltetrahydrofurylether such as ether, propyltetrahydrofurylether, butyltetrahydrofurylether, hexyltetrahydrofurylether, octyltetrahydrofurylether, tetrahydrofuran, 2,2- (bistetrahydrofurfuryl) propane, bistetrahydrofurfuryl Formal, te Methyl ether of rahydrofurfuryl alcohol, ethyl ether of tetrahydrofurfuryl alcohol, butyl ether of tetrahydrofurfuryl alcohol, α-methoxytetrahydrofuran, dimethoxybenzene and dimethoxyethane, and butyl ether of triethylamine, pyridine, N, N, N ', Tertiary amine compounds such as N'-tetramethylethylenediamine, dipiperidinoethane, methylether of N, N-diethylethanolamine, N, N-diethylethanolamine and ethylether of N, N-diethylethanolamine Although there is, it is not limited to these.

Coupling Agent The coupling agent includes tin tetrachloride, tin tetrabromide, tin (IV) fluoride, tin tetraiodide, silicon tetrachloride, silicon tetrabromide, silicon tetrafluoride, silicon tetrafluoride, silicon tetraiodide, alkyl tin and Alkyl silicon trihalides or dialkyl tins and dialkyl silicon trihalides are included. Polymers combined with tin or silicon trihalides have at most four arms, polymers bonded with alkyltin and alkylsilicon trihalides have at most three arms, dialkyltins and dialkylsilicon trihalides The polymer bound to the hydride has at most two arms. Hexahalodisilanes or hexahalodisiloxanes may be used as coupling agents, resulting in polymers with up to 6 arms. Useful tin and silicon halide coupling agents are SnCl ₄ , (R ₁ ) ₂ SnCl ₂ , R ₁ SnCl ₃ , SiCl ₄ , (R ₁ ) ₂ SiCl ₂ , R ₁ SiCl ₃ , Cl ₃ Si—SiCl _3, includes a _{Cl 3 Si-O-SiCl 3} , Cl 3 Sn-SnCl 3 and _{Cl 3 Sn-O-SnCl 3} , R 1 is a hydrocarbyl group, preferably an alkyl group. Coupling agents for tin and silicon alkoxide further include Sn (OMe) ₄ , Si (OMe) ₄ , Sn (OEt) ₄ and Si (OEt) ₄ . The most preferred coupling agents are SnCl _4, SiCl _4, Sn (OMe) ₄ and Si (OMe) ₄ .

  The coupling agent may be added intermittently (or at regular or irregular intervals) or continuously during the polymerization, but the conversion of polymerization is higher than 80%, more preferably higher than 90%. Preferably, it is added at a conversion rate.

  For example, the coupling agent can be added continuously during the polymerization if asymmetric binding is desired. This continuous addition is usually carried out in a reaction zone separate from the zone in which the majority of the polymerization takes place. The coupling agent can be added to a hydrocarbon solution, such as cyclohexane, added to the polymerization mixture, and stirred appropriately for distribution and reaction. Coupling agents are typically added only after a high degree of conversion has already been obtained. For example, the coupling agent is usually added only after monomer conversion greater than about 80 percent is achieved. It is typically preferred that the monomer conversion reaches at least about 90 percent before the coupling agent is added. The polymer bound to the coupling agent has a minimum of two polymer chain arms.

  In one embodiment, the substantial amount of living polymer chain ends is not terminated with a terminating agent (ie, an inorganic or organic acid such as water, alcohol, hydrochloric acid, sulfuric acid, and carboxylic acid, preferably alcohol or water), and the coupling agent It is also not reacted with the silane sulfide modifier of the present invention prior to reaction with. That is, a living polymer chain end is present, which can react with the coupling agent in the polymer chain bonding reaction. The coupling reaction via the coupling agent takes place before, after or during the addition of the silane sulfide modifier. Preferably, the coupling reaction via the coupling agent is completed prior to the addition of the silane sulfide modifier. In one embodiment, as a result of the binding reaction, as determined by GPC, up to 80 percent of the living polymer chains react with the coupling agent. Preferably, no more than 65 percent of the polymer chains react with the coupling agent, and more preferably no more than 50 percent of the polymer chains react with the coupling agent.

  In some preferred embodiments, 10 to 30 percent of the living polymer chain ends react with the coupling agent (s) prior to the addition of the silane sulfide modifier, as determined by GPC. In other embodiments, 20 to 35 percent of the living polymer chain ends are reacted with the coupling agent (s) prior to the addition of the silane sulfide modifier. In still other embodiments, 35 to 50 percent of the living polymer chain ends are reacted with the coupling agent (s) prior to the addition of the silane sulfide modifier. The coupling agent may be added directly to the polymer solution without dilution. However, it may be more advantageous to add the coupling agent in solution, such as an inert solvent (e.g. cyclohexane). For example, when different types of coupling agents are used, 0.01 to 2.0 mol, preferably 0.02 to 1.5 mol, more preferably 0.04 to 0.6 mol of the coupling agent is 4.0, It is used per mole of living, that is, at the end of the anionic polymer chain.

As explained earlier, the combination of coupling agents comprising tin or silicon may optionally be used to bind the polymers. Various coupling agent combinations such as Bu ₂ SnCl ₂ and SnCl ₄ , Me ₂ SiCl ₂ and Si (OMe) ₄ , Me ₂ SiCl ₂ and SiCl ₄ , SnCl ₄ and Si (OMe) ₄ , SnCl ₄ and SiCl ₄ May be used to attach polymer chains. It is particularly desirable to use a combination of tin and silicon coupling agents for tire tread compounds that contain both silica and carbon black. In such cases, the molar ratio of tin to silicon compound used to bond the elastomeric polymer is usually in the range of 20:80 to 95: 5, more typically 40:60 to 90:10, and Preferably, it will be in the range of 60:40 to 85:15. Most typically, coupling agents (tin and silicon compounds, silicon coupling agents) are used in the range of about 0.001 to 4.5 mmol for every 100 grams of elastomeric polymer. Generally, it is preferred to use about 0.05 to about 0.5 mmol of coupling agent per 100 grams of polymer to obtain the desired Mooney viscosity to allow for subsequent chain end functionalization of the remaining living polymer portion. Higher amounts tend to produce polymers containing terminal reactive groups or obtaining poor bonding, and only poor chain end modification is possible.

  In one embodiment, less than 0.01-5.0 mol, preferably 0.05-2.5 mol, more preferably 0.1-1.5 mol of coupling agent per 10.0 moles of living lithium polymer chain end Is used. The coupling agent may be added to the polymerization mixture in the reactor in a hydrocarbon solution (e.g. cyclohexane), suitably mixed to be distributed and reacted.

  The polymer attachment reaction may be carried out in a temperature range of 0 ° C to 150 ° C, preferably 15 ° C to 120 ° C, and even more preferably 40 ° C to 100 ° C. There is no limitation on the duration of the binding reaction. However, in view of an economical polymerization process, for example, in the case of a batch polymerization process, the bonding reaction is usually stopped about 5 to 60 minutes after the coupling agent is added.

  The coupling agent is added to a hydrocarbon solution, such as cyclohexane, added to the polymerization mixture in the reactor, appropriately mixed and distributed and reacted.

Silane Sulfide Modifiers In accordance with the present invention, silane sulfide modification agents (also referred to as silane sulfide modifiers or modifier agents) are used to control polymer properties. . The term "silane sulfide modifier" includes the silane sulfide modifiers of Formula 1 of the present invention, including compounds of Formula 5 and Formula 6, as described more particularly below.

式５中、Ｍはケイ素原子またはスズ原子であり、
Ｒ³は少なくとも二価であり、（Ｃ₈−Ｃ₁₆）アルキルアリールアルキル、（Ｃ₇−Ｃ₁₆）アリールアルキル、（Ｃ₇−Ｃ₁₆）アルキルアリール、または（Ｃ₁−Ｃ₁₆）アルキルであり、各基は以下の基：第三級アミン基、シリル基、（Ｃ₇−Ｃ₁₈）アラルキル基および（Ｃ₆−Ｃ₁₈）アリール基の１つ以上で置換されていてもよく、
Ｒ¹およびＲ¹²はそれぞれ独立して、（Ｃ₁−Ｃ₄）アルキルから選択され、
Ｒ²およびＲ¹³はそれぞれ独立して、（Ｃ₁−Ｃ₁₆）アルキル、（Ｃ₇−Ｃ₁₆）アルキルアリールおよび（Ｃ₇−Ｃ₁₆）アリールアルキルから選択され、
Ｒ⁴およびＲ¹⁴はそれぞれ独立して、（Ｃ₁−Ｃ₁₆）アルキルおよび（Ｃ₇−Ｃ₁₆）アルキルアリールから選択され、
ｂおよびｄはそれぞれ独立して、０、１、および２の整数から選択され、ａおよびｃはそれぞれ独立して、１、２、および３の整数から選択され、ａ＋ｂ＝３であり、ｃ＋ｄ＝３である。 The silane sulfide modifiers of the present invention include compounds of Formula 5:

In Formula 5, M is a silicon atom or a tin atom,
R ³ is at least bivalent and is (C ₈ -C ₁₆ ) alkylarylalkyl, (C ₇ -C ₁₆ ) arylalkyl, (C ₇ -C ₁₆ ) alkylaryl, or (C ₁ -C ₁₆ ) alkyl And each group may be substituted by one or more of the following groups: tertiary amine group, silyl group, (C ₇ -C ₁₈ ) aralkyl group and (C ₆ -C ₁₈ ) aryl group,
R ¹ and R ¹² are each independently selected from (C ₁ -C ₄ ) alkyl;
R ² and R ¹³ are each independently selected from (C ₁ -C ₁₆ ) alkyl, (C ₇ -C ₁₆ ) alkylaryl and (C ₇ -C ₁₆ ) arylalkyl,
R ⁴ and R ¹⁴ are each independently selected from (C ₁ -C ₁₆ ) alkyl and (C ₇ -C ₁₆ ) alkylaryl;
b and d are each independently selected from the integers of 0, 1 and 2; a and c are each independently selected from the integers of 1, 2 and 3; a + b = 3, c + d = It is three.

In one embodiment, R ³ is a (C ₁ -C ₁₆ ) bivalent alkyl group or a (C ₈ -C ₁₆ ) bivalent alkylarylalkyl group.

In one embodiment, R ³ is alkylene. In a further embodiment, the alkylene is -CH ₂ - (methylene), - (CH _{2) 2} - (ethylidene), - (CH _{2) 3} - (propylidene) and - is selected from (butylidene) - (CH _{2) 4} Ru.

In one embodiment, R ³ is a divalent aralkylene group. In a further embodiment, the aralkylene group is _{-CH 2 -C 6 H 4 -CH 2} - is selected from - (cyclohexylidene) and _{-C 6 H 4 -C (CH 3} ) 2 -C 6 H 4.

In one embodiment, R ² , R ⁴ , R ¹³ and R ¹⁴ are each independently (C ₁ -C ₁₆ ) alkyl. In a further embodiment, the alkyl is CH ₃ - (methyl), CH ₃ -CH ₂ - _{(ethyl), CH 3 - (CH 2} ) 2 - ( _{propyl), CH 3 - (CH 2} ) 3 (n- butyl) And CH ₃ -C (CH ₃ ) ₂ (tert-butyl).

In one embodiment of Formula 5, R ³ is linear C ₁ -C ₁₀ alkyl (divalent), cyclic C ₆ -C ₁₂ alkyl (divalent), C ₆ -C ₁₅ aryl (divalent) and C ₇ It is selected from the group consisting of -C ₁₂ alkylaryl (divalent).

  In one embodiment of Formula 5, b and d are each independently selected from the integers of 0 and 1, and a and c are each independently selected from the integers of 2 and 3.

  In one embodiment of the silane sulfide modifier of Formula 5, M is a silicon atom, a and c are integers selected from 2 and 3 respectively, and b and d are integers selected from 0 and 1 respectively is there.

  Although not explicitly shown in Formula 5, it is understood that the silane sulfide modifiers of the present invention also include their corresponding Lewis base adducts (eg, solvent molecules tetrahydrofuran, diethyl ether, dimethoxyethane which coordinate silicon atoms) Be done.

Specific preferred species of the silane sulfide modifiers of the present invention include the following compounds and their corresponding Lewis base adducts.
_{(MeO) 3 Si- (CH 2} ) 3 -S-Si (Me) 2 -S- (CH 2) 3 -Si (OMe) 3,
_{(MeO) 3 Si- (CH 2} ) 3 -S-Si (Et) 2 -S- (CH 2) 3 -Si (OMe) 3,
_{(MeO) 3 Si- (CH 2} ) 3 -S-Si (Bu) 2 -S- (CH 2) 3 -Si (OMe) 3,
_{(EtO) 3 Si- (CH 2} ) 3 -S-Si (Me) 2 -S- (CH 2) 3 -Si (OEt) 3,
_{(EtO) 3 Si- (CH 2} ) 3 -S-Si (Et) 2 -S- (CH 2) 3 -Si (OEt) 3,
_{(EtO) 3 Si- (CH 2} ) 3 -S-Si (Bu) 2 -S- (CH 2) 3 -Si (OEt) 3,
_{(PrO) 3 Si- (CH 2} ) 3 -S-Si (Me) 2 -S- (CH 2) 3 -Si (OPr),
_{(PrO) 3 Si- (CH 2} ) 3 -S-Si (Et) 2 -S- (CH 2) 3 -Si (OPr) 3,
_{(PrO) 3 Si- (CH 2} ) 3 -S-Si (Bu) 2 -S- (CH 2) 3 -Si (OPr) 3,
_{(MeO) 3 Si- (CH 2} ) 2 -S-Si (Me) 2 -S- (CH 2) 2 -Si (OMe) 3,
_{(MeO) 3 Si- (CH 2} ) 2 -S-Si (Et) 2 -S- (CH 2) 2 -Si (OMe) 3,
_{(MeO) 3 Si- (CH 2} ) 2 -S-Si (Bu) 2 -S- (CH 2) 2 -Si (OMe) 3,
_{(EtO) 3 Si- (CH 2} ) 2 -S-Si (Me) 2 -S- (CH 2) 2 -Si (OEt) 3,
_{(EtO) 3 Si- (CH 2} ) 2 -S-Si (Et) 2 -S- (CH 2) 2 -Si (OEt) 3,
_{(EtO) 3 Si- (CH 2} ) 2 -S-Si (Bu) 2 -S- (CH 2) 2 -Si (OEt) 3,
_{(PrO) 3 Si- (CH 2} ) 2 -S-Si (Me) 2 -S- (CH 2) 2 -Si (OPr) 3,
_{(PrO) 3 Si- (CH 2} ) 2 -S-Si (Et) 2 -S- (CH 2) 2 -Si (OPr) 3,
_{(PrO) 3 Si- (CH 2} ) 2 -S-Si (Bu) 2 -S- (CH 2) 2 -Si (OPr) 3,
_{(MeO) 3 Si-CH 2} -S-Si (Me) 2 -S-CH 2 -Si (OMe) 3,
_{(MeO) 3 Si-CH 2} -S-Si (Et) 2 -S-CH 2 -Si (OMe) 3,
_{(MeO) 3 Si-CH 2} -S-Si (Bu) 2 -S-CH 2 -Si (OMe) 3,
_{(EtO) 3 Si-CH 2} -S-Si (Me) 2 -S-CH 2 -Si (OEt) 3,
_{(EtO) 3 Si-CH 2} -S-Si (Et) 2 -S-CH 2 -Si (OEt) 3,
_{(EtO) 3 Si-CH 2} -S-Si (Bu) 2 -S-CH 2 -Si (OEt) 3,
_{(PrO) 3 Si-CH 2} -S-Si (Me) 2 -S-CH 2 -Si (OPr) 3,
_{(PrO) 3 Si-CH 2} -S-Si (Et) 2 -S-CH 2 -Si (OPr) 3,
_{(PrO) 3 Si-CH 2} -S-Si (Bu) 2 -S-CH 2 -Si (OPr) 3,
_{(MeO) 3 Si-CH 2} -CMe 2 -CH 2 -S-Si (Me) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OMe) 3,
_{(MeO) 3 Si-CH 2} -CMe 2 -CH 2 -S-Si (Et) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OMe) 3,
_{(MeO) 3 Si-CH 2} -CMe 2 -CH 2 -S-Si (Bu) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OMe) 3,
_{(EtO) 3 Si-CH 2} -CMe 2 -CH 2 -S-Si (Me) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OEt) 3,
_{(EtO) 3 Si-CH 2} -CMe 2 -CH 2 -S-Si (Et) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OEt) 3,
_{(EtO) 3 Si-CH 2} -CMe 2 -CH 2 -S-Si (Bu) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OEt) 3,
_{(PrO) 3 Si-CH 2} -CMe 2 -CH 2 -S-Si (Me) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OPr) 3,
_{(PrO) 3 Si-CH 2} -CMe 2 -CH 2 -S-Si (Et) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OPr) 3,
_{(PrO) 3 Si-CH 2} -CMe 2 -CH 2 -S-Si (Bu) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OPr) 3,
_{(MeO) 3 Si-CH 2} -C (H) Me-CH 2 -S-Si (Me) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OMe) 3,
_{(MeO) 3 Si-CH 2} -C (H) Me-CH 2 -S-Si (Et) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OMe) 3,
_{(MeO) 3 Si-CH 2} -C (H) Me-CH 2 -S-Si (Bu) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OMe) 3,
_{(EtO) 3 Si-CH 2} -C (H) Me-CH 2 -S-Si (Me) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OEt) 3,
_{(EtO) 3 Si-CH 2} -C (H) Me-CH 2 -S-Si (Et) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OEt) 3,
_{(EtO) 3 Si-CH 2} -C (H) Me-CH 2 -S-Si (Bu) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OEt) 3,
_{(PrO) 3 Si-CH 2} -C (H) Me-CH 2 -S-Si (Me) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OPr) 3,
_{(PrO) 3 Si-CH 2} -C (H) Me-CH 2 -S-Si (Et) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OPr) 3,
_{(PrO) 3 Si-CH 2} -C (H) Me-CH 2 -S-Si (Bu) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OPr) 3,
_{(MeO) 2 (Me) Si-} (CH 2) 3 -S-Si (Me) 2 -S- (CH 2) 3 -Si (OMe) 2 (Me),
_{(MeO) 2 (Me) Si-} (CH 2) 3 -S-Si (Et) 2 -S- (CH 2) 3 -Si (OMe) 2 (Me),
_{(MeO) 2 (Me) Si-} (CH 2) 3 -S-Si (Bu) 2 -S- (CH 2) 3 -Si (OMe) 2 (Me),
_{(EtO) 2 (Me) Si-} (CH 2) 3 -S-Si (Me) 2 -S- (CH 2) 3 -Si (OEt) 2 (Me),
_{(EtO) 2 (Me) Si-} (CH 2) 3 -S-Si (Et) 2 -S- (CH 2) 3 -Si (OEt) 2 (Me),
_{(EtO) 2 (Me) Si-} (CH 2) 3 -S-Si (Bu) 2 -S- (CH 2) 3 -Si (OEt) 2 (Me),
_{(PrO) 2 (Me) Si-} (CH 2) 3 -S-Si (Me) 2 -S- (CH 2) 3 -Si (OPr) 2 (Me),
_{(PrO) 2 (Me) Si-} (CH 2) 3 -S-Si (Et) 2 -S- (CH 2) 3 -Si (OPr) 2 (Me),
_{(PrO) 2 (Me) Si-} (CH 2) 3 -S-Si (Bu) 2 -S- (CH 2) 3 -Si (OPr) 2 (Me),
_{(MeO) 2 (Me) Si-} (CH 2) 2 -S-Si (Me) 2 -S- (CH 2) 2 -Si (OMe) 2 (Me),
_{(MeO) 2 (Me) Si-} (CH 2) 2 -S-Si (Et) 2 -S- (CH 2) 2 -Si (OMe) 2 (Me),
_{(MeO) 2 (Me) Si-} (CH 2) 2 -S-Si (Bu) 2 -S- (CH 2) 2 -Si (OMe) 2 (Me),
_{(EtO) 2 (Me) Si-} (CH 2) 2 -S-Si (Me) 2 -S- (CH 2) 2 -Si (OEt) 2 (Me),
_{(EtO) 2 (Me) Si-} (CH 2) 2 -S-Si (Et) 2 -S- (CH 2) 2 -Si (OEt) 2 (Me),
_{(EtO) 2 (Me) Si-} (CH 2) 2 -S-Si (Bu) 2 -S- (CH 2) 2 -Si (OEt) 2 (Me),
_{(PrO) 2 (Me) Si-} (CH 2) 2 -S-Si (Me) 2 -S- (CH 2) 2 -Si (OPr) 2 (Me),
_{(PrO) 2 (Me) Si-} (CH 2) 2 -S-Si (Et) 2 -S- (CH 2) 2 -Si (OPr) 2 (Me),
_{(PrO) 2 (Me) Si-} (CH 2) 2 -S-Si (Bu) 2 -S- (CH 2) 2 -Si (OPr) 2 (Me),
_{(MeO) 2 (Me) Si} -CH 2 -S-Si (Me) 2 -S-CH 2 -Si (OMe) 2 (Me),
_{(MeO) 2 (Me) Si} -CH 2 -S-Si (Et) 2 -S-CH 2 -Si (OMe) 2 (Me),
_{(MeO) 2 (Me) Si} -CH 2 -S-Si (Bu) 2 -S-CH 2 -Si (OMe) 2 (Me),
_{(EtO) 2 (Me) Si} -CH 2 -S-Si (Me) 2 -S-CH 2 -Si (OEt) 2 (Me),
_{(EtO) 2 (Me) Si} -CH 2 -S-Si (Et) 2 -S-CH 2 -Si (OEt) 2 (Me),
_{(EtO) 2 (Me) Si} -CH 2 -S-Si (Bu) 2 -S-CH 2 -Si (OEt) 2 (Me),
_{(PrO) 2 (Me) Si} -CH 2 -S-Si (Me) 2 -S-CH 2 -Si (OPr) 2 (Me),
_{(PrO) 2 (Me) Si} -CH 2 -S-Si (Et) 2 -S-CH 2 -Si (OPr) 2 (Me),
_{(PrO) 2 (Me) Si} -CH 2 -S-Si (Bu) 2 -S-CH 2 -Si (OPr) 2 (Me),
_{(MeO) 2 (Me) Si} -CH 2 -CMe 2 -CH 2 -S-Si (Me) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OMe) 2 (Me),
_{(MeO) 2 (Me) Si} -CH 2 -CMe 2 -CH 2 -S-Si (Et) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OMe) 2 (Me),
_{(MeO) 2 (Me) Si} -CH 2 -CMe 2 -CH 2 -S-Si (Bu) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OMe) 2 (Me),
_{(EtO) 2 (Me) Si} -CH 2 -CMe 2 -CH 2 -S-Si (Me) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OEt) 2 (Me),
_{(EtO) 2 (Me) Si} -CH 2 -CMe 2 -CH 2 -S-Si (Et) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OEt) 2 (Me),
_{(EtO) 2 (Me) Si} -CH 2 -CMe 2 -CH 2 -S-Si (Bu) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OEt) 2 (Me),
_{(PrO) 2 (Me) Si} -CH 2 -CMe 2 -CH 2 -S-Si (Me) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OPr) 2 (Me),
_{(PrO) 2 (Me) Si} -CH 2 -CMe 2 -CH 2 -S-Si (Et) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OPr) 2 (Me),
_{(PrO) 2 (Me) Si} -CH 2 -CMe 2 -CH 2 -S-Si (Bu) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OPr) 2 (Me),
_{(MeO) 2 (Me) Si} -CH 2 -C (H) Me-CH 2 -S-Si (Me) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OMe) 2 (Me ),
_{(MeO) 2 (Me) Si} -CH 2 -C (H) Me-CH 2 -S-Si (Et) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OMe) 2 (Me ),
_{(MeO) 2 (Me) Si} -CH 2 -C (H) Me-CH 2 -S-Si (Bu) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OMe) 2 (Me ),
_{(EtO) 2 (Me) Si} -CH 2 -C (H) Me-CH 2 -S-Si (Me) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OEt) 2 (Me ),
_{(EtO) 2 (Me) Si} -CH 2 -C (H) Me-CH 2 -S-Si (Et) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OEt) 2 (Me ),
_{(EtO) 2 (Me) Si} -CH 2 -C (H) Me-CH 2 -S-Si (Bu) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OEt) 2 (Me ),
_{(PrO) 2 (Me) Si} -CH 2 -C (H) Me-CH 2 -S-Si (Me) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OPr) 2 (Me ),
_{(PrO) 2 (Me) Si} -CH 2 -C (H) Me-CH 2 -S-Si (Et) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OPr) 2 (Me ),
_{(PrO) 2 (Me) Si} -CH 2 -C (H) Me-CH 2 -S-Si (Bu) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OPr) 2 (Me ),
_{(MeO) 3 Si- (CH 2} ) 3 -S-Sn (Me) 2 -S- (CH 2) 3 -Si (OMe) 3,
_{(MeO) 3 Si- (CH 2} ) 3 -S-Sn (Et) 2 -S- (CH 2) 3 -Si (OMe) 3,
_{(MeO) 3 Si- (CH 2} ) 3 -S-Sn (Bu) 2 -S- (CH 2) 3 -Si (OMe) 3,
_{(EtO) 3 Si- (CH 2} ) 3 -S-Sn (Me) 2 -S- (CH 2) 3 -Si (OEt) 3,
_{(EtO) 3 Si- (CH 2} ) 3 -S-Sn (Et) 2 -S- (CH 2) 3 -Si (OEt) 3,
_{(EtO) 3 Si- (CH 2} ) 3 -S-Sn (Bu) 2 -S- (CH 2) 3 -Si (OEt) 3,
_{(PrO) 3 Si- (CH 2} ) 3 -S-Sn (Me) 2 -S- (CH 2) 3 -Si (OPr),
_{(PrO) 3 Si- (CH 2} ) 3 -S-Sn (Et) 2 -S- (CH 2) 3 -Si (OPr) 3,
_{(PrO) 3 Si- (CH 2} ) 3 -S-Sn (Bu) 2 -S- (CH 2) 3 -Si (OPr) 3,
_{(MeO) 3 Si- (CH 2} ) 2 -S-Sn (Me) 2 -S- (CH 2) 2 -Si (OMe) 3,
_{(MeO) 3 Si- (CH 2} ) 2 -S-Sn (Et) 2 -S- (CH 2) 2 -Si (OMe) 3,
_{(MeO) 3 Si- (CH 2} ) 2 -S-Sn (Bu) 2 -S- (CH 2) 2 -Si (OMe) 3,
_{(EtO) 3 Si- (CH 2} ) 2 -S-Sn (Me) 2 -S- (CH 2) 2 -Si (OEt) 3,
_{(EtO) 3 Si- (CH 2} ) 2 -S-Sn (Et) 2 -S- (CH 2) 2 -Si (OEt) 3,
_{(EtO) 3 Si- (CH 2} ) 2 -S-Sn (Bu) 2 -S- (CH 2) 2 -Si (OEt) 3,
_{(PrO) 3 Si- (CH 2} ) 2 -S-Sn (Me) 2 -S- (CH 2) 2 -Si (OPr) 3,
_{(PrO) 3 Si- (CH 2} ) 2 -S-Sn (Et) 2 -S- (CH 2) 2 -Si (OPr) 3,
_{(PrO) 3 Si- (CH 2} ) 2 -S-Sn (Bu) 2 -S- (CH 2) 2 -Si (OPr) 3,
_{(MeO) 3 Si-CH 2} -S-Sn (Me) 2 -S-CH 2 -Si (OMe) 3,
_{(MeO) 3 Si-CH 2} -S-Sn (Et) 2 -S-CH 2 -Si (OMe) 3,
_{(MeO) 3 Si-CH 2} -S-Sn (Bu) 2 -S-CH 2 -Si (OMe) 3,
_{(EtO) 3 Si-CH 2} -S-Sn (Me) 2 -S-CH 2 -Si (OEt) 3,
_{(EtO) 3 Si-CH 2} -S-Sn (Et) 2 -S-CH 2 -Si (OEt) 3,
_{(EtO) 3 Si-CH 2} -S-Sn (Bu) 2 -S-CH 2 -Si (OEt) 3,
_{(PrO) 3 Si-CH 2} -S-Sn (Me) 2 -S-CH 2 -Si (OPr) 3,
_{(PrO) 3 Si-CH 2} -S-Sn (Et) 2 -S-CH 2 -Si (OPr) 3,
_{(PrO) 3 Si-CH 2} -S-Sn (Bu) 2 -S-CH 2 -Si (OPr) 3,
_{(MeO) 3 Si-CH 2} -CMe 2 -CH 2 -S-Sn (Me) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OMe) 3,
_{(MeO) 3 Si-CH 2} -CMe 2 -CH 2 -S-Sn (Et) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OMe) 3,
_{(MeO) 3 Si-CH 2} -CMe 2 -CH 2 -S-Sn (Bu) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OMe) 3,
_{(EtO) 3 Si-CH 2} -CMe 2 -CH 2 -S-Sn (Me) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OEt) 3,
_{(EtO) 3 Si-CH 2} -CMe 2 -CH 2 -S-Sn (Et) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OEt) 3,
_{(EtO) 3 Si-CH 2} -CMe 2 -CH 2 -S-Sn (Bu) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OEt) 3,
_{(PrO) 3 Si-CH 2} -CMe 2 -CH 2 -S-Sn (Me) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OPr) 3,
_{(PrO) 3 Si-CH 2} -CMe 2 -CH 2 -S-Sn (Et) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OPr) 3,
_{(PrO) 3 Si-CH 2} -CMe 2 -CH 2 -S-Sn (Bu) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OPr) 3,
_{(MeO) 3 Si-CH 2} -C (H) Me-CH 2 -S-Sn (Me) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OMe) 3,
_{(MeO) 3 Si-CH 2} -C (H) Me-CH 2 -S-Sn (Et) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OMe) 3,
_{(MeO) 3 Si-CH 2} -C (H) Me-CH 2 -S-Sn (Bu) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OMe) 3,
_{(EtO) 3 Si-CH 2} -C (H) Me-CH 2 -S-Sn (Me) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OEt) 3,
_{(EtO) 3 Si-CH 2} -C (H) Me-CH 2 -S-Sn (Et) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OEt) 3,
_{(EtO) 3 Si-CH 2} -C (H) Me-CH 2 -S-Sn (Bu) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OEt) 3,
_{(PrO) 3 Si-CH 2} -C (H) Me-CH 2 -S-Sn (Me) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OPr) 3,
_{(PrO) 3 Si-CH 2} -C (H) Me-CH 2 -S-Sn (Et) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OPr) 3,
_{(PrO) 3 Si-CH 2} -C (H) Me-CH 2 -S-Sn (Bu) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OPr) 3,
_{(MeO) 2 (Me) Si-} (CH 2) 3 -S-Sn (Me) 2 -S- (CH 2) 3 -Si (OMe) 2 (Me),
_{(MeO) 2 (Me) Si-} (CH 2) 3 -S-Sn (Et) 2 -S- (CH 2) 3 -Si (OMe) 2 (Me),
_{(MeO) 2 (Me) Si-} (CH 2) 3 -S-Sn (Bu) 2 -S- (CH 2) 3 -Si (OMe) 2 (Me),
_{(EtO) 2 (Me) Si-} (CH 2) 3 -S-Sn (Me) 2 -S- (CH 2) 3 -Si (OEt) 2 (Me),
_{(EtO) 2 (Me) Si-} (CH 2) 3 -S-Sn (Et) 2 -S- (CH 2) 3 -Si (OEt) 2 (Me),
_{(EtO) 2 (Me) Si-} (CH 2) 3 -S-Sn (Bu) 2 -S- (CH 2) 3 -Si (OEt) 2 (Me),
_{(PrO) 2 (Me) Si-} (CH 2) 3 -S-Sn (Me) 2 -S- (CH 2) 3 -Si (OPr) 2 (Me),
_{(PrO) 2 (Me) Si-} (CH 2) 3 -S-Sn (Et) 2 -S- (CH 2) 3 -Si (OPr) 2 (Me),
_{(PrO) 2 (Me) Si-} (CH 2) 3 -S-Sn (Bu) 2 -S- (CH 2) 3 -Si (OPr) 2 (Me),
_{(MeO) 2 (Me) Si-} (CH 2) 2 -S-Sn (Me) 2 -S- (CH 2) 2 -Si (OMe) 2 (Me),
_{(MeO) 2 (Me) Si-} (CH 2) 2 -S-Sn (Et) 2 -S- (CH 2) 2 -Si (OMe) 2 (Me),
_{(MeO) 2 (Me) Si-} (CH 2) 2 -S-Sn (Bu) 2 -S- (CH 2) 2 -Si (OMe) 2 (Me),
_{(EtO) 2 (Me) Si-} (CH 2) 2 -S-Sn (Me) 2 -S- (CH 2) 2 -Si (OEt) 2 (Me),
_{(EtO) 2 (Me) Si-} (CH 2) 2 -S-Sn (Et) 2 -S- (CH 2) 2 -Si (OEt) 2 (Me),
_{(EtO) 2 (Me) Si-} (CH 2) 2 -S-Sn (Bu) 2 -S- (CH 2) 2 -Si (OEt) 2 (Me),
_{(PrO) 2 (Me) Si-} (CH 2) 2 -S-Sn (Me) 2 -S- (CH 2) 2 -Si (OPr) 2 (Me),
_{(PrO) 2 (Me) Si-} (CH 2) 2 -S-Sn (Et) 2 -S- (CH 2) 2 -Si (OPr) 2 (Me),
_{(PrO) 2 (Me) Si-} (CH 2) 2 -S-Sn (Bu) 2 -S- (CH 2) 2 -Si (OPr) 2 (Me),
_{(MeO) 2 (Me) Si} -CH 2 -S-Sn (Me) 2 -S-CH 2 -Si (OMe) 2 (Me),
_{(MeO) 2 (Me) Si} -CH 2 -S-Sn (Et) 2 -S-CH 2 -Si (OMe) 2 (Me),
_{(MeO) 2 (Me) Si} -CH 2 -S-Sn (Bu) 2 -S-CH 2 -Si (OMe) 2 (Me),
_{(EtO) 2 (Me) Si} -CH 2 -S-Sn (Me) 2 -S-CH 2 -Si (OEt) 2 (Me),
_{(EtO) 2 (Me) Si} -CH 2 -S-Sn (Et) 2 -S-CH 2 -Si (OEt) 2 (Me),
_{(EtO) 2 (Me) Si} -CH 2 -S-Sn (Bu) 2 -S-CH 2 -Si (OEt) 2 (Me),
_{(PrO) 2 (Me) Si} -CH 2 -S-Sn (Me) 2 -S-CH 2 -Si (OPr) 2 (Me),
_{(PrO) 2 (Me) Si} -CH 2 -S-Sn (Et) 2 -S-CH 2 -Si (OPr) 2 (Me),
_{(PrO) 2 (Me) Si} -CH 2 -S-Sn (Bu) 2 -S-CH 2 -Si (OPr) 2 (Me),
_{(MeO) 2 (Me) Si} -CH 2 -CMe 2 -CH 2 -S-Sn (Me) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OMe) 2 (Me),
_{(MeO) 2 (Me) Si} -CH 2 -CMe 2 -CH 2 -S-Sn (Et) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OMe) 2 (Me),
_{(MeO) 2 (Me) Si} -CH 2 -CMe 2 -CH 2 -S-Sn (Bu) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OMe) 2 (Me),
_{(EtO) 2 (Me) Si} -CH 2 -CMe 2 -CH 2 -S-Sn (Me) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OEt) 2 (Me),
_{(EtO) 2 (Me) Si} -CH 2 -CMe 2 -CH 2 -S-Sn (Et) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OEt) 2 (Me),
_{(EtO) 2 (Me) Si} -CH 2 -CMe 2 -CH 2 -S-Sn (Bu) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OEt) 2 (Me),
_{(PrO) 2 (Me) Si} -CH 2 -CMe 2 -CH 2 -S-Sn (Me) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OPr) 2 (Me),
_{(PrO) 2 (Me) Si} -CH 2 -CMe 2 -CH 2 -S-Sn (Et) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OPr) 2 (Me),
_{(PrO) 2 (Me) Si} -CH 2 -CMe 2 -CH 2 -S-Sn (Bu) 2 -S-CH 2 -CMe 2 -CH 2 -Si (OPr) 2 (Me),
_{(MeO) 2 (Me) Si} -CH 2 -C (H) Me-CH 2 -S-Sn (Me) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OMe) 2 (Me ),
_{(MeO) 2 (Me) Si} -CH 2 -C (H) Me-CH 2 -S-Sn (Et) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OMe) 2 (Me ),
_{(MeO) 2 (Me) Si} -CH 2 -C (H) Me-CH 2 -S-Sn (Bu) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OMe) 2 (Me ),
_{(EtO) 2 (Me) Si} -CH 2 -C (H) Me-CH 2 -S-Sn (Me) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OEt) 2 (Me ),
_{(EtO) 2 (Me) Si} -CH 2 -C (H) Me-CH 2 -S-Sn (Et) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OEt) 2 (Me ),
_{(EtO) 2 (Me) Si} -CH 2 -C (H) Me-CH 2 -S-Sn (Bu) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OEt) 2 (Me ),
_{(PrO) 2 (Me) Si} -CH 2 -C (H) Me-CH 2 -S-Sn (Me) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OPr) 2 (Me ),
_{(PrO) 2 (Me) Si} -CH 2 -C (H) Me-CH 2 -S-Sn (Et) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OPr) 2 (Me ),
_{(PrO) 2 (Me) Si} -CH 2 -C (H) Me-CH 2 -S-Sn (Bu) 2 -S-CH 2 -C (H) Me-CH 2 -Si (OPr) 2 (Me ).

式６中、Ｍはケイ素原子またはスズ原子であり、
Ｒ³は少なくとも二価であり、（Ｃ₈−Ｃ₁₆）アルキルアリールアルキル、（Ｃ₇−Ｃ₁₆）アリールアルキル、（Ｃ₇−Ｃ₁₆）アルキルアリール、または（Ｃ₁−Ｃ₁₆）アルキルであり、各基は以下の基：第三級アミン基、シリル基、（Ｃ₇−Ｃ₁₈）アラルキル基および（Ｃ₆−Ｃ₁₈）アリール基のうちの１つ以上で置換されていてもよく、
Ｒ¹、Ｒ¹²およびＲ¹⁶はそれぞれ独立して、（Ｃ₁−Ｃ₄）アルキルから選択され、
Ｒ²、Ｒ¹³およびＲ¹⁵はそれぞれ独立して、（Ｃ₁−Ｃ₁₆）アルキル、（Ｃ₇−Ｃ₁₆）アルキルアリールおよび（Ｃ₇−Ｃ₁₆）アリールアルキルから選択され、
Ｒ⁴は（Ｃ₁−Ｃ₁₆）アルキルおよび（Ｃ₇−Ｃ₁₆）アルキルアリールから選択され、ｂ、ｄおよびｆはそれぞれ独立して、０、１、および２の整数から選択され、ａ、ｃおよびｅはそれぞれ独立して、１、２、および３の整数から選択され、ａ＋ｂ＝３であり、ｃ＋ｄ＝３であり、ｅ＋ｆ＝３である。 The silane sulfide modifiers of the present invention further comprise a compound of Formula 6 below.

In Formula 6, M is a silicon atom or a tin atom,
R ³ is at least bivalent and is (C ₈ -C ₁₆ ) alkylarylalkyl, (C ₇ -C ₁₆ ) arylalkyl, (C ₇ -C ₁₆ ) alkylaryl, or (C ₁ -C ₁₆ ) alkyl And each group may be substituted by one or more of the following groups: tertiary amine group, silyl group, (C ₇ -C ₁₈ ) aralkyl group and (C ₆ -C ₁₈ ) aryl group ,
R ¹ , R ¹² and R ¹⁶ are each independently selected from (C ₁ -C ₄ ) alkyl,
R ² , R ¹³ and R ¹⁵ are each independently selected from (C ₁ -C ₁₆ ) alkyl, (C ₇ -C ₁₆ ) alkylaryl and (C ₇ -C ₁₆ ) arylalkyl,
R ⁴ is selected from (C ₁ -C ₁₆ ) alkyl and (C ₇ -C ₁₆ ) alkylaryl; b, d and f are each independently selected from the integers of 0, 1 and 2 and a, c and e are each independently selected from the integers of 1, 2 and 3 and a + b = 3, c + d = 3 and e + f = 3.

In one embodiment, R ³ is a (C ₁ -C ₁₆ ) bivalent alkyl group or a (C ₈ -C ₁₆ ) bivalent allylalalalkyl group.

In one embodiment, R ³ is alkylene. In a further embodiment, the alkylene is -CH ₂ - (methylene), - (CH _{2) 2} - (ethylidene), - (CH _{2) 3} - (propylidene) and - is selected from (butylidene) - (CH _{2) 4} Ru.

In one embodiment, R ³ is a divalent aralkylene group. In a further embodiment, the aralkylene group is _{-CH 2 -C 6 H 4 -CH 2} - is selected from - (cyclohexylidene) and _{-C 6 H 4 -C (CH 3} ) 2 -C 6 H 4.

In one embodiment, R ² , R ⁴ , R ¹³ and R ¹⁵ are each independently (C ₁ -C ₁₆ ) alkyl. In a further embodiment, the alkyl is CH ₃ - (methyl), CH ₃ -CH ₂ - _{(ethyl), CH 3 - (CH 2} ) 2 - ( _{propyl), CH 3 - (CH 2} ) 3 (n- butyl) And CH ₃ -C (CH ₃ ) ₂ (tert-butyl).

In one embodiment of Formula 6, R ³ is linear C ₁ -C ₁₀ alkyl (divalent), cyclic C ₆ -C ₁₂ alkyl (divalent), C ₆ -C ₁₅ aryl (divalent) and C ₇ It is selected from the group consisting of -C ₁₂ alkylaryl (divalent).

  In one embodiment of Formula 6, b, d and f are each independently selected from the integers of 0 and 1, and a, c and e are each independently selected from the integers of 2 and 3.

  In one embodiment of the silane sulfide modifier of Formula 6, M is a silicon atom, a, c and e are integers selected from 2 and 3 respectively, b, d and f are selected from 0 and 1 respectively Is an integer.

  Although not explicitly illustrated in Formula 6, it is understood that the silane sulfide modifiers of the present invention also include their corresponding Lewis base adducts (eg, solvent molecules tetrahydrofuran, diethyl ether, dimethoxyethane that coordinate silicon atoms). Be done.

Specific preferred species of the silane sulfide modifiers of the present invention include the following compounds and their corresponding Lewis base adducts.
_{{(MeO) 3 Si- (CH} 2) 3 -S} 3 Si (Me), {(MeO) 3 Si- (CH 2) 3 -S} 3 Si (Et),
_{{(MeO) 3 Si- (CH} 2) 3 -S} 3 Si (Bu), {(EtO) 3 Si- (CH 2) 3 -S} 3 Si (Me),
_{{(EtO) 3 Si- (CH} 2) 3 -S} 3 Si (Et), {(EtO) 3 Si- (CH 2) 3 -S} 3 Si (Bu),
_{{(PrO) 3 Si- (CH} 2) 3 -S} 3 Si (Me), {(PrO) 3 Si- (CH 2) 3 -S} 3 Si (Et),
_{{(PrO) 3 Si- (CH} 2) 3 -S} 3 Si (Bu), {(MeO) 3 Si- (CH 2) 2 -S} 3 Si (Me),
_{{(MeO) 3 Si- (CH} 2) 2 -S} 3 Si (Et), {(MeO) 3 Si- (CH 2) 2 -S} 3 Si (Bu),
_{{(EtO) 3 Si- (CH} 2) 2 -S} 3 Si (Me), {(EtO) 3 Si- (CH 2) 2 -S} 3 Si (Et),
_{{(EtO) 3 Si- (CH} 2) 2 -S} 3 Si (Bu), {(PrO) 3 Si- (CH 2) 2 -S} 3 Si (Me),
_{{(PrO) 3 Si- (CH} 2) 2 -S} 3 Si (Et), {(PrO) 3 Si- (CH 2) 2 -S} 3 Si (Bu),
_{{(MeO) 3 Si-CH} 2 -S} 3 Si (Me), {(MeO) 3 Si-CH 2 -S} 3 Si (Et), {(MeO) 3 Si-CH 2 -S} 3 Si (Bu), {(EtO) 3 Si-CH 2 -S} 3 Si (Me), {(EtO) 3 Si-CH 2 -S} 3 Si (Et), {(EtO) 3 Si-CH 2 - _{S} 3 Si (Bu),} {(PrO) 3 Si-CH 2 -S} 3 Si (Me), {(PrO) 3 Si-CH 2 -S} 3 Si (Et), {(PrO) 3 Si -CH ₂ -S} ₃ Si (Bu),
_{(PrO) 3 Si-CH 2} -S} 3 Si (Bu), {(MeO) 3 Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Me),
_{{(MeO) 3 Si-CH} 2 -CMe 2 -CH 2 -S} 3 Si (Et), {(MeO) 3 Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Bu), {( _{EtO) 3 Si-CH 2 -CMe} 2 -CH 2 -S} 3 Si (Me), {(EtO) 3 Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Et), {(EtO) _{3 Si-CH 2 -CMe 2 -CH} 2 -S} 3 Si (Bu), {(PrO) 3 Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Me), {(PrO) 3 Si _{-CH 2 -CMe 2 -CH 2 -S}} 3 Si (Et), {(MeO) 3 Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Me),
_{{(MeO) 3 Si-CH} 2 -C (H) Me-CH 2 -S} 3 Si (Et), {(MeO) 3 Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Bu), {(EtO) 3 Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Me), {(EtO) 3 Si-CH 2 -C (H) Me-CH 2 - _{S} 3 Si (Et),} {(EtO) 3 Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Bu), {(PrO) 3 Si-CH 2 -C (H) Me -CH ₂ -S} ₃ Si (Me), {(PrO) ₃ Si-CH ₂ -C (H) Me-CH ₂ -S} ₃ Si (Et), {(MeO) ₂ (Me) Si- ( _{CH 2) 3 -S} 3 Si} (Me), {(MeO) 2 (Me) Si- (CH 2) 3 -S} 3 Si (Et), {(MeO) 2 (Me) Si- (CH 2 ) ₃ -S} ₃ Si _{Bu), {(EtO) 2} (Me) Si- (CH 2) 3 -S} 3 Si (Me), {(EtO) 2 (Me) Si- (CH 2) 3 -S} 3 Si (Et) ,
_{{(EtO) 2 (Me)} Si- (CH 2) 3 -S} 3 Si (Bu), {(PrO) 2 (Me) Si- (CH 2) 3 -S} 3 Si (Me), {( _{PrO) 2 (Me) Si- (} CH 2) 3 -S} 3 Si (Et), {(PrO) 2 (Me) Si- (CH 2) 3 -S} 3 Si (Bu), {(MeO) _{2 (Me) Si- (CH 2} ) 2 -S} 3 Si (Me), {(MeO) 2 (Me) Si- (CH 2) 2 -S} 3 Si (Et), {(MeO) 2 ( _{Me) Si- (CH 2) 2} -S} 3 Si (Bu), {(EtO) 2 (Me) Si- (CH 2) 2 -S} 3 Si (Me), {(EtO) 2 (Me) _{Si- (CH 2) 2 -S}} 3 Si (Et), {(EtO) 2 (Me) Si- (CH 2) 2 -S} 3 Si (Bu),
_{{(PrO) 2 (Me)} Si- (CH 2) 2 -S} 3 Si (Me), {(PrO) 2 (Me) Si- (CH 2) 2 -S} 3 Si (Et),
_{{(PrO) 2 (Me)} Si- (CH 2) 2 -S} 3 Si (Bu), {(MeO) 2 (Me) Si-CH 2 -S} 3 Si (Me),
_{{(MeO) 2 (Me)} Si-CH 2 -S} 3 Si (Et), {(MeO) 2 (Me) Si-CH 2 -S} 3 Si (Bu),
_{{(EtO) 2 (Me)} Si-CH 2 -S} 3 Si (Me), {(EtO) 2 (Me) Si-CH 2 -S} 3 Si (Et),
_{{(EtO) 2 (Me)} Si-CH 2 -S} 3 Si (Bu), {(PrO) 2 (Me) Si-CH 2 -S} 3 Si (Me),
_{{(PrO) 2 (Me)} Si-CH 2 -S} 3 Si (Et), {(PrO) 2 (Me) Si-CH 2 -S} 3 Si (Bu),
_{(PrO) 2 (Me) 3} Si-CH 2 -S} 3 Si (Bu), {(MeO) 2 (Me) Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Me),
_{{(MeO) 2 (Me)} Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Et),
_{{(MeO) 2 (Me)} Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Bu),
_{{(EtO) 2 (Me)} Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Me),
_{{(EtO) 2 (Me)} Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Et),
_{{(EtO) 2 (Me)} Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Bu),
_{{(PrO) 2 (Me)} Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Me),
_{{(PrO) 2 (Me)} Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Et),
_{{(MeO) 2 (Me)} Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Me),
_{{(MeO) 2 (Me)} Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Et),
_{{(MeO) 2 (Me)} Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Bu),
_{{(EtO) 2 (Me)} Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Me),
_{{(EtO) 2 (Me)} Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Et),
_{{(EtO) 2 (Me)} Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Bu),
_{{(PrO) 2 (Me)} Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Me),
_{{(PrO) 2 (Me)} Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Et),
_{{(MeO) 3 Si- (CH} 2) 3 -S} 3 Sn (Me), {(MeO) 3 Si- (CH 2) 3 -S} 3 Sn (Et),
_{{(MeO) 3 Si- (CH} 2) 3 -S} 3 Sn (Bu), {(EtO) 3 Si- (CH 2) 3 -S} 3 Sn (Me),
_{{(EtO) 3 Si- (CH} 2) 3 -S} 3 Sn (Et), {(EtO) 3 Si- (CH 2) 3 -S} 3 Sn (Bu),
_{{(PrO) 3 Si- (CH} 2) 3 -S} 3 Sn (Me), {(PrO) 3 Si- (CH 2) 3 -S} 3 Sn (Et),
_{{(PrO) 3 Si- (CH} 2) 3 -S} 3 Sn (Bu), {(MeO) 3 Si- (CH 2) 2 -S} 3 Sn (Me),
_{{(MeO) 3 Si- (CH} 2) 2 -S} 3 Sn (Et), {(MeO) 3 Si- (CH 2) 2 -S} 3 Sn (Bu),
_{{(EtO) 3 Si- (CH} 2) 2 -S} 3 Sn (Me), {(EtO) 3 Si- (CH 2) 2 -S} 3 Sn (Et),
_{{(EtO) 3 Si- (CH} 2) 2 -S} 3 Sn (Bu), {(PrO) 3 Si- (CH 2) 2 -S} 3 Sn (Me),
_{{(PrO) 3 Si- (CH} 2) 2 -S} 3 Sn (Et), {(PrO) 3 Si- (CH 2) 2 -S} 3 Sn (Bu),
_{{(MeO) 3 Si-CH} 2 -S} 3 Sn (Me), {(MeO) 3 Si-CH 2 -S} 3 Sn (Et),
_{{(MeO) 3 Si-CH} 2 -S} 3 Sn (Bu), {(EtO) 3 Si-CH 2 -S} 3 Sn (Me), {(EtO) 3 Si-CH 2 -S} 3 Sn (Et), {(EtO) 3 Si-CH 2 -S} 3 Sn (Bu), {(PrO) 3 Si-CH 2 -S} 3 Sn (Me), {(PrO) 3 Si-CH 2 - _{S} 3 Sn (Et),} {(PrO) 3 Si-CH 2 -S} 3 Sn (Bu), (PrO) 3 Si-CH 2 -S} 3 Sn (Bu),
_{{(MeO) 3 Si-CH} 2 -CMe 2 -CH 2 -S} 3 Sn (Me), {(MeO) 3 Si-CH 2 -CMe 2 -CH 2 -S} 3 Sn (Et), {( _{MeO) 3 Si-CH 2 -CMe} 2 -CH 2 -S} 3 Sn (Bu), {(EtO) 3 Si-CH 2 -CMe 2 -CH 2 -S} 3 Sn (Me), {(EtO) _{3 Si-CH 2 -CMe 2 -CH} 2 -S} 3 Sn (Et), {(EtO) 3 Si-CH 2 -CMe 2 -CH 2 -S} 3 Sn (Bu), {(PrO) 3 Si _{-CH 2 -CMe 2 -CH 2 -S}} 3 Sn (Me), {(PrO) 3 Si-CH 2 -CMe 2 -CH 2 -S} 3 Sn (Et), {(MeO) 3 Si-CH _{2 -C (H) Me-CH} 2 -S} 3 Sn (Me),
_{{(MeO) 3 Si-CH} 2 -C (H) Me-CH 2 -S} 3 Sn (Et),
_{{(MeO) 3 Si-CH} 2 -C (H) Me-CH 2 -S} 3 Sn (Bu),
_{{(EtO) 3 Si-CH} 2 -C (H) Me-CH 2 -S} 3 Sn (Me), {(EtO) 3 Si-CH 2 -C (H) Me-CH 2 -S} 3 Sn (Et), {(EtO) 3 Si-CH 2 -C (H) Me-CH 2 -S} 3 Sn (Bu), {(PrO) 3 Si-CH 2 -C (H) Me-CH 2 - _{S} 3 Sn (Me),} {(PrO) 3 Si-CH 2 -C (H) Me-CH 2 -S} 3 Sn (Et), {(MeO) 2 (Me) Si- (CH 2) 3 _{-S} 3 Sn (Me),} {(MeO) 2 (Me) Si- (CH 2) 3 -S} 3 Sn (Et), {(MeO) 2 (Me) Si- (CH 2) 3 -S _{} 3 Sn (Bu), {} (EtO) 2 (Me) Si- (CH 2) 3 -S} 3 Sn (Me), {(EtO) 2 (Me) Si- (CH 2) 3 -S} 3 Sn (Et),
_{{(EtO) 2 (Me)} Si- (CH 2) 3 -S} 3 Sn (Bu), {(PrO) 2 (Me) Si- (CH 2) 3 -S} 3 Sn (Me), {( _{PrO) 2 (Me) Si- (} CH 2) 3 -S} 3 Sn (Et), {(PrO) 2 (Me) Si- (CH 2) 3 -S} 3 Sn (Bu), {(MeO) _{2 (Me) Si- (CH 2} ) 2 -S} 3 Sn (Me), {(MeO) 2 (Me) Si- (CH 2) 2 -S} 3 Sn (Et), {(MeO) 2 ( _{Me) Si- (CH 2) 2} -S} 3 Sn (Bu), {(EtO) 2 (Me) Si- (CH 2) 2 -S} 3 Sn (Me), {(EtO) 2 (Me) _{Si- (CH 2) 2 -S}} 3 Sn (Et), {(EtO) 2 (Me) Si- (CH 2) 2 -S} 3 Sn (Bu),
_{{(PrO) 2 (Me)} Si- (CH 2) 2 -S} 3 Sn (Me), {(PrO) 2 (Me) Si- (CH 2) 2 -S} 3 Sn (Et),
_{{(PrO) 2 (Me)} Si- (CH 2) 2 -S} 3 Si (Bu), {(MeO) 2 (Me) Si-CH 2 -S} 3 Si (Me),
_{{(MeO) 2 (Me)} Si-CH 2 -S} 3 Si (Et), {(MeO) 2 (Me) Si-CH 2 -S} 3 Si (Bu),
_{{(EtO) 2 (Me)} Si-CH 2 -S} 3 Si (Me), {(EtO) 2 (Me) Si-CH 2 -S} 3 Si (Et),
_{{(EtO) 2 (Me)} Si-CH 2 -S} 3 Si (Bu), {(PrO) 2 (Me) Si-CH 2 -S} 3 Si (Me),
_{{(PrO) 2 (Me)} Si-CH 2 -S} 3 Si (Et), {(PrO) 2 (Me) Si-CH 2 -S} 3 Si (Bu),
_{(PrO) 2 (Me) 3} Si-CH 2 -S} 3 Si (Bu), {(MeO) 2 (Me) Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Me),
_{{(MeO) 2 (Me)} Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Et),
_{{(MeO) 2 (Me)} Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Bu),
_{{(EtO) 2 (Me)} Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Me),
_{{(EtO) 2 (Me)} Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Et),
_{{(EtO) 2 (Me)} Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Bu),
_{{(PrO) 2 (Me)} Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Me),
_{{(PrO) 2 (Me)} Si-CH 2 -CMe 2 -CH 2 -S} 3 Si (Et),
_{{(MeO) 2 (Me)} Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Me),
_{{(MeO) 2 (Me)} Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Et),
_{{(MeO) 2 (Me)} Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Bu),
_{{(EtO) 2 (Me)} Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Me),
_{{(EtO) 2 (Me)} Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Et),
_{{(EtO) 2 (Me)} Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Bu),
_{{(PrO) 2 (Me)} Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Me),
_{{(PrO) 2 (Me)} Si-CH 2 -C (H) Me-CH 2 -S} 3 Si (Et).

  The silane sulfide modifier may be added intermittently (or at regular or irregular intervals) or continuously during polymerization, but when the conversion of polymerization is preferably higher than 80 percent, more preferably the conversion is 90 It is added when it is higher than a percentage. Preferably, a substantial amount of polymer chain ends are not terminated prior to reaction with the silane sulfide modifier. That is, living polymer chain ends are present and can react with silane sulfide end modifiers. The silane sulfide modification reaction may occur before, after or during the addition of the coupling agent (if used) or any other modifier (if used). Preferably, if any coupling agent is employed, the silane sulfide modification reaction is completed after adding the coupling agent. See, for example, WO 2009/148932, which is incorporated herein by reference. Preferably, when an additional modifier that is not a silane sulfide modifier of Formula 1, including Formula 5 or Formula 6, is used in addition to the silane sulfide modifier of the present invention, reaction with the silane sulfide modifier of the present invention Is preferably completed prior to the addition of the further modifier. The preferred order of addition is to cause the silane sulfide modifier of the present invention to react with two or more living polymer chains forming a modified binding polymer compound (however, the ratio of the number of living polymer chains to the number of silane sulfide modifiers is remarkable) More than one, preferably more than two), while the further modifiers form an essentially linear modified macromolecular compound, provided that the reaction with the silane sulfide modifiers according to the invention with respect to the number of further modifiers When the ratio of the number of living polymer chains still remaining after completion is relatively close to 1, for example less than 1.4 or more preferably less than 1.0).

  In one embodiment, more than 20 percent, preferably more than 35 percent, even more preferably more than 50 percent of the living polymer chains, as determined by GPC, formed in the polymerization process are treated with polymeric silane sulfide modification It is linked with a silane sulfide modifier.

  In one embodiment, more than 20 percent of the living polymer chain ends determined by GPC react with the coupling agent (s) prior to the addition of the silane sulfide modifying agent (s). In still other embodiments, more than 35 percent of the living polymer chain ends react with the coupling agent (s) prior to the addition of the silane sulfide modifying agent (s).

  In one embodiment, 20 to 35 percent of the living polymer chain ends, as determined by GPC, are reacted with the coupling agent (s) prior to the addition of the silane sulfide modifying agent (s). In another embodiment, 35 to 50 percent of the living polymer chain ends, as determined by GPC, are reacted with the coupling agent (s) prior to the addition of the silane sulfide modifying agent (s). In still other embodiments, 50 to 80 percent of the living polymer chain ends react with the coupling agent (s) prior to the addition of the silane sulfide modifying agent (s).

  In one embodiment, more than 20 percent, preferably 20 to 35 percent, of the living polymer chain ends determined by GPC are silane sulfide modifying agent (s) of the invention prior to the addition of further modifying agent (s) React with. In yet another embodiment, more than 35 percent, preferably 50 to 80 percent, of the living polymer chain ends are reacted with the silane sulfide modifying agent (s) of the invention prior to the addition of the additional modifying agent (s). Do.

  In one embodiment, more than 50 percent, preferably more than 60 percent, and more preferably more than 75 percent of the living polymer polymers (still remaining after the coupling reaction) as determined by GPC are silane sulfide modifiers React with. The silane sulfide modified polymer polymer according to the present invention comprises functionality derived from a silane sulfide modifier.

式中、
Ｍ¹はケイ素またはスズであり、ｘは１、２、および３から選択される整数であり、ｙは０、１、および２から選択される整数であり、ｘ＋ｙ＝３であり、Ｒは独立して、（Ｃ₁−Ｃ₁₆）アルキルから選択され、Ｒ’は（Ｃ₁−Ｃ₁₆）アルキル、（Ｃ₈−Ｃ₁₆）アルキルアリールアルキル、（Ｃ₇−Ｃ₁₆）アリールアルキルまたは（Ｃ₇−Ｃ₁₆）アルキルアリールである。
さらなる変性剤(複数可)の具体的な例は、参照によって本明細書に引用される、国際公開第２００７／０４７９４３号に記載される。 The nature of the optional further modifier (s) preferably corresponds to the formula 7 below:

During the ceremony
M ¹ is silicon or tin, x is an integer selected from 1, 2 and 3, y is an integer selected from 0, 1 and 2 and x + y = 3, R is independent Are selected from (C ₁ -C ₁₆ ) alkyl, and R ′ is (C ₁ -C ₁₆ ) alkyl, (C ₈ -C ₁₆ ) alkylarylalkyl, (C ₇ -C ₁₆ ) arylalkyl or (C ₇ -C ₁₆₎ alkylaryl.
Specific examples of further modifier (s) are described in WO 2007/047943, which is incorporated herein by reference.

（式中、Ｈは水素であり、他の記号は式１にて規定されるものと同じ意味を有する）を式４の化合物：

（式中、Ｍはケイ素またはスズであり、ｕは２、３、および４から選択される整数であり、Ｒ⁴、Ｘおよびｔは上に規定されるとおりであり、ｔ＋ｕ＝４である）と、任意に、例えば式３ａおよび式３ｂの化合物が挙げられるがこれに限られない強力なルイス塩基の存在下にて、

（式中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰およびＲ¹¹はそれぞれ独立して、水素、（Ｃ₁−Ｃ₁₆）アルキル、（Ｃ₇−Ｃ₁₆）アルキルアリール、（Ｃ₇−Ｃ₁₆）アリールアルキルおよび（Ｃ₆−Ｃ₁₆）アリールから選択され、ｖは１〜１０から選択される整数である）反応させることで調製されてもよい。 Preparation of Silane Sulfide Modifier The silane sulfide modifier of formula 1 of the present invention is a sulfur containing compound of formula 2

Wherein H is hydrogen and the other symbols have the same meaning as defined in formula 1 to a compound of formula 4:

(Wherein, M is silicon or tin, u is an integer selected from 2, 3 and 4; R ⁴ , X and t are as defined above, and t + u = 4) And optionally, in the presence of a strong Lewis base including, but not limited to, compounds of Formula 3a and Formula 3b,

(Wherein, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently hydrogen, (C ₁ -C ₁₆ ) alkyl, (C ₇ -C ₁₆ ) alkyl aryl , (C ₇ -C ₁₆ ) arylalkyl and (C ₆ -C ₁₆ ) aryl, wherein v is an integer selected from 1 to 10).

  In a preferred embodiment, the Lewis base is selected from compounds of Formula 3a.

In a preferred embodiment, the Lewis base is selected from compounds of Formula 3a, and R ⁵ , R ⁶ and R ⁷ are each independently methyl (Me), ethyl (Et), propyl (Pr) and butyl (Bu) It is selected from

  In a preferred embodiment, u in formula 4 is 2.

（式中、Ｍ²はリチウム、ナトリウムまたはカリウムであり、他の記号は式１にて規定されたものと同じ意味を有する）を、式４の化合物、

（式中、Ｍはケイ素またはスズであり、ｕは２、３、および４から選択される整数であり、Ｒ⁴、Ｘおよびｔは上に規定されるとおりであり、ｔ＋ｕ＝４である）と反応させることで調製されてもよい。 The silane sulfide modifiers of formula 1 of the present invention are also sulfur containing compounds of formula 11

Wherein M ² is lithium, sodium or potassium, and the other symbols have the same meaning as defined in formula 1), a compound of formula 4

(Wherein, M is silicon or tin, u is an integer selected from 2, 3 and 4; R ⁴ , X and t are as defined above, and t + u = 4) It may be prepared by reacting with

  In a preferred embodiment, u in formula 4 is 2.

Silane Sulfide Modification Treatment Silane sulfide end modifiers may be added directly to the solution of the living anionic elastomeric polymer, but may be advantageously added to the drug, for example in solution in an inert solvent (eg cyclohexane) . The amount of silane sulfide modifying agent added to the living anionic elastomeric polymer can vary depending on the type of monomeric species, the type and amount of any coupling agent, the type and amount of additional modifying agent, the reaction conditions, and the desired end properties Generally, however, 0.05 to 5 molar equivalents, preferably 0.1 to 2.0 molar equivalents, and most preferably 0.2 to 1.5 molar equivalents per molar equivalent of alkali metal in the initiator compound. It is a molar equivalent. In one embodiment, the silane sulfide modifier is used to form the branched modified polymer compound and is used in an amount of 0.1 to 0.5 molar equivalents per molar equivalent of alkali metal in the initiator compound . In another embodiment, the silane sulfide modifier is used to form a linear modified polymeric compound, in an amount of 0.6 to 1.5 molar equivalents per molar equivalent of alkali metal in the initiator compound Used in The polymeric silane sulfide modification reaction may be carried out within a temperature range of 0 ° C to 150 ° C, preferably 15 ° C to 120 ° C, even more preferably 40 ° C to 100 ° C. There is no limitation on the duration of the silane sulfide modification reaction. However, in view of an economical polymerization process, for example in the case of batch polymerization processes, the silane sulfide modification reaction is usually stopped about 5 to 60 minutes after the addition of the modifier.

The present invention also provides a method of producing a silane sulfide modified elastomeric polymer compound comprising the following steps A to D: Step A, as described herein, polymerizes the polymerization initiator with one or more monomer types and preferably a monomer selected from butadiene, styrene, isoprene, alpha methyl-styrene and combinations thereof. The reaction is carried out in a solvent to form a reaction mixture A. Suitable polymerization solvents include nonpolar aliphatic and nonpolar aromatic solvents, preferably hexane, heptane, butane, pentane, isoper, cyclohexane, toluene and benzene. Step B optionally includes at least one reaction mixture A, preferably SnCl ₄ , (R ¹ ) ₃ SnCl, (R ¹ ) ₂ SnCl ₂ , R ¹ SnCl ₃ , SiCl ₄ , (R ¹ ) ₃ SiCl, (R ¹ ) ₂ SiCl ₂ , R ¹ SiCl ₃ , Cl ₃ Si-SiCl ₃ , Cl ₃ Si-O-SiCl ₃ , Cl ₃ Sn-SnCl ₃ , Cl ₃ Sn-O-SnCl ₃ (wherein, R ¹ Is as defined above), Sn (OMe) ₄ , Si (OMe) ₄ , Sn (OEt) ₄ and Si (OEt) ₄ for reaction with a coupling agent selected from the group consisting of Form B Step C reacts the reaction mixture A or B with at least one silane sulfide modifier of Formula 1 defined above including Formula 5 and Formula 6 to form a silane sulfide modified polymeric compound of the invention It is usually produced in the form of polymer composition C. Step D optionally reacts the silane sulfide modified polymeric compound or polymer composition C obtained in step C with a further modifier, preferably having a compound of Formula 7.

  In a preferred embodiment, the initiator compound is first reacted with the monomer to form a living polymer (Step A). Some of these polymer molecules are optionally reacted with a coupling agent to form branched polymer molecules (optional step B). In step C, some living polymer molecules are reacted with a silane sulfide chain end modifier to form linear silane sulfide modified polymeric compound (s). A linear silane sulfide modified polymeric compound is formed when one equivalent of living polymer chain is modified (or reacted) to one equivalent of silane sulfide modifier.

  In another preferred embodiment, the initiator compound is first reacted with the monomer to form a living polymer (Step A). Some polymer molecules are reacted with a silane sulfide modifier to form branched modified polymer molecules (Step C). Branched silane sulfide modified polymeric compounds are formed when two or more equivalents of living polymer chains are modified (or reacted) with one equivalent of silane sulfide modifier. For example, when 3 (equivalents) of living polymer chains are modified with 1 (equivalents) silane sulfide modifier, a silane sulfide modified polymeric compound is formed comprising 3 polymer chain arms. In optional step D, some living polymer molecules are reacted with additional modifiers to form linear modified polymeric compound (s).

In another embodiment, optional coupling agents are selected from: SnCl ₄ , Bu ₃ SnCl, Bu ₂ SnCl ₂ , BuSnCl ₃ , Me ₃ SiCl, Me ₂ SiCl ₂ , Cl ₃ Si—SiCl ₃ , Cl _{3 Si-O-SiCl 3,} Sn (OMe) 4, Si (OMe) 4, Sn (OEt) 4, Si (OEt) 4 , and combinations thereof.

  In a preferred embodiment, the silane sulfide modifier is a compound of Formula 5. In another preferred embodiment, the silane sulfide modifier is a compound of Formula 6.

Monomers Useful monomers for preparing the living anionic elastomeric polymer, and thus the polymer composition comprising the silane sulfide-modified polymer compound of the invention and the polymer compound (s), include conjugated olefins and α-olefins, internals Included are olefins selected from olefins, cyclic olefins, polar olefins and non-conjugated diolefins. Suitable conjugated unsaturated monomers are preferably conjugated dienes such as 1,3-butadiene, 2-alkyl-1,3-butadiene and the like, preferably 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, cyclo Pentadiene, 2,4-hexadiene, and 1,3-cyclooctadiene. Preferred olefins are _C2-20 alpha-olefins, including but not limited to long chain polymeric alpha-olefins, especially aromatic vinyl compounds. The preferred aromatic vinyl compound is styrene, including C _1-4 alkyl substituted styrene, such as 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethyl Styrene, α-methylstyrene and stilbene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, vinylbenzyldimethylamine, (4-vinylbenzyl) dimethylaminoethyl ether, N, N-dimethylaminoethylstyrene, tert- Butoxystyrene, vinylpyridine, and mixtures thereof. Suitable polar olefins include acrylonitrile, methacrylate, methyl methacrylate. Suitable non-conjugated olefins are C _4-20 diolefins, in particular norbornadiene, ethylidene norbornene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 4-vinylcyclohexene, 1,2-divinylbenzene, 1 And divinylbenzene, including 3-divinylbenzene and 1,4-divinylbenzene, and mixtures thereof. Preferred conjugated dienes include butadiene, isoprene and cyclopentadiene, and preferred aromatic alpha-olefins include styrene and 4-methylstyrene.

式中、
Ｐは以下のモノマー基：ブタジエン、イソプレン、スチレンおよびアルファ−メチルスチレン、の少なくとも１つに由来するモノマー単位を含むポリマー鎖であり、１高分子あたりのモノマー単位数が１０〜５０．０００、好ましくは２０〜４０．０００の範囲内であり、Ｍはケイ素原子またはスズ原子であり、
ｘは１、２、および３から選択される整数であり、ｙは０、１、および２から選択される整数であり、ｒは１、２、および３から選択される整数であり、ｘ＋ｙ＋ｒ＝３であり、
ｓは２、３、および４から選択される整数であり、ｔは０、１、および２から選択される整数であり、ｕは０、１、および２から選択される整数であり、ｓ＋ｔ＋ｕ＝４であり、
Ｒ¹は独立して、水素原子および（Ｃ₁−Ｃ₆）アルキルから選択され、
Ｒ²は独立して、（Ｃ₁−Ｃ₁₆）アルキル、（Ｃ₇−Ｃ₁₆）アルキルアリールおよび（Ｃ₇−Ｃ₁₆）アリールアルキルから選択され、
Ｒ³は少なくとも二価であり、独立して、（Ｃ₁−Ｃ₁₆）アルキル、（Ｃ₈−Ｃ₁₆）アルキルアリールアルキル、（Ｃ₇−Ｃ₁₆）アリールアルキルおよび（Ｃ₇−Ｃ₁₆）アルキルアリールから選択され、各基は以下の基：第三級アミン基、シリル基、（Ｃ₇−Ｃ₁₈）アラルキル基および（Ｃ₆−Ｃ₁₈）アリール基のうちの１つ以上で置換されてもよく、
Ｒ⁴は独立して、（Ｃ₁−Ｃ₁₆）アルキルおよび（Ｃ₇−Ｃ₁₆）アルキルアリールから選択され、
Ｘは独立して、塩化物、臭化物および−ＯＲ⁵から選択され、式中、Ｒ⁵は（Ｃ₁−Ｃ₁₆）アルキルおよび（Ｃ₇−Ｃ₁₆）アリールアルキルから選択される。
好ましい実施形態では、Ｒ³は二価であり、（Ｃ₁−Ｃ₁₆）アルキルである。
一実施形態では、Ｘは−ＯＲ⁵であり、式中、Ｒ⁵は（Ｃ₁−Ｃ₁₆）アルキルから選択される。
別の実施形態では、Ｘは塩化物または臭化物である。
好ましい一実施形態では、Ｒ²およびＲ⁴は独立して、（Ｃ₁−Ｃ₁₆）アルキルから選択される。
好ましい一実施形態では、Ｒ¹、Ｒ²、Ｒ⁴およびＲ⁵は独立して、（Ｃ₁−Ｃ₄）アルキルから選択される。
一実施形態では、ｓおよびｔはそれぞれ２であり、ｕは０である。
別の実施形態では、ｓは３であり、ｔは１であり、ｕは０である。
一実施形態では、ｒは１であり、ｘは１であり、ｙは１である。
一実施形態では、ｒは１であり、ｘは０であり、ｙは２である。 Silane Sulfide Modified Polymeric Polymer The term "silane sulfide modified polymeric compound" is intended to mean the reaction product of one or more living polymer chains with the silane sulfide modifier of the present invention. The silane sulfide modified polymer compound may be represented by the following formula P1,

During the ceremony
P is a polymer chain containing a monomer unit derived from at least one of the following monomer groups: butadiene, isoprene, styrene and alpha-methylstyrene, and the number of monomer units per one polymer is preferably 10 to 50.000, Is in the range of 20 to 40.000, and M is a silicon atom or a tin atom,
x is an integer selected from 1, 2 and 3; y is an integer selected from 0, 1 and 2; r is an integer selected from 1, 2 and 3; x + y + r = 3 and
s is an integer selected from 2, 3 and 4; t is an integer selected from 0, 1 and 2; u is an integer selected from 0, 1 and 2; s + t + u = 4 and
R ¹ is independently selected from hydrogen atom and (C ₁ -C ₆ ) alkyl,
R ² is independently selected from (C ₁ -C ₁₆ ) alkyl, (C ₇ -C ₁₆ ) alkylaryl and (C ₇ -C ₁₆ ) arylalkyl;
R ³ is at least bivalent and is independently (C ₁ -C ₁₆ ) alkyl, (C ₈ -C ₁₆ ) alkylarylalkyl, (C ₇ -C ₁₆ ) arylalkyl and (C ₇ -C ₁₆ ) Selected from alkylaryl, each group being substituted with one or more of the following groups: tertiary amine group, silyl group, (C ₇ -C ₁₈ ) aralkyl group and (C ₆ -C ₁₈ ) aryl group May be
R ⁴ is independently selected from (C ₁ -C ₁₆ ) alkyl and (C ₇ -C ₁₆ ) alkylaryl;
X is independently chloride, is selected from bromide and -OR ^5, wherein, R ⁵ is selected from (C ₁ -C ₁₆₎ alkyl and (C ₇ -C ₁₆₎ arylalkyl.
In a preferred embodiment, R ³ is divalent and (C ₁ -C ₁₆ ) alkyl.
In one embodiment, X is -OR ⁵ where R ⁵ is selected from (C ₁ -C ₁₆ ) alkyl.
In another embodiment, X is chloride or bromide.
In a preferred embodiment, R ² and R ⁴ are independently selected from (C ₁ -C ₁₆ ) alkyl.
In a preferred embodiment, R ¹ , R ² , R ⁴ and R ⁵ are independently selected from (C ₁ -C ₄ ) alkyl.
In one embodiment, s and t are each 2 and u is 0.
In another embodiment, s is 3, t is 1 and u is 0.
In one embodiment, r is one, x is one and y is one.
In one embodiment, r is one, x is zero and y is two.

上記式では、Ｐは以下のモノマー基、ブタジエン、イソプレン、スチレンおよびアルファ−メチルスチレン、の少なくとも１つに由来するモノマー単位を含むポリマー鎖であり、１高分子あたりのモノマー単位数が１０〜５０．０００、好ましくは２０〜４０．０００の範囲内であり、Ｒ³は少なくとも二価であり、（Ｃ₈−Ｃ₁₆）アルキルアリールアルキル、（Ｃ₇−Ｃ₁₆）アリールアルキル、（Ｃ₇−Ｃ₁₆）アルキルアリール、または（Ｃ₁−Ｃ₁₆）アルキルであり、各基は以下の基：第三級アミン基、シリル基、（Ｃ₇−Ｃ₁₈）アラルキル基および（Ｃ₆−Ｃ₁₈）アリール基のうちの１つ以上で置換されていてもよく、
Ｍはケイ素原子またはスズ原子であり、
Ｒ¹、Ｒ¹²およびＲ¹⁶はそれぞれ独立して、水素原子および（Ｃ₁−Ｃ₄）アルキルから選択され、
Ｒ⁴は（Ｃ₁−Ｃ₁₆）アルキルおよび（Ｃ₇−Ｃ₁₆）アルキルアリールから選択され、
Ｒ²、Ｒ¹³およびＲ¹⁵はそれぞれ独立して、（Ｃ₁−Ｃ₁₆）アルキル、（Ｃ₇−Ｃ₁₆）アルキルアリールおよび（Ｃ₇−Ｃ₁₆）アリールアルキルから選択され、
ｐ、ｏおよびｉはそれぞれ独立して、１、２、および３の整数から選択され、ｇ、ｈおよびｊはそれぞれ独立して、０、１、および２の整数から選択され、ｂ、ｄおよびｆはそれぞれ独立して、０、１、および２の整数から選択され、
ｐ＋ｂ＋ｇ＝３であり、ｏ＋ｄ＋ｈ＝３であり、ｉ＋ｆ＋ｊ＝３である。 The silane sulfide modified polymer compound can be exemplified by the following formulas P2 to P6.

In the above formulae, P is a polymer chain containing monomer units derived from at least one of the following monomer groups, butadiene, isoprene, styrene and alpha-methylstyrene, and the number of monomer units per one polymer is 10 to 50. .000, preferably in the range of 20 to 40.000, R ³ is at least divalent, (C ₈ -C ₁₆₎ alkylaryl alkyl, (C ₇ -C ₁₆₎ arylalkyl, (C ₇ - C ₁₆ ) alkyl aryl or (C ₁ -C ₁₆ ) alkyl, each group comprising the following groups: tertiary amine group, silyl group, (C ₇ -C ₁₈ ) aralkyl group and (C ₆ -C ₁₈₎ ) May be substituted by one or more of aryl groups,
M is a silicon atom or a tin atom,
R ¹ , R ¹² and R ¹⁶ are each independently selected from hydrogen atom and (C ₁ -C ₄ ) alkyl;
R ⁴ is selected from (C ₁ -C ₁₆ ) alkyl and (C ₇ -C ₁₆ ) alkylaryl,
R ² , R ¹³ and R ¹⁵ are each independently selected from (C ₁ -C ₁₆ ) alkyl, (C ₇ -C ₁₆ ) alkylaryl and (C ₇ -C ₁₆ ) arylalkyl,
p, o and i are each independently selected from the integers of 1, 2 and 3; g, h and j are each independently selected from the integers of 0, 1 and 2; b, d and f is independently selected from integers of 0, 1 and 2;
p + b + g = 3, o + d + h = 3, and i + f + j = 3.

In one embodiment in Formulas P2 and P3, R ³ is divalent and (C ₁ -C ₁₆ ) alkyl, and R ² , R ⁴ , R ¹³ , R ¹⁴ are each independently (C _1-). C ₁₆ ) alkyl selected, R ¹ and R ¹² are each independently selected from (C ₁ -C ₄ ) alkyl, p and o are each independently selected from the integers of 1 and 2, g And h are each independently selected from the integers of 1 and 2; b and d are each independently selected from the integers of 0 and 1;

In one embodiment of Formulas P4, P5 and P6, R ³ is divalent and (C ₁ -C ₁₆ ) alkyl, and R ² , R ⁴ , R ¹³ and R ¹⁵ are each independently is selected from ₁ -C ₁₆₎ alkyl, R ^1, R ¹² and R ¹⁶ are each independently, (C ₁ -C ₄₎ is selected from alkyl, p, o and i are each, independently, 1 and 2 G, h and j are each independently selected from integers of 1 and 2; b, d and f are each independently selected from integers of 0 and 1;

  Although not specified in Formula P1 to Formula P6, compounds are understood to include their corresponding Lewis base adducts.

  Of the formulas P1 to P6 mentioned above, the formulas P1 and P2 are preferred.

理論で縛られたくはないが、式Ｐ１、Ｐ２、Ｐ３、Ｐ４、Ｐ５およびＰ６の、ジアルキルシレンジイル、ジアラルキルシレンジイルおよびジアリールシレンジイルを含むジヒドロカルビルシレンジイル、ジアルキルスタンネンジイル、ジアラルキルスタンネンジイルおよびジアリールスタンネンジイル基を含むジヒドロカルビルスタンネンジイル、ならびにアルキルシレントリイル、アラルキルシレントリイルおよびアリールシレントリイルを含むヒドロカルビルシレントリイル、アルキルスタンネントリイル、アラルキルスタンネントリイルおよびアリールスタンネントリイル基を含むヒドロカルビルスタンネントリイルは、それぞれ保護基として機能し、意図しない後続反応を防ぐと信じられている。これらの「保護」基、（−ＳｉＲ⁴Ｒ⁸−）、（−ＳｎＲ⁴Ｒ⁸−）、（−ＳｉＲ⁴＝）および（−ＳｎＲ⁴＝）は、水などの−ＯＨ基、アルコール、アニオン酸または有機酸（たとえば、塩酸、硫酸またはカルボン酸）を含有する化合物に暴露されることで除去され得て、「無保護」チオール（−ＳＨ）基を形成してもよい。このような条件は加硫中に典型的に存在する。ポリマーの「ワークアップ（ｗｏｒｋ ｕｐ）」条件によって、無保護および保護変性高分子化合物の片方または両方が得られてもよい。例えば、式Ｐ１、Ｐ２、Ｐ３、Ｐ４、Ｐ５およびＰ６の変性高分子化合物を含有するポリマー溶液の水蒸気蒸留は、トリアルキル、トリアラルキル、またはトリアリールシリル基を含む保護トリヒドロカルビル基を一定のパーセンテージで除去し、無保護チオール（−ＳＨ）基を結果として得て、式Ｐ７（式Ｐ１に対応する）、式Ｐ８、式Ｐ９または式Ｐ１０の化合物を一定のパーセンテージで形成する。

式Ｐ７中、
Ｐ、ｘ、ｙ、ｒ、Ｒ¹；Ｒ²およびＲ³は式Ｐ１に規定されるとおりであり、
ｘ＋ｙ＋ｒ＝３であり、
式Ｐ８、式Ｐ９および式Ｐ１０中、
Ｐは、以下のモノマー基、ブタジエン、イソプレン、スチレンおよびアルファ−メチルスチレン、の少なくとも１つに由来するモノマー単位を含むポリマー鎖であり、１高分子あたりのモノマー単位数が１０〜５０，０００ｇ／ｍｏｌ、好ましくは２０〜４０，０００ｇ／ｍｏｌの範囲内であり、Ｏは酸素原子であり、Ｓｉはケイ素原子であり、Ｓは硫黄原子であり、Ｈは水素原子であり、Ｒ³は少なくとも二価であり、（Ｃ₁−Ｃ₁₈）アルキルであり、以下の基：第三級アミン基、シリル基、（Ｃ₇−Ｃ₁₈）アラルキル基および（Ｃ₆−Ｃ₁₈）アリール基のうちの１つ以上で置換されていてもよく、
Ｒ¹、Ｒ¹²およびＲ¹⁶は独立して、水素原子および（Ｃ₁−Ｃ₄）アルキルから選択され、
Ｒ²、Ｒ¹³およびＲ¹⁵はそれぞれ独立して、（Ｃ₁−Ｃ₁₈）アルキルから選択され、
ｇ、ｈおよびｊはそれぞれ独立して、０、１、および２の整数から選択され、ｂ、ｄおよびｆはそれぞれ独立して、０、１、および２の整数から選択され、
文字ｐ、ｂおよびｇの合計が３（ｐ＋ｂ＋ｇ＝３）であり、文字ｏ、ｄおよびｈの合計は３（ｏ＋ｄ＋ｈ＝３）であり、文字ｉ、ｆおよびｊの合計が３（ｉ＋ｆ＋ｊ＝３）である。 Specific preferred modified polymeric compounds include the following polymers (and their corresponding Lewis base adducts):

Although not wishing to be bound by theory, dihydrocarbyl silendiyl, dialkyl stannene diyl, diaralkyl stannins, including dialkyl silendiyl, diaralkyl silendiyl and diaryl silendiyl, of formulas P1, P2, P3, P4, P5 and P6 Dihydrocarbylstannene diyl containing nendiyl and diarylstannenediyl groups, and hydrocarbyl cylentriyl, alkylstannentriyl, aralkylstannentriyl and arylstannes containing alkylcylentriyl, aralkylcylentriyl and arylcylentriyl It is believed that each hydrocarbylstannenetriyl containing a nentriyl group functions as a protecting group to prevent unintended subsequent reactions. These "protecting" ^{groups, (- SiR 4 R 8 -} ), (- SnR 4 R 8 -), (- SiR 4 =) and (-SnR ⁴ =) is, -OH groups such as water, alcohols, anionic It may be removed by exposure to a compound containing an acid or an organic acid (e.g. hydrochloric acid, sulfuric acid or carboxylic acid) to form a "unprotected" thiol (-SH) group. Such conditions are typically present during vulcanization. Depending on the “work up” conditions of the polymer, one or both of the unprotected and protected modified polymeric compounds may be obtained. For example, steam distillation of a polymer solution containing modified polymeric compounds of the formulas P1, P2, P3, P4, P5 and P6 may contain a certain percentage of protected trihydrocarbyl groups containing trialkyl, triaralkyl or triarylsilyl groups To obtain an unprotected thiol (-SH) group, which forms a compound of formula P7 (corresponding to formula P1), formula P8, formula P9 or formula P10 at a certain percentage.

In formula P7,
P, x, y, r, R ¹ ; R ² and R ³ are as defined in formula P 1,
x + y + r = 3,
In the formula P8, the formula P9 and the formula P10,
P is a polymer chain containing monomer units derived from at least one of the following monomer groups, butadiene, isoprene, styrene and alpha-methylstyrene, and the number of monomer units per one polymer is 10 to 50,000 g / mol, preferably in the range of 20 to 40,000 g / mol, O is an oxygen atom, Si is a silicon atom, S is a sulfur atom, H is a hydrogen atom, R ³ is at least two Of (C ₁ -C ₁₈ ) alkyl, among the following groups: tertiary amine group, silyl group, (C ₇ -C ₁₈ ) aralkyl group and (C ₆ -C ₁₈ ) aryl group It may be substituted by one or more,
R ¹ , R ¹² and R ¹⁶ are independently selected from hydrogen atom and (C ₁ -C ₄ ) alkyl,
R ² , R ¹³ and R ¹⁵ are each independently selected from (C ₁ -C ₁₈ ) alkyl;
g, h and j are each independently selected from the integers of 0, 1 and 2; b, d and f are each independently selected from the integers of 0, 1 and 2;
The sum of letters p, b and g is 3 (p + b + g = 3), the sum of letters o, d and h is 3 (o + d + h = 3), and the sum of letters i, f and j is 3 (i + f + j = 3) ).

In a preferred embodiment, R ³ is divalent and (C ₁ -C ₁₈ ) alkyl, and R ¹ , R ⁶ or R ¹⁰ is independently selected from hydrogen and (C ₁ -C ₁₈ ) alkyl And p, o or i is selected from the integers of 1 and 2, g, h or j is selected from the integers of 1 and 2, b, d or f is selected from the integers of 0 and 1.

  Although not explicitly shown in the formulas P1 to P6, the silane sulfide modified polymer compounds of the present invention are understood to include their corresponding Lewis base adducts.

The ratio of the thiol group-containing polymer compound of Formula P7, Formula P8, Formula P9, and Formula P10 obtained by the treatment is the same as that of the polymer compound of Formula P1, Formula P2, Formula P3, Formula P4, Formula P5, and Formula P6. _{^{- (R 2) y Si -}} ), (- SiR 4 R 8 -), (- SnR 4 R 8 -), (- SiR 4 =) and (vary considerably depending on the structure of R groups in the -SnR ⁴ =) moiety It can. Alternatively, a water-free workup procedure can be used to prepare the silane sulfide modified polymeric compounds of Formula P1, Formula P2, Formula P3, Formula P4, Formula P5 and Formula P6.

  It is believed that the hydrocarbyl oxysilyl (-SiOR) group of the modified polymeric compound is reactive with a filler such as silica and / or carbon black, preferably in the presence of silica. This interaction is believed to result in the formation of bonds with the filler, or, in the case of some fillers, electrostatic interactions, which further results in a uniform distribution of the filler within the polymer composition. Be

Specific preferred modified polymeric compounds based on Formula P1 to Formula P6 include the following polymers (and their corresponding Lewis base adducts):

  The reaction product, ie, the polymer composition comprising the silane sulfide modified polymer compound (s) of the present invention, typically comprises one or more alkoxysilyls represented by formula P7, formula P8, formula P9 and formula P10 Or silanol group-containing compounds, typically in a total amount of 0.0001 to 1.50 mmol / gram, preferably 0.0005 to 0.9 mmol / gram, more preferably 0.0010 to 0.5 mmol / gram, and further More preferably, it contains 0.0020 to 0.1 mmol / gram of polymer.

  The polymer composition comprising the silane sulfide modified polymeric compound (s) of the present invention preferably comprises a sulfide group containing compound, and the sulfide group in the form of a hydrocarbyl silyl or hydrocarbyl stannyl protecting group and / or a thiol group (sulfide And thiol groups) in a total amount of 0.0001 to 0.50 mmol / gram of polymer, preferably 0.0005 to 0.30 mmol / gram, more preferably 0.0010 to 0.20 mmol / gram, still more preferably 0 Typically present at .0020-0.10 mmol / gram of polymer. In another embodiment, the sulfide group is in the range of 0.0001 to 0.50 mmol / gram of polymer, preferably in the range of 0.0005 to 0.30 mmol / gram, more preferably 0.0010 to 0.20 mmol / gram And even more preferably in the range of 0.0020 to 0.10 mmol / gram of polymer. In another embodiment, the thiol group is in the range of 0.0001 to 0.50 mmol / gram of polymer, preferably in the range of 0.0005 to 0.30 mmol / gram, more preferably 0.0010 to 0.20 mmol / gram And even more preferably in the range of 0.0020 to 0.10 mmol / gram of polymer.

  In most applications, the silane sulfide modified polymeric compound is preferably a pomopolymer derived from conjugated diolefins, a copolymer derived from conjugated diolefin monomers and aromatic vinyl monomers, and / or one or two conjugated diolefins and one Or a terpolymer with two aromatic vinyl compounds.

  Content of 1,2-bond and / or 3,4-bond (hereinafter referred to as "vinyl bond") of conjugated diolefin moiety in polymer composition containing the silane sulfide modified polymer compound (s) of the present invention There is no specific limitation on, but in most applications the content of vinyl bonds is preferably 10 to 90 wt%, particularly preferably 15 to 80 wt% (based on the total amount of polymer). If the content of vinyl bonds in the polymer composition is less than 10% by weight, the resulting product may have low wet slip resistance. When the vinyl content in the elastomeric polymer is greater than 90% by weight, the product may exhibit weakened tensile strength and abrasion resistance, as well as relatively large hysteresis loss.

  Although there is no specific limitation on the amount of aromatic vinyl monomer used in preparation of the modified polymer compound of the present invention, in most applications, the aromatic vinyl monomer constitutes 5 to 60% by weight of the total monomer content More preferably, it constitutes 10 to 50% by weight (based on the total weight of the polymer). Values less than 5% by weight may cause poor wet slip performance, abrasion resistance, and tensile strength, and values greater than 60% by weight may cause an increase in hysteresis loss. The silane sulfide modified polymer compound may be a block or random copolymer, preferably 40% by weight or more of the aromatic vinyl compound units are singly linked, and 10% by weight or less of the 8 or more aromatic vinyl compounds are continuous Are "blocks" that are linked together. Copolymers falling outside this range often exhibit increased hysteresis. The length of sequentially linked aromatic vinyl units can be measured by ozonolysis gel permeation chromatography developed by Tanaka et al. (Polymer, Vol. 22, pages 1721-1723 (1981)).

  The first polymer composition, such as a polymer product obtainable by a method of producing a silane sulfide modified polymer compound, comprising at least one of the silane sulfide modified polymer compounds of the present invention, depending on the specific polymer and the desired end use The product has a Mooney viscosity (ML 1 +4, 100 ° C., ASTM D 1646 (2004) within the range of 0 to 150, preferably 0 to 100, more preferably 20 to 100, as determined using a Monsanto MV 2000 instrument. Therefore, it is preferable to have a measurement. If the polymer Mooney viscosity (ML1 + 4, 100 ° C.) is greater than 150 MU, the processability (internal mixing) is because the compounding equipment used by the tire manufacturer is not designed to handle rubber grades with such high Mooney There is a high possibility that the introduction of the filler into the vessel and the heat generation, the roll mill banding, the extrusion speed, the extrusion die expansion, the smoothness, etc.) adversely affect the processing cost. In some cases, Mooney viscosities (ML 1 + 4, 100 ° C.) of less than 20 are difficult to handle as a result of increased tack and cold flow of uncrosslinked elastomeric polymers, resulting in green strength degradation and dimensions during storage It may not be preferred because it leads to a decrease in stability. In some further cases, when the first polymer composition comprising at least one silane sulfide modified polymeric compound is used as a softener, compatibilizer, or processing aid in a polymer formulation, a Mooney viscosity of less than 20 (ML1 + 4, 100 ° C.) may be preferred.

The preferred molecular weight distribution of the total polymer contained in the first polymer composition comprising at least one silane sulfide modified polymer compound represented by the ratio of weight average molecular weight to number average molecular weight (M _w / M _n ) is 1.0 to 10.0, preferably 1.1 to 8.0, more preferably 1.2 to 4.5.

Reactive Formulations In a preferred embodiment, the first polymer composition comprising at least one silane sulfide modified polymeric compound comprises silica, carbon-silica dual phase filler, carbon black, carbon nanotube filler, lignin, glass filler , Magadiite, etc., layered silicates comprising silica as main filler component in some preferred embodiments, and vulcanizing agents, and optionally, processing aids, oils, vulcanizing agents, silane coupling agents And mixed and reacted with filler (s) selected from additional components including, but not limited to, non-modified crosslinked elastomeric polymers to form a second polymer composition comprising the filler.

  The first polymer composition is not identical to at least one silane sulfide modified polymeric compound, and optionally (i) an oil (often referred to as an oil extended polymer) and (ii) a modified polymeric compound according to the present invention Includes one or both of the polymers. Polymers that are not identical to the modified polymeric compound of the present invention may be produced as by-products in the process of preparation of the modified polymeric compound (see above), modified polymeric compound (s) in solution (e.g. after polymerization) It may be produced by blending the obtained form) with another polymer solution and subsequently removing the solvent. The first polymer composition preferably comprises at least 25% by weight, more preferably at least 35% by weight, even more preferably at least 45% by weight of the silane sulfide modified polymeric compound relative to the total polymer in the composition Contains The remaining polymer portion contained in the polymer composition is a non-modified elastomeric polymer or a polymer modified in a manner different from that according to the invention. Examples of preferred non-modified elastomeric polymers are listed in WO 2009/148932 and preferably include styrene-butadiene copolymers, natural rubber, polyisoprene and polybutadiene. It is desirable for the non-modified polymer to have a Mooney viscosity (measured according to ASTM D 1 646 (2004), ML 1 + 4, at 100 ° C.) in the range of 20-200, preferably 25-150.

Oil A second polymer composition (cured) by using an oil in combination with a non-crosslinked elastomeric polymer to reduce viscosity or Mooney value, or to improve the processability of the first and second polymer compositions Various performance characteristics of the object may be improved.

  The oil (s) can be added to the modified polymer compound as a separate component prior to the completion of the preparation process, or in the first or second polymer composition preparation process. See WO 2009/148932 and US Patent Application Publication No. 2005/0159513, each of which is incorporated herein by reference for representative examples and classifications of oils.

  Representative oils include MES (Mild Extraction Solvate), TDAE (Treated Distillate Aromatic Extract), T-RAE and S-RAE. RAE (Residual Aromatic Extract) without limitation to them, DAE including T-DAE, and NAP including but not limited to Nytex 4700, Nytex 8450, Nytex 5450, Nytex 832, Tufflo 2000, and Tufflo 1200 These include, but are not limited to (light and heavy naphthenic oils). In addition, natural oils, including but not limited to vegetable oils, can be used as extender oils. Representative oils also include functional modifications of the above oils, particularly epoxidized or hydroxylated oils. The above oils contain various concentrations of polycyclic aromatic compounds, paraffinic, naphthenic and aromatic and have different glass transition temperatures. Oils of the type described above have been characterized (Kautschuk Gummi Kunststoffe, vol. 52, pages 799-805). In some embodiments, MES, RAE and TDAE are rubber extension oils.

Processing Aids Processing aids may optionally be added to the first and second polymer compositions, but are preferably added to the second polymer composition of the present invention. Processing aids are usually added to reduce the viscosity of the first and / or second polymer compositions. As a result, the mixing period can be shortened and / or the number of mixing steps can be reduced, thereby consuming less energy and / or obtaining higher throughput in the rubber compound extrusion process. Representative processing aids that may optionally be used as components of the first polymer composition of the present invention are each incorporated by reference herein in its entirety: Rubber Handbook, SGF, The Swedish Institution of Rubber Technology 2000 and Werner Kleema, Kurt Weber, Elastverarbeitung-Kennwerte und Berechnungsmethoden, Deutscher Verlag fuer Grundstoffindustrie (Leipzig, 1990). Representative processing aids that can optionally be used as components in the first polymer composition of the present invention can be classified as follows.
(A) Fatty acids, including, but not limited to, oleic acid, priorene, pristerene and stearic acid
(B) Aktiplast GT, PP, ST, T, T-60, 8, F; Deoflow S; Kettlitz Dispergator FL, FL Plus; Dispergum 18, C, E, K, L, N, T, R; Polyplastol 6, 15, 19, 21, 23; fatty acid salts, including but not limited to Struktol A50P, A60, EF44, EF66, EM16, EM50, WA48, WB16, WB42, WS180, WS280, and ZEHDL
(C) Aflux 12, 16, 42, 54, 25; Deoflow A, D; Deogum 80; Deosol H; Kettlitz Dispergator DS, KB, OX; Kettlitz-Mediaplast 40, 50, Pertac / GR; Kettlitz-Dispergator SI; Struktol FL and WB 212 Dispersants and processing aids, including, but not limited to, (D) Dispersants for highly active white fillers, including but not limited to Struktol W33 and WB42.

  Difunctionalized silanes and monofunctionalized silanes (also referred to herein as "silane coupling agents") are also sometimes referred to as processing aids, but are described separately below.

Silane Coupling Agent In some embodiments, a silane coupling agent (used to solubilize the polymer and the filler) is added to the polymer composition and at least one silane sulfide modified as described herein. Polymeric compounds and silica, layered silicates (including but not limited to magadiite) or carbon-silica dual phase fillers that may be used as filler components. Typical amounts of silane coupling agents added are from about 1 to about 20 parts by weight per 100 parts by weight total of silica and / or carbon-silica biphasic filler, and in some embodiments About 5 to about 15 parts by weight.

Silane coupling agents can be classified according to Fritz Roethemeyer, Franz Sommer: Kautschuk Technologie, (Carl Hanser Verlag 2006):
(A) Si 230 (EtO) ₃ Si (CH ₂ ) ₃ Cl, Si 225 (EtO) ₃ SiCH = CH _{2, A} 189 (EtO) ₃ Si (CH ₂ ) ₃ SH, Si 69 [(EtO) ₃ Si (CH ₂ ) _{3 S 2] 2, Si264 (} EtO) 3 Si- (CH 2) 3 SCN and Si363 (EtO) Si ((CH 2 -CH 2 -O) 5 (CH 2) 12 CH 3) 2 (CH2) 3 SH A difunctionalized silane, including but not limited to (Evonic Industries AG);

_{(B) Si203 (EtO) 3} -Si-C 3 H 7, and Si208 (EtO) including ₃ -Si-C ₈ H ₁₇ are not limited to, monofunctional silanes.
Further examples of silane coupling agents are given in WO 2009/148932, bis- (3-hydroxy-dimethylsilyl-propyl) tetrasulfide, bis- (3-hydroxy-dimethylsilyl-propyl) -disulfide Bis- (2-hydroxy-dimethylsilyl-ethyl) tetrasulfide, bis- (2-hydroxy-dimethylsilyl-ethyl) disulfide, 3-hydroxy-dimethylsilyl-propyl-N, N-dimethyl-thiocarbamoyl tetrasulfide and Examples include, but are not limited to, 3-hydroxy-dimethylsilyl-propylbenzothiazole tetrasulfide.

Vulcanizing agent As described herein, a vulcanizing agent is added to the first or second polymer composition as described herein. The addition of vulcanizing agents to the first or second polymer composition represents an important basis for the formation of a vulcanized polymer composition.

  Sulfur, sulfur containing compounds that act as sulfur donors, sulfur promoter systems and peroxides are the most common vulcanizing agents. Examples of sulfur containing compounds that act as sulfur donors include dithiodimorpholine (DTDM), tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), and dipentamethylenethiuram tetrasulfide (DPTT). It is not restricted to these. Examples of sulfur promoters include, but are not limited to, amine derivatives, guanidine derivatives, aldehyde amine condensates, thiazoles, thiuram sulfides, dithiocarbamates and thiophosphates. Examples of peroxides used as vulcanizing agents include di-tert. -Butyl-peroxide, di- (tert.-butyl-peroxy-trimethyl-cyclohexane), di- (tert.-butyl-peroxy-isopropyl-) benzene, dichloro-benzoyl peroxide, dicumyl peroxide, tert. -Butyl-cumyl-peroxide, dimethyl-di (tert.-butyl-peroxy) hexane, dimethyl-di (tert.-butyl-peroxy) hexyne and butyl-di (tert.-butyl-peroxy) valerate (Rubber Handbook, SGF) , The Swedish Institution of Rubber Technology 2000), but not limited thereto.

Additional examples and additional information regarding vulcanizing agents, Kirk-Othmer, Encyclopedia of Chemical technology 3 rd, Ed. , (Wiley Interscience, N. Y. 1982), volume 20, pp. 365-468, (in particular, "Vulcanizing Agents and Auxiliary Materials" pp. 390-402).

  Sulfenamide-type, guanidine-type or thiuram-type vulcanization accelerators can be used together with the vulcanizing agent, if necessary. Other additives such as zinc flower, vulcanization aids, anti-aging agents, processing aids and the like may optionally be added. The vulcanizing agent is typically added to the polymer composition in an amount of 0.5 to 10 parts by weight, and in some embodiments 1 to 6 parts by weight, based on 100 parts by weight of the total elastomeric polymer. Examples of vulcanization accelerators and the amount of accelerator added to the total polymer are given in WO 2009/148932. The expression "total polymer" denotes the sum of all individual quantities of different polymer types, including silane sulfide modified (elastomer) polymeric compounds.

  The sulfur promoter system may or may not contain zinc oxide. Preferably, zinc oxide is used as a component of a sulfur promoter system.

Fillers Fillers are added to the first polymer composition to form a second polymer composition. The second polymer composition, when cured, forms a filler-containing vulcanized polymer composition. Thus, the second polymer composition and the product produced therefrom, as well as the vulcanized polymer composition produced from the second polymer composition and the product containing such a vulcanized polymer composition, as reinforcing agents Contains a working filler. Examples of suitable fillers include carbon black, silica, carbon-silica biphasic fillers, clays (layered silicates), calcium carbonate, magnesium carbonate, lignin, carbon nanotubes, glass particle based fillers, starch based fillers Amorphous fillers such as agents, as well as combinations thereof. Examples of fillers are described in WO 2009/148932, which is hereby incorporated by reference. Carbon black is produced by furnace methods, and in some embodiments, has a nitrogen adsorption specific surface area of 50 to 200 m ² / g and a DBP oil absorption of 80 to 200 ml / 100 grams, eg, FEF, HAF, ISAF, or SAF Carbon black is used. In some embodiments, highly agglomerated carbon black is used. The carbon black is typically 2 to 100 parts by weight, in some embodiments 5 to 100 parts by weight, in some embodiments 10 to 100 parts by weight, and several to 100 parts by weight total elastomeric polymer In embodiments of 10 to 95 parts by weight are added.

Examples of silica fillers include, but are not limited to, wet silica, dry silica, synthetic silicate silica and combinations thereof. Silicas with small particle size and high surface area show high reinforcement effect. Small diameter, highly agglomerated silica (ie, having high surface area and high oil absorption) exhibits excellent dispersibility in elastomeric polymer compositions and exhibits desirable properties and superior processability. The average particle size of the silica, in terms of primary particle size, is in some embodiments 5 to 60 nm, and in some embodiments 10 to 35 nm. Also, the specific surface area of the silica particles (as measured by the BET method) is, in some embodiments, 35 to 300 m ² / g. See WO 2009/148932 for examples of silica filler diameter, particle size and BET surface. The silica is added in 10 to 100 parts by weight, in some embodiments 30 to 100 parts by weight, and in some embodiments 30 to 95 parts by weight, per 100 parts by weight total elastomeric polymer. Silica fillers may be used in combination with other fillers including, but not limited to, carbon black, carbon-silica dual phase fillers, clays, calcium carbonate, carbon nanotubes, magnesium carbonate and combinations thereof, and the like.

  Carbon black and silica may be added together, in which case the total amount of carbon black and silica added is 30 to 100 parts by weight per 100 parts by weight of total elastomeric polymer, and in some embodiments It is 30 to 95 parts by weight. As long as such a filler is uniformly dispersed in the elastomeric composition, increasing the amount (within the above range) results in the composition having excellent rolling and extrudability, and the vulcanized product Products containing the vulcanized polymer composition result in favorable hysteresis loss properties, rolling resistance, improved wet-slip resistance, abrasion resistance, and tensile strength.

  The carbon-silica biphasic filler may be used alone or in combination with carbon black and / or silica according to the present teachings. The carbon-silica biphasic filler, even when added alone, can exhibit the same effect as obtained by the combined use of carbon black and silica. A carbon-silica two-phase filler is a so-called silica-coated carbon black which is produced by coating on the surface of carbon black with silica and is commercially available under the trademarks CRX2000, CRX2002 or CRX2006 (product of Cabot). The carbon-silica biphasic filler is added in the same amount as described above for silica. Carbon-silica dual phase fillers can be used in combination with other fillers including, but not limited to, carbon black, silica, clays, calcium carbonate, carbon nanotubes, magnesium carbonate and combinations thereof. In some embodiments, carbon black and silica can be used individually or in combination.

  Silica, carbon black or carbon black-silica biphasic fillers or combinations thereof may be used in combination with natural fillers including but not limited to starch or lignin.

In some embodiments, the second polymer composition, the product produced from the second polymer composition and the vulcanized polymer composition, and the silica incorporated in the product comprising such a vulcanized polymer composition is 150 to 300 m ² / g, with a surface area determined by nitrogen adsorption (hereinafter referred to as “N ^{2 A} ”). Silica having N2A less than 150 m ² / g may disadvantageously have a low reinforcing effect. Silicas with N2A greater than 300 m ² / g can provide rubber compounds with increased viscosity and degraded processability. A second polymer composition, a product produced from the second polymer composition and a vulcanized polymer composition, and in the case of carbon black incorporated in a product comprising such a vulcanized polymer composition, 60 to 150 m ² / g N2A is appropriate. Carbon blacks having an N2A of less than 60 m ² / g may have a low reinforcing effect. Carbon blacks with N2A greater than 150 m ² / g are processed to increase the hysteresis loss of products formed from the second polymer composition and vulcanized polymer compositions, and products comprising such vulcanized polymer compositions Degrade the sex.

Polymer Composition A second polymer composition comprising the filler according to the invention comprises an oil-containing first polymer composition as described above (comprising at least one modified polymer compound according to the invention as defined above, A first polymer composition), a non-modified polymer or a polymer (including oil spreads) modified by methods other than those according to the invention, a filler (s) (carbon black, silica, A carbon-silica two-phase filler, etc., and optionally processing aids, oils, silane coupling agents and other additives are prepared by kneading in a kneader at 140 ° C. to 180 ° C. A “step 1” filler-containing second composition may be formed.

  Alternatively, the second polymer composition according to the present invention is at least one filler (for example, carbon black, silica, carbon-silica two-phase filler, etc.) formed as a result of the process of producing the modified polymer compound. C. at 140 ° C., polymer compositions already comprising, optionally processing aids, oils, silane coupling agents, fillers (eg carbon black, silica, carbon-silica biphasic fillers etc) and other additives The “first stage” second polymer composition containing a filler may be formed by kneading in a kneader at ̃180 ° C. The formation of the "first stage" second polymer composition may comprise one or more mixing steps, preferably 2 to 7 mixing steps.

  The silane sulfide-modified polymer compound contained in the second polymer composition enables mixing under predetermined treatment conditions with a relatively low Mooney viscosity compared to the corresponding polymer composition not containing the silane sulfide-modified polymer compound Thus, mixed throughput can be increased and / or energy consumption per unit of time can be reduced.

  After cooling, a vulcanizing agent such as sulfur, a vulcanization accelerator, optionally zinc oxide, is added to the second composition of the "first stage", also called the second composition of the "second stage" The resulting mixture is blended by a Brabender mixer, a Banbury mixer, or an open roll machine to form the desired shape. The second composition of the “second stage” is then vulcanized at 140 ° C. to 180 ° C. to obtain a vulcanizate also referred to as “vulcanized polymer composition” or “vulcanized elastomeric polymer composition”. obtain.

  Alternatively, a vulcanizing agent such as sulfur, a vulcanization accelerator, optionally zinc oxide, can be added to the first polymer composition described above, and the resulting mixture is a Brabender mixer, a Banbury mixer, or an open roll. Blend to form the desired shape, and the mixture is vulcanized at 140.degree. C. to 180.degree. C. to obtain a vulcanizate also referred to as a "vulcanized polymer composition" or a "vulcanized elastomeric polymer composition". .

Industrial Applicability Since the "vulcanized elastomeric polymer composition" of the present invention exhibits low rolling resistance, low dynamic heat generation and excellent wet-slip performance, these are tires, tire treads, sidewalls, and tire carcass, And are suitable for the preparation of other industrial products such as belts, hoses, damping bodies and parts of footwear.

Silane Sulfide Modified Polymer Compound and Additional Polymer When the modified polymer compound of the present invention is prepared by a polymerization reaction, a living anionic elastomeric polymer is produced ("living polymer"). A part or all of the living polymer is modified with the silane sulfide modifying agent of the present invention to produce the modified polymer compound of the present invention. Unmodified polymers can also be produced within the reaction. Also, if the modification reaction is performed using a combination of a silane sulfide modifier of the present invention and a further chain end modifying compound or a coupling agent such as an alkoxysilane, eg tetraethoxysilane, the resulting polymer composition is It comprises both the modified macromolecular compound (s) according to the invention and the further modified or non-modified polymer ("the further polymer").

  Examples of living anionic elastomeric polymers and further polymers which are modified according to the invention are, in particular, homopolymers of conjugated dienes of butadiene or of isoprene and at least one conjugated diene, especially of at least one conjugated diene, in particular of butadiene or isoprene. Mention may be made of random or block copolymers and terpolymers with at least one aromatic alpha-olefin, in particular styrene and 4-methylstyrene, aromatic diolefins, in particular divinylbenzene. In particular, at least one conjugated diene and at least one aromatic alpha-olefin, and optionally at least one aromatic diolefin or aliphatic alpha-olefin, in particular butadiene or isoprene and styrene, 4-methylstyrene and / or divinylbenzene Random copolymerization with, optionally ternary polymerization is preferred. Furthermore, particularly preferred is random copolymerization of butadiene and isoprene.

  Examples of living anionic elastomeric polymers to be modified and further polymers include: BR-polybutadiene, butadiene / C1-C4 alkyl acrylate copolymer, IR-polyisoprene, styrene content 1 to 60, preferably 10 to 50 weight SBR-Styrene / Butadiene Copolymer, in which the polymer is prepared in solution, the styrene content is 1 to 60, preferably 10 to 50 weight percent, and the polymer is in solution, containing SSIR SIR-Styrene / isoprene copolymers to be prepared, BRIR-butadiene / isoprene copolymers having an isoprene content of 1 to 60, preferably 10 to 50 weight percent, containing BRIR, the polymer being prepared in solution, IIR-isobutyrate / Isoprene copolymers, IBR- isoprene / butadiene copolymers, NBR-butadiene / acrylonitrile copolymers, HNBR- partially hydrogenated or fully hydrogenated NBR rubber, and mixtures thereof rubber, modified EPDM. The acronym "EPDM" stands for ethylene / propylene / diene copolymer.

  In one embodiment, the living polymer or the further polymer is polybutadiene.

  In another embodiment, the living polymer or additional polymer is butadiene / styrene copolymer (SSBR) prepared in solution.

  In another embodiment, the living or additional polymer is isoprene / styrene copolymer (SSIR) prepared in solution.

  In another embodiment, the living polymer or the further polymer is butadiene / isoprene copolymer (BRIR) prepared in solution.

  In another embodiment, the living polymer or the additional polymer is polyisoprene, including synthetic polyisoprene.

  In another embodiment, the living polymer or additional polymer is a styrene / butadiene copolymer having a styrene unit content of 1 to 60 weight percent, preferably 10 to 50 weight percent based on the total weight of the copolymer.

  In another embodiment, the living polymer or additional polymer has a content of 1,2-polybutadiene units of 5 to 70 weight percent, preferably 50 to 70, or 5 to 25 weight percent based on the total weight of the polybutadiene units portion of the copolymer Percent styrene / butadiene copolymer.

  In another embodiment, the living polymer or additional polymer is a styrene / isoprene copolymer having a styrene unit content of 1 to 60 weight percent, preferably 10 to 50 weight percent based on the total weight of the copolymer.

  In another embodiment, the living polymer or the additional polymer has a content of 1,2-polyisoprene units of 5 to 70 weight percent, preferably 50 to 70, or 5 to 25 based on the total weight of the polybutadiene unit portion of the copolymer. Weight percent styrene / isoprene copolymer.

  In another embodiment, the living polymer or the further polymer is a butadiene / isoprene copolymer having an isoprene unit content of 0.1 to 70 weight percent, preferably 5 to 50 weight percent based on the total weight of the copolymer.

  In another embodiment, the living polymer or the further polymer is an isobutylene / isoprene copolymer. In another embodiment, the living polymer or additional polymer is partially hydrogenated butadiene.

  In another embodiment, the living polymer or the further polymer is a partially hydrogenated styrene-butadiene copolymer.

Definitions As used herein, the term "alkyl" refers to an aliphatic group. The alkyl group may be linear, branched or cyclic, or may contain a combination of linear, branched and / or cyclic moieties, and may be saturated or unsaturated. Examples of linear aliphatic hydrocarbon groups include methyl (Me), ethyl (Et), n-propyl (Pr), n-butyl (Bu), n-pentyl and n-hexyl and are branched Examples of aliphatic hydrocarbon groups include isopropyl and tert-butyl.

  The term "aryl" as used herein denotes an aromatic group which may contain more than one aromatic ring. Examples include phenyl, biphenyl and other benzenoid compounds, each optionally substituted with alkyl, alkoxy or other heteroatom such as oxygen, nitrogen, sulfur and / or phosphorous containing sites.

  The term "alkoxy" is understood to include methoxy (MeO), ethoxy (EtO), propoxy (PrO), butoxy (BuO), isopropoxy (iPrO), isobutoxy (iBuO), pentoxy and the like.

  As used herein, the term "aralkyl" refers to a group comprising at least one aromatic ring in the alkyl group.

The notation (C _a -C _b ), such as (C ₁ -C ₁₂ ), as used herein, is intended to mean a range of the number of carbon atoms from a to b and from a Includes all individual values as well as subranges to b.

  The term "hydrocarbon group" is understood to include any group comprising saturated, unsaturated, linear, branched, cyclic and aromatic groups consisting only of hydrogen and carbon elements.

  The following examples are provided to further illustrate the present invention and are not to be taken as limiting. Examples are preparation of silane sulfide modifiers, preparation and testing of modified (elastomer) polymers (i.e., polymer compositions containing the silane sulfide modified polymer compound of the present invention), and first polymer composition and second The preparation and testing of a non-crosslinked polymer composition comprising the polymer composition of the invention and a crosslinked or cured polymer composition, also referred to as a vulcanized polymer composition. Unless otherwise stated, all parts and percentages are expressed on a weight basis. The term "overnight" refers to a time of about 16-18 hours, and "room temperature" refers to about 20-25 ° C. The polymerization was carried out in a nitrogen environment, excluding humidity and oxygen.

The vinyl content of the conjugated diolefin moiety was additionally determined by means of an infrared absorption spectrum (Morello method, IFS 66 FT of the Bruker Analytic GmbH-infrared spectrometer). Infrared samples were prepared using CS ₂ as a swelling agent.

Bound styrene content: A calibration curve was prepared by infrared absorption spectrum (infrared (IFS 66 FT-infrared spectrometer from Bruker Analytik GmbH). An infrared sample was prepared using CS ₂ as a swelling agent). Styrene - bound styrene-butadiene copolymer in order to determine IR was assessed four bands: a) band for trans-1,4-polybutadiene units in the 966cm ^-1, b) cis-1 in 730 cm ^-1, 4- Bands for polybutadiene units c) Bands for 1,2-polybutadiene units at 910 cm ^-1 and bands for bound styrene (styrene aromatic bonds) at 700 cm ^-1 . The heights of the bands were scaled according to the appropriate extinction coefficient and aggregated to a total of 100%. The normalization was performed via ¹ H- and ¹³ C-NMR. The styrene content was instead determined by NMR (NMR (Avance 400 device from Bruker Analytik GmbH ( ¹ H = 400 MHz, ¹³ C = 100 MHz))).

  1D NMR spectra were collected on a BRUKER Avance 200 NMR spectrometer (BRUKER BioSpin GmbH) using a "5 mm dual detection probe". Field uniformity was optimized by maximizing the deuterium lock signal. The sample was leveled by the shim by optimizing the deuterium lock signal. The samples were run at room temperature (298 K). The following deuterated solvents were used: C6D6 (7.16 ppm for 1H, 128.06 ppm for 13C), CDCl3 (7.24 ppm for 1H, 77.03 ppm for 13C), d8-THF (1.73 for 1H, 3.58 ppm for 13C) 25.35 ppm), and the signals of the remaining protons of the deuterated solvent were used as internal references, respectively.

ＧＰＣ法 細く分布されたポリスチレン基準によってＳＥＣ較正される
試料調製
ａ１）油フリーポリマー試料
１０ｍＬの大きさの茶色いバイアル瓶を用いて、約「９〜１１ｍｇ」の乾燥ポリマー試料（含水量＜０．６％）をテトラヒドロフラン１０ｍＬに溶解した。バイアルを２０分間、２００ｕ／分で振ることによってポリマーを溶解した。
ａ２）油含有ポリマー試料
１０ｍＬの大きさの茶色いバイアル瓶を用いて、約「１２〜１４ｍｇ」の乾燥ポリマー試料（含水量＜０．６％）をテトラヒドロフラン１０ｍＬに溶解した。バイアルを２０分間、２００ｕ／分で振ることによってポリマーを溶解した。
ｂ）ポリマー溶液を、０．４５μｍの使い捨てフィルターを用いて２ｍｌバイアルに移した。
ｃ）２ｍｌバイアルを、ＧＰＣ分析にかけるために試料採取器に載置した。
溶出速度：１．００ｍＬ／分
注入量：１００．００μｍ（ＧＰＣ法Ｂ ５０．００μｍ）
測定はＴＨＦにて４０℃で行われた。器具：Ａｇｉｌｅｎｔ Ｓｅｒｉｅ １１００／１２００、モジュールセットアップ、
Ｉｓｏポンプ、オートサンプラ、サーモスタット、ＶＷ−検知器、ＲＩ−検知器、脱ガス装置、カラムＰＬ混合Ｂ／ＨＰ混合Ｂ。 For spectral processing, BRUKER 1D WIN NMR software (version 6.0) was used. The resulting spectral phase, baseline correction and spectral integration were performed in manual mode. See Table 1 for acquisition parameters.

GPC method Sample preparation SEC calibrated with a finely distributed polystyrene standard a1) Oil free polymer sample Using a brown vial of 10 mL size, approximately "9 to 11 mg" of dry polymer sample (water content <0.6 %) Was dissolved in 10 mL of tetrahydrofuran. The polymer was dissolved by shaking the vial for 20 minutes at 200 u / min.
a2) Oil-containing polymer sample A brown vial with a size of 10 mL was used to dissolve about "12-14 mg" of a dry polymer sample (water content <0.6%) in 10 mL of tetrahydrofuran. The polymer was dissolved by shaking the vial for 20 minutes at 200 u / min.
b) The polymer solution was transferred to a 2 ml vial using a 0.45 μm disposable filter.
c) 2 ml vials were placed on the sampler for GPC analysis.
Dissolution rate: 1.00 mL / min Injection volume: 100.00 μm (GPC method B 50.00 μm)
The measurement was performed at 40 ° C. in THF. Instruments: Agilent Serie 1100/1200, module setup,
Iso pump, auto sampler, thermostat, VW-detector, RI-detector, degassing apparatus, column PL mixed B / HP mixed B.

In each GPC apparatus, three columns were used in connected mode. Length of each column: 300 mm, column type: 79911 GP-MXB, Plgel 10 μm MIXED-B GPC / SEC column, Fa. Agilent Technologies (eigentlicher Hersteller ist auch Polymer Laboratories)
GPC standard: EasiCal PS-1 polystyrene standard, Spatula A + B
Styrene Standard Manufacturer:
Polymer Laboratories Polymer Laboratories
Currently, Varian, Inc. Corporation of Varian Deutschland GmbH
Website: http: // www. polymerlabs. com

  Polydispersity (Mw / Mn) was used as a measure for the breadth of the molecular weight distribution. Calculations of Mw and Mn (quantity average molecular weight (Mw) and number average molecular weight (Mn)) were made based on one of two procedures.

  Mp1, Mp2 and Mp3 respectively correspond to the (maximum peak) molecular weight measured at the first, second or third peak of the GPC curve [the first peak Mp1 (lowest molecular weight) is located to the right of the curve The final peak (highest molecular weight) is located to the left of the curve]. The maximum peak molecular weight means the molecular weight of the peak at the position of the maximum peak intensity. Mp2 and Mp3 are two or three polymer chains linked to one macromolecule. Mp1 is one polymer chain (reference molecular weight-two or more polymer chains do not bind to one polymer).

The total bond percentage represents the sum of the weight fraction of bound polymer to the total polymer weight, including the sum of the polymerization fractions of all bound and non-bound polymers. The total binding rate is calculated as shown below.
CR (total) = ((area ratio of all binding peaks (the peak with the highest Mp2 to the highest peak with the highest peak)) / (all peaks [the peak with the highest peak Mp1 to the highest indexed peak率 area ratio) to the peak].

The individual binding rate (eg, two polymer arms bound corresponding to the peak with peak maximum Mp2) is calculated as illustrated below.
CR (2 arms) = (area ratio of peak having peak maximum Mp2) / (Σ area ratio of all peaks [from peak having peak maximum Mp1 to peak of highest index peak]].

The modification efficiency with sulfanylsilane was determined by NMR method (NMR by Bruker Analytic GmbH (Avance 400 device ( ¹ H = 400 MHz, ¹³ C = 100 MHz)) of (-SiMe ₃ ) group and (-Si-OMe) group concentration alkoxy groups and containing over to the determined at .3.3~3.5.ppm (-Si-OMe) in the signal and 0.1~0.2ppm (-SiMe ₃₎ signal. sulfanylsilane compound The value was divided by the number-average molecular weight (Mn) measured by GPC in order to determine the modification efficiency of in%, since the measured value is the amount of Si-C bond per unit weight .

  The modification efficiency with sulfanylsilane was also determined via the sulfur content as sulfate. The procedure is to burn the sample in a constant temperature drier (burner 02 at GAMAB, Bad Duerrenberg, Germany), followed by absorption of the flue gas in water with 0.1% hydrazinium hydroxide, followed by ion chromatography. (Metrohm, column: It was necessary to determine the sulfate concentration by Dionex IonPacAS 12A.

  The rubber compounds were prepared by combining the components listed in Tables 4, 8 and 12 below in a "380 cc Banbury mixer (Brabender GmbH & CoKG Labstation 350 S)" according to a two-step mixing process. Stage 1 mixed all the ingredients together, except the ingredients of the vulcanized package, to form the stage 1 formulation. In stage 2, the components of the vulcanized package were mixed into the stage 1 formulation to form a stage 2 formulation.

  Mooney viscosity was measured according to ASTM D 1646 (2004) with MV2000E from Alpha Technologies UK at a temperature of 100 ° C. [ML1 + 4 (100 ° C.)] with a preheat time of 1 minute and a rotor run time of 4 minutes. The Mooney viscosity measurement of rubber was performed on dry (solvent-free) raw material polymer (non-vulcanized rubber). The Mooney values of the starting polymers are listed in Table 3. The Mooney viscosity of the compounds was measured on the uncured (non-vulcanized) second state polymer compound samples prepared according to Tables 4, 8 and 12. The Mooney values of the compounds are listed in Tables 7, 11 and 15.

  The measurement of non-vulcanizing rheological properties is according to ASTM D 5289-95 (reapproved in 2001) in order to measure scorch time (TS) and curing time (TC), a Rotorless shear rheometer (manufactured by Alpha Technologies UK, It was performed using MDR2000E). Rheometer measurements were performed on the uncured second stage polymer formulations according to Tables 5, 9 and 13 at a constant temperature of 160 ° C. The amount of polymer sample is about 4.5 g. The sample shape and shape preparation are standardized and defined by a measuring device (manufactured by Alpha Technologies UK, MDR2000E).

  The values "TC50" and "TC90" are respectively the time required to obtain 50% as well as 90% conversion of the vulcanization reaction. The torque is measured as a function of the time of reaction. Vulcanization conversion is automatically calculated based on the generated torque versus time curve. The “TS1” and “TS2” values are respectively the time required to raise the torque by 1 dNm as well as 2 dNm over the corresponding torque minimum (ML) during vulcanization. Preferably, TS1 is greater than 1.5 minutes, TS2 is greater than 2.5 minutes, TC50 is 3-8 minutes, and TC90 is 8-19 minutes.

  The tensile strength, elongation at break and modulus at 300% elongation (coefficient 300) were measured using a dumbbell die C specimen in Zwick Z010 by ASTM D412-98A (reapproved in 2002). Among the standardized dumbbell die C test pieces, those of “2 mm thickness” were used. Tensile strength measurements were performed on the cured (cured) second stage polymer samples prepared according to Tables 6, 10 and 14 at room temperature. The formulation of step 2 was vulcanized to TC 95 (95% vulcanization conversion) at 160 ° C. within 16-25 minutes (see cure data in Tables 5, 9 and 13).

  The exotherm was measured according to ASTM D623, method A, with Doli's "Goodrich" flexometer. Exothermic measurements were performed on the second stage polymer samples vulcanized according to Tables 5, 9 and 13. The stage 2 formulation was vulcanized at 160 ° C. to TC 95 (95% vulcanization conversion) (see cure data in Tables 5, 9 and 13).

  The measurement of tan δ at 60 ° C. and tan δ at 0 ° C. and tan δ at −10 ° C. is 0.2% using a dynamic mechanical thermal spectrometer “Eplexor 150 N” manufactured by Gabo Qualimeter Testanlagen GmbH (Germany) Was performed on a cylindrical specimen by applying a compressive dynamic strain of at a frequency of 2 Hz at the corresponding temperature. The smaller the index at a temperature of 60 ° C., the lower the rolling resistance (lower = better). Tan δ (0 ° C.) was measured at 0 ° C. using the same equipment and the same load conditions. The higher the index at this temperature, the better the wet slip resistance (higher = better). Tan δ at 60 ° C. and tan δ at 0 ° C. and tan δ at −10 ° C. were determined (see Tables 6, 10 and 14). The stage 2 formulation was vulcanized at 160 ° C. to TC 95 (95% vulcanization conversion) (see cure data in Tables 5, 9 and 13). This process leads to the production of visually "bubble free", "60 mm diameter" and "10 mm height" uniform cured rubber discs. The specimens are drilled out of the dish and have dimensions of "10 mm diameter" and "10 mm height".

  DIN wear was measured according to DIN 5316 (1987-06-01). The larger the index, the lower the wear resistance (lower = better). Abrasion measurements were performed on the second stage polymer formulations vulcanized according to Tables 5, 9 and 13.

  In general, the higher the elongation at break, the tensile strength, the coefficient of 300 and the value of tan δ at 0 ° C, the better the sample performance, while the tan δ at 60 ° C, the lower the heat generation and the wear. The lower the better the sample performance. Preferably, TS1 is greater than 1.5 minutes, TS2 is greater than 2.5 minutes, TC50 is 3-8 minutes, and TC90 is 8-19 minutes.

Modifier Preparation Six modifiers and one coupling agent were used in the examples. The structural formula and the method of preparation (or the source to obtain) are as follows. Modifiers 3, 4, 5 and 6 are representative of those of the present invention and Modifiers 1 and 2 are for comparison purposes.

Coupling Agent Coupling Agent C1 is represented by Formula C1. Tin tetrachloride (C1) was purchased from Aldrich. SnCl ₄ (formula C1)

Further Modifiers Modifier 1 is represented by the following Formula M1 and was prepared as follows.

Preparation route 1 (M1)
In a 100 mL Schlenk tube, 25 ml of tetrahydrofuran (THF), 79.5 mg (10 mmol) of lithium hydroxide, and then 1.18 g (10 mmol) of gamma-mercaptopropyl (methyl) dimethoxysilane P1 obtained from ABCR GmbH. It was thrown in. The reaction mixture was stirred at room temperature for 24 hours and at 50 ° C. for a further 2 hours. Next, tert-butyldimethylchlorosilane (1.51 g (10 mmol)) was dissolved in 10 g of THF and the resulting solution was subsequently added dropwise to a Schlenk tube. Lithium chloride precipitated. The suspension was stirred at room temperature for about 24 hours and at 50 ° C. for an additional 2 hours. The THF solvent was removed under vacuum. Subsequently, cyclohexane (30 ml) was added. The white precipitate was then filtered off. The cyclohexane solvent was removed under vacuum (under reduced pressure). The resulting colorless liquid solution was found to be 99% pure by GC so no further purification was necessary. A yield of 3.1 g (9.3 mmol) of the modifier M1 was obtained.

Preparation route 2 (M1)
In a 100 mL Schlenk tube, 1.18 g (10 mmol) of gamma-mercaptopropyl (methyl) dimethoxysilane P1 obtained from ABCR GmbH, 25 mL of tetrahydrofuran (THF) and then sodium methanolate (NaOMe) dissolved in 10 mL of THF ) 0.594 g (11 mmol) was added. The reaction mixture was stirred at room temperature for 18 hours. Then, tert-butyldimethylchlorosilane (1.51 g (10 mmol)) was dissolved in 10 g of THF and the resulting solution was subsequently added dropwise to the Schlenk tube. Sodium chloride precipitated. The suspension was stirred for about 24 hours at room temperature and for a further 2 hours at 50 ° C. The THF solvent was removed under vacuum. Then cyclohexane (30 ml) was added. The white precipitate was subsequently filtered off. The cyclohexane solvent was removed under vacuum (under reduced pressure). The resulting colorless liquid solution was found to be 89% pure by GC. Further purification was carried out by preparative distillation, yielding 2.6 g (7.9 mmol) of modifier M1.
Modifier 2 is represented by the following Formula M2 and was prepared as follows:

Preparation route 1 (M2)
In a 100 mL Schlenk tube, 25 mL of tetrahydrofuran (THF), 79.5 mg (10 mmol) of lithium hydroxide, and then gamma-mercaptopropyltrimethoxysilane P2 [Silquest A-189] obtained from Cromton GmbH, 1. 96 g (10 mmol) were charged. The reaction mixture was stirred at room temperature for 24 hours and at 50 ° C. for a further 2 hours. Thereafter, tert-butyldimethylchlorosilane (1.51 g (10 mmol)) was dissolved in 10 g of THF and the resulting solution was then added dropwise to a Schlenk tube. Lithium chloride precipitated. The suspension was stirred at room temperature for about 24 hours and at 50 ° C. for an additional 2 hours. The THF solvent was removed under vacuum. Then cyclohexane (30 ml) was added. The white precipitate was subsequently filtered off. The cyclohexane solvent was removed under vacuum (under reduced pressure). The resulting colorless liquid solution was found to be 99% pure by GC so no further purification was necessary. A yield of 2.9 g (9.2 mmol) of the modifier M2 was obtained.

Alternative preparation route 2 (M2)
In a 100 mL Schlenk tube, 1.96 g (10 mmol) of gamma-mercaptopropyltrimethoxysilane P2 [Silquest A-189] obtained from Cromton GmbH, 25 mL of tetrahydrofuran (THF), and then dissolved in 10 mL of THF 0.594 g (11 mmol) of sodium methanolate (NaOMe) was added. The reaction mixture was stirred at room temperature for 18 hours. Next, tert-butyldimethylchlorosilane (1.51 g (10 mmol)) was dissolved in 10 g of THF and the resulting solution was then added dropwise to a Schlenk tube. Sodium chloride precipitated. The suspension was stirred at room temperature for about 24 hours and at 50 ° C. for an additional 2 hours. The THF solvent was removed under vacuum. Next, cyclohexane (30 ml) was added. The white precipitate was subsequently filtered off. The cyclohexane solvent was removed under vacuum (under reduced pressure). The resulting colorless solution was found to be 89% pure by GC. Further purification was carried out by preparative distillation to give a yield of 2.2 g (7.2 mmol) of modifier M2.

Alternative preparation route 3 (M2)
Into a 500 mL Schlenk tube, 100 g of cyclohexane, 8.6 g (85 mmol) of triethylamine, and 13.12 g (80 mmol) of gamma-mercaptopropyltrimethoxysilane [Silquest A-189] obtained from Cromton GmbH were charged. 24.91 g (165 mmol) of tert-butyldimethylchlorosilane were diluted with 170 g of cyclohexane and the resulting solution was then added dropwise to a Schlenk tube. Shortly thereafter, white triethylammonium chloride precipitated. The suspension was stirred at room temperature for about 24 hours and at 60 ° C. for an additional 3 hours. The white precipitate was subsequently filtered off. The resulting colorless solution was distilled under vacuum to give a yield of 20.7 g (67.7 mmol) of modifier M2.

Silane Sulfide Modifier Modifier 3 is represented by Formula M3 below, and was prepared as follows.

Preparation route 1
In a 100 mL Schlenk tube, 50 ml of tetrahydrofuran (THF), 159 mg (20 mmol) of lithium hydroxide, and then 3.6 g (20 mmol) of gamma-mercaptopropyl (methyl) dimethoxysilane P1 obtained from ABCR GmbH, It was thrown in. The reaction mixture was stirred at 65 ° C. for 2 hours. The reaction mixture was allowed to cool to room temperature. Next, a solution of di-n-butyl dichlorostannane (3.3 g (10 mmol)) in 10 g of THF was then added dropwise to a Schlenk tube. The reaction mixture was warmed to 65 ° C. and held at that temperature for 2 hours. Subsequently, the THF solvent was removed from the resulting mixture at room temperature under vacuum (vacuum) and the residue was dissolved in 50 mL of cyclohexane. The precipitated lithium chloride was separated by filtration from the reaction product dissolved in cyclohexane. The cyclohexane solvent was removed under vacuum (under reduced pressure). The resulting colorless liquid solution was found to be 89% pure by GC and therefore no further purification was necessary. A yield of 5.5 g (8.9 mmol) of the modifier M3 was obtained.

Preparation route 2
A 100 mL Schlenk tube was charged with 100 mL of cyclohexane, 2.02 g (20 mmol) of triethylamine, and 3.6 g (20 mmol) of gamma-mercaptopropyl (methyl) dimethoxysilane P1 obtained from ABCR GmbH. The reaction mixture was stirred at room temperature for 5 minutes. Next, a solution of di-n-butyl dichlorostannane (3.30 g (10 mmol)) in 20 g of cyclohexane was added dropwise to a Schlenk tube. The reaction mixture was warmed to 65 ° C. and held at that temperature for 2 hours. The precipitated triethylammonium chloride was separated by filtration from the reaction product dissolved in cyclohexane. The cyclohexane solvent was then removed under vacuum (under reduced pressure). The resulting colorless liquid solution was found to be 95% pure by GC and therefore no further purification was necessary. A yield of 5.9 g (9.5 mmol) of the modifier M3 was obtained.
¹ H-NMR (400 MHz, 23 ° C., C ₆ D ₆ ): δ = 3.35 (s, 12 H, SiOCH ₃ ), 2.82 (t, 4 H, S—CH ₂ CH ₂ CH ₂ —Si), _{1.87 (m, 4H, CH 2} CH 2 CH 2 -Si), 1.61 (m, 4H, SnCH 2 CH 2 CH 2 CH 3), 1,30 (m, 8H, SnCH 2 CH 2 CH 2 _{CH 3), 0.83 (t,} 6H, SnCH 2 CH 2 CH 2 CH 3), 0.78 (t, 4H, S-CH 2 CH 2 CH 2 -Si), 0.06 (s, 6H, Si (OMe) ₂ CH ₃ ) ppm;
¹³ C (101 MHz, 23 ° C., C ₆ D ₆ ): δ = 49.95 (OCH ₃ ), 31.01 (S—CH ₂ CH ₂ CH ₂ —Si), 28.70 (SCH ₂ CH ₂ CH ₂₎ ) & (SnCH ₂ CH ₂ CH ₂ CH ₃ ), 27.06 (SnCH ₂ CH ₂ CH ₂ CH ₃ ), 17.90 (SnCH ₂ CH ₂ CH ₂ CH ₃ ), 13.76 (SnCH ₂ CH ₂ CH) _{2 CH 3), 13.21 (S} -CH 2 CH 2 CH 2 -Si), - 5.47 (SiCH 3) ppm.
Modifier 4 is represented by the following Formula M4 and was prepared as follows.

Preparation route 1
In a 100 mL Schlenk tube, 50 ml of tetrahydrofuran (THF), 159 mg (20 mmol) of lithium hydroxide, and then 3.6 g (20 mmol) of gamma-mercaptopropyl (methyl) dimethoxysilane P1 obtained from ABCR GmbH, are introduced did. The reaction mixture was stirred at 65 ° C. for 2 hours. The reaction mixture was allowed to cool to room temperature. Subsequently, a solution of dimethyldichlorosilane (1.30 g (10 mmol)) in 10 g of THF was then added dropwise to a Schlenk tube. The reaction mixture was warmed to 65 ° C. and held at that temperature for 2 hours. Subsequently, the THF solvent was removed from the resulting mixture at room temperature under vacuum (vacuum) and the residue was dissolved in 50 mL of cyclohexane. The precipitated lithium chloride was separated by filtration from the reaction product dissolved in cyclohexane. The cyclohexane solvent was removed under vacuum (under reduced pressure). The resulting colorless liquid solution was found to be 95% pure by GC and thus no further purification was necessary. A yield of 3.9 g (9.3 mmol) of modifier M4 was obtained.

Preparation route 2
150 mL of cyclohexane, 5.05 g (50 mmol) of triethylamine in a 250 mL Schlenk tube, 9.02 g (50 mmol) of gamma-mercaptopropyl (methyl) dimethoxysilane P1 obtained from ABCR GmbH, and then Sigma-Aldrich 3.23 g (25 mmol) of dimethyldichlorosilane, which was obtained from H.K. The reaction mixture was stirred at 65 ° C. overnight. The reaction mixture was allowed to cool to room temperature. The mixture was filtered to remove all volatiles under reduced pressure to give 9.20 g (88%) yield of compound M4. The resulting solution of the colorless liquid modifier M4 was found by NMR to be 95% pure, thus no further purification was necessary.
¹ H-NMR (400 MHz, 23 ° C., C ₆ D ₆ ): δ = 3.32 (s, 12 H, SiOCH ₃ ), 2.57 (t, 4 H, S—CH ₂ ), 1.70 (m, _{4H, CH 2 CH 2 CH 2} ), 0.66 (m, 4H, CH 2 SiMe (OMe) 2), 0.43 (s, 6H, Si (OMe) CH 3), 0.01 (s, 6H , Si (OCH ₃ ) ₂ CH ₃ ) ppm; ¹³ C (101 MHz, 23 ° C., C ₆ D ₆ ): δ = 49.96 (OCH ₃ ), 30.90 (S-CH ₂ ), 26.67 (CH) _{2 CH 2 CH 2), 13.15} (CH 2 SiMe (OMe) 2), 2.06 (SiCH 3), - 5.48 (SiCH 3) ppm.
Modifier 5 is represented by Formula M5 below, and was prepared as follows.

Preparation route 50 ml of tetrahydrofuran (THF) in a 100 ml Schlenk tube, 360 mg (45.25 mmol) of lithium hydroxide and then 4.0 g (20 g) of gamma-mercaptopropyl (methyl) dimethoxysilane P1 obtained from ABCR GmbH .37 mmol) was charged. The reaction mixture was stirred at 25 ° C. for 1.5 hours. Next, a solution of n-butyl trichlorostannane (1.915 g (6.79 mmol)) in 10 g THF was subsequently added dropwise to the Schlenk tube. The reaction mixture was warmed to 65 ° C. and held at that temperature for 1.5 hours. The THF solvent was then removed from the resulting mixture at room temperature under vacuum (vacuum) and the residue was dissolved in 50 mL of pentane. The precipitated lithium chloride was separated by filtration from the reaction product dissolved in pentane. The pentane solvent was removed under vacuum (under reduced pressure). The resulting colorless liquid solution was found to be pure by NMR and thus no further purification was necessary. A yield of 4.3 g (5.5 mmol) of modifier M5 was obtained.
¹ H-NMR (400 MHz, 23 ° C., C ₆ D ₆ ): δ = 3.42 (s, 27 H, SiOCH ₃ ), 2.93 (t, 6 H, S—CH ₂ CH ₂ CH ₂ —Si), _{1.93 (m, 6H, CH 2} CH 2 CH 2 -Si), 1,47 (m, 2H, SnCH 2 CH 2 CH 2 CH 3), 1.44 (m, 2H, SnCH 2 CH 2 CH 2 _{CH 3), 1.18 (m,} 2H, SnCH 2 CH 2 CH 2 CH 3), 0.80 (t, 3H, SnCH 2 CH 2 CH 2 CH 3), 0.77 (t, 6H, S- _{CH 2 CH 2 CH 2 -Si)} ppm;
¹³ C (101 MHz, 23 ° C., C ₆ D ₆ ): δ = 50.34 (OCH ₃ ), 31.56 (S—CH ₂ CH ₂ CH ₂ —Si), 28.28 (SCH ₂ CH ₂ CH _{2) -Si), 27.58 (SnCH 2 CH} 2 CH 2 CH 3), 26.16 (SnCH 2 CH 2 CH 2 CH 3), 13.48 (SnCH 2 CH 2 CH 2 CH 3), 9.08 ( _{S-CH 2 CH 2 CH 2} -Si) ppm.
Modifier 6 is represented by Formula M6 below and was prepared as follows.

Preparation Route In a 250 mL Schlenk tube, 100 ml of tetrahydrofuran (THF), 716 mg (90.0 mmol) of lithium hydroxide, and then gamma-mercaptopropyltrimethoxysilane P2 [Silquest A-189] obtained from Cromton GmbH. 8.835 g (45 mmol) was charged. The reaction mixture was stirred at 25 ° C. for 2 hours. Thereafter, a solution of di-n-butyl dichlorostannane (6.84 g (22.5 mmol)) in 50 g of THF was then added dropwise to a Schlenk tube. The reaction mixture was warmed to 65 ° C. and held at that temperature for 1.25 hours. Subsequently, the THF solvent was removed under vacuum (vacuum) from the resulting mixture at room temperature and the residue was dissolved in 100 mL of pentane. The precipitated lithium chloride was separated by filtration from the reaction product dissolved in pentane. The pentane solvent was removed under vacuum (under reduced pressure). The resulting colorless liquid solution was found to be 83% pure by NMR. The yield was 10.4 g (16.7 mmol) of modifier M6, calculated on the pure modifier M6 isolated.
¹ H-NMR (400 MHz, 23 ° C., C ₆ D ₆ ): δ = 3.43 (s, 18 H, SiOCH ₃ ), 2.87 (t, 4 H, S—CH ₂ CH ₂ CH ₂ —Si), _{1.98 (m, 4H, CH 2} CH 2 CH 2 -Si), 1.64 (m, 4H, SnCH 2 CH 2 CH 2 CH 3), 1,30 (m, 8H, SnCH 2 CH 2 CH 2 _{CH 3), 0.88 (t,} 6H, SnCH 2 CH 2 CH 2 CH 3), 0.78 (t, 4H, S-CH 2 CH 2 CH 2 -Si) ppm;
¹³ C (101 MHz, 23 ° C., C ₆ D ₆ ): δ = 50.34 (OCH ₃ ), 28.59 (S-CH ₂ CH ₂ CH ₂ -Si), 28. 68 (SCH ₂ CH ₂ CH _{2) -Si), 30.79 (SnCH 2 CH} 2 CH 2 CH 3), 27.04 (SnCH 2 CH 2 CH 2 CH 3), 17.88 (SnCH 2 CH 2 CH 2 CH 3), 13.73 ( _{SnCH 2 CH 2 CH 2 CH 3} ), 9.25 (S-CH 2 CH 2 CH 2 -Si) ppm.

以下に式ＰＲ２で表されるガンマ−メルカプトプロピルトリメトキシシラン、Ｃｒｏｍｔｏｎ ＧｍｂＨ社より購入された。

Modifier Precursor Compound Gamma-mercaptopropyl (methyl) dimethoxysilane represented by the formula PR1 below, purchased from ABCR GmbH.

The gamma-mercaptopropyltrimethoxysilane represented by the formula PR2 below was purchased from Cromton GmbH.

Copolymerization of 1,3-Butadiene and Styrene (Example 3-28)
The copolymerization was carried out in a double walled 20 liter steel reactor which was first purged with nitrogen prior to the addition of the organic solvent, monomer, polar coordinator compound, initiator compound or other components. The polymerization reactor is adjusted to 40 ° C. unless otherwise stated. The following ingredients were then added in the following order: cyclohexane solvent (9000 grams), butadiene monomer, styrene monomer, tetramethylethylenediamine (TMEDA). The mixture was stirred for 1 hour and subsequently titrated with n-butyllithium to remove traces of water or other impurities. Additional n-butyllithium was added to initiate the polymerization reaction. The polymerization was carried out for 80 minutes such that the polymerization temperature did not exceed 60.degree. Thereafter, 0.5% of the total butadiene monomer amount is added followed by either the coupling agent or the modifier (1, 2, 3, 4, 5, or 6) unless otherwise stated. The To complete the polymerization process, after 45 minutes the polymer solution is another double-walled steel reactor containing 100 mL of ethanol as a polymer stabilizer and 1.4 g of concentrated HCl (36% strength) and 5 g of Irganox 1520. Was transferred to The mixture was stirred for 15 minutes. The resulting polymer solution is then exposed to steam for 1 hour to remove solvent and other volatiles and dried in an oven at 70 ° C. for 30 minutes, for an additional 1 to 3 days at room temperature. The

  The polymerization components are summarized in Table 2 below, the resulting polymer properties are summarized in Table 3, and the components of the polymer composition are summarized in Tables 4, 8 and 12. Unless otherwise stated, the amounts in Table 2 are expressed in mmol. The amounts in Tables 4, 8 and 12 are expressed in phr (parts by 100 parts of the total rubber component of the composition). Applied to the preparation of the polymer compositions according to the recipes shown in Tables 4, 8 and 12 under the same processing conditions (in the same Banbury mixer, under the same processing temperature and timeline, by the same operator on the same day) Examples of polymers to be added are indicated by the same letter adjacent to the example number (e.g. 3A, 4A).

The dash "-" notation used in the following table indicates that no component is added. The abbreviation "NM" is intended to indicate that no measurement was made or the corresponding data was absent.

The polymer composition was prepared by combining the components listed under Table 4 in a 350 cc Banbury mixer and vulcanizing at 160 ° C. for 20 minutes. The vulcanization data and physical properties of each elastomeric composition example are shown in Tables 5, 6 and 7.

Additional polymer compositions were prepared by combining the components listed under Table 8 in a 350 cc Banbury mixer and vulcanized at 160 ° C. for 20 minutes. The vulcanisation data and physical properties for each elastomeric composition example are shown in Tables 9, 10 and 11.

Additional polymer compositions were prepared by mixing and blending the components listed under Table 12 in a 350 cc Banbury mixer and vulcanizing at 160 ° C. for 20 minutes. The vulcanization data and properties of each elastomeric composition example are shown in Tables 13, 14 and 15.

  A silane sulfide modified polymer compound of the formula P1, P2, P3, P4, P5 or P6 is a silane sulfide modifier of the formula 1 comprising the formulas 5 and 6, optionally a coupling agent and optionally preferably the formula 7 It has been found that, in combination with the further modifier (s) selected from, one forms a polymer which can be used for the preparation of elastomeric and vulcanized elastomeric polymer compositions.

  The present invention provides (second) polymer compositions comprising silane sulfide modified polymeric compound (s) in addition to silica and / or carbon black, which comprise silane sulfide modified polymeric compound (s) It exhibits a lower increase in Mooney viscosity during the mixing of the individual components as compared to the corresponding polymer composition. This results in a lower Mooney viscosity of the resulting second polymer composition (Option 1), or a silane sulfide modified high having a higher Mooney viscosity compared to a reference polymer that does not contain silane sulfide modification By permitting the use of molecular compounds, a second polymer composition having a Mooney viscosity in the range close to the reference composition not containing the silane sulfide modified polymer compound is reached (Option 2).

  The low Mooney viscosity allows to increase the mixing throughput, or to reduce the number of individual mixing steps, and also to increase the extrusion rate of the final polymer composition. Based on Example 18H (Money viscosity 54.8 MU) of Table 15 containing the silane sulfide modified polymer 18 of Table 3 (Money viscosity 63.9 MU), and Table 15 based on Reference Polymer 17 (63.6 MU) of Table 3. Reference is made to Comparative Example 17H (Money viscosity 65.7 MU).

In order to carry out the formation of silane sulfide chain end modifiers according to formulas 1, 5 and 6, the structures of silane sulfide chain end modifiers M3, M4, M5 and M6 are ¹ H- and ¹³ C-NMR spectroscopy ( The method of preparation of M3, M4, M5 and M6 is as described above. Subsequently, the silane sulfide chain end modifier formed was used to prepare the polymer.

  In combination with the above mentioned application properties, it has surprisingly been found that silane sulfide modifiers lead to a higher degree of polymer chain bonding than polymers modified by equivalent (alternative) non-inventive modifiers. The For example, the modified polymer 3 of the present invention produced using the target silane sulfide chain end modifier M3 in Table 3 has a binding degree of 55.9% of the total amount of living polymer chains, but the target modifier The reference polymers 1 and 2 which were not produced with using resulted in a degree of bonding of 24.9 and 19.6%. It is generally accepted that increasing the degree of polymer binding results in relatively low polymer solution viscosities if the polymer weight average molecular weight (Mw) or the corresponding Mooney viscosity of the solvent free polymer is kept constant. In this case, it is possible to advantageously increase the productivity of the polymerization process and thus the throughput of polymer production. Alternatively, having an increased degree of polymer attachment means that the same polymer solution but with an increased weight average molecular weight (Mw) or an increased Mooney viscosity of the solventless polymer compared to a polymer with a relatively low degree of attachment It is generally accepted that it allows the preparation of polymers having a viscosity. Polymers with increased amount average molecular weight (Mw) or high solvent free Mooney viscosity are usually more difficult to process during extrusion of mechanical mixers, roll mills, or filler containing polymer compositions. It has surprisingly been found that the Mooney viscosity is relatively reduced when the silane sulfide modified polymer compound is mixed with silica or carbon black. As described above, in mechanical mixing of a silane sulfide modified polymer compound with a filler such as carbon black and silica, the silane sulfide modified polymer of the present invention, for example by conditions such as the presence of water at elevated temperature Cleavage of Si-S and Sn-S bonds present in the compound is caused. Thus, the silane sulfide-modified polymer compound having a relatively high degree of bonding can be a silane sulfide-modified polymer compound having a relatively low degree of bonding and / or a relatively low weight average molecular weight (Mw) during mechanical mixing with the filler. Or converted to a linear modified polymer compound having a relatively low Mooney viscosity value. Thus, the treatment of the silane sulfide-modified polymer compound during the formation of the polymer filler composition in the extrusion of a roll mill or polymer filler composition in addition to a mechanical mixer is significantly simplified and the mixing, roll mill or extrusion throughput Can be increased.

  The polymer compound of the present invention is included in the first composition. The first composition can be converted to a "second polymer composition" (according to Tables 4, 8 and 12 by adding a carbon black or silica filler to the modified polymer compound of the present invention) First stage mixing and second stage mixing), which may then be converted into a vulcanized polymer composition, which may for example be the result of the second stage mixing according to Tables 4, 8 and 12 Formed when cured at 20 ° C for 20 minutes. A second polymer composition (as listed in Tables 5, 9 and 13) and a vulcanized polymer composition (as listed in Tables 6, 10 and 14) prepared by the same operator and under the same conditions on the same day , For example A, B etc. are identified. The polymers contained in the vulcanized polymer composition are, for example, reflected in the polymer numbers such as 1, 2 and so on. As a result, there is a series of vulcanized polymer compositions such as 1A, 2A, 3A and 4A that can be compared directly to one another.

  Polymeric compound based second polymer compositions (Examples 16G and 11E of Table 7 and Examples 3A and 8C of Table 11) produced using the silane sulfide modifiers of the invention have relatively low Mooney viscosities A second polymer composition comprising a silane sulfide-modified polymer compound and carbon black as compared to a corresponding polymer composition comprising silica or carbon black and a reference polymer not comprising a silane sulfide-modified polymer compound. Calculated as the difference between the Mooney viscosity (also referred to as compounds Mooney in Tables 7 and 11) and the Mooney viscosity of the silane sulfide modified polymeric compound (also referred to as polymer Mooney). The second polymer compositions according to Examples 16G and 11E in Table 7 contain carbon black fillers as shown in Table 4. More specifically, the increase in Mooney viscosity as a result of adding carbon black to the polymer is 25.6 or 37.5 Mooney units (MU), respectively, when the reference polymer 14G or 15G is replaced with the silane sulfide modified composition 16G. Diminished. Furthermore, the increase in Mooney viscosity as a result of the addition of carbon black to the polymer was reduced by 24.7 or 27.3 MU, respectively, when polymer 9E or 10E was replaced with the silane sulfide modifying composition 11E. The second polymer compositions according to Examples 3A and 8C in Table 11 exhibit the silica fillers shown in Table 8. The increase in Mooney viscosity when silica was added to the polymer decreased by 17.1 or 16.1 MU, respectively, when replacing the reference polymer 1A or 2A with the silane sulfide modified polymer 3A. Furthermore, the increase in Mooney viscosity when silica is added to the polymer decreased by 6.1 MU when replacing the reference polymer 7C with the silane sulfide modified polymer 8C.

  The use of a silane sulfide modified polymer compound results in lower "Tan δ" values at 60 ° C., higher "Tan δ" values at 0 ° C., and higher "-" values compared to the reference polymer without silane sulfide modification. At least one of the properties of the "Tan δ" value at 10 ° C. is improved, making it possible to produce a vulcanized polymer composition according to option 2, the other properties being of comparable level. Process of combining the A) polymerization initiator compounds of the present invention with B) a silane sulfide modifier, optionally C) a coupling agent and optionally D) other modifiers to increase the degree of polymer modification and improve performance provide.

  Vulcanized carbon black containing polymer compositions (see Examples 13F of Tables 5 and 6) based on polymers formed from the silane sulfide modifiers of the present invention are elastomeric vulcanized polymer compositions (Table 5) based on other polymers. Relatively low (or decreased) values for tan δ at 60 ° C., and relatively high (or increased) values for tan δ at 0 ° C., as compared to Examples 12 F and 6 of It has relatively high (or elevated) values for tan δ at 10 ° C., and relatively reduced tire heat. The exemplary vulcanized composition 13F obtained with the silane sulfide modifying agent M4 of the present invention and the further modifying agent M1 based on the silane sulfide modified polymer 13 has tan δ values at 60 ° C. and 85.5 ° C. 0.079, based on non-inventive chain end modifiers M1 and M2, based on non-modified polymer 12, having a tan δ value at 0.7 ° C. and a tan δ value at −10 ° C. of 1.187 The vulcanized composition 12F has a relatively high exotherm of 86.1 ° C., a tan δ value of 60 ° C. of relatively high 0.086, a tan δ value of 0 ° C. of relatively low 0.667, and 1.151 Have relatively low tan δ values at -10 ° C.

  Vulcanized silica-containing polymer compositions (see Examples 3A in Tables 9 and 10) based on polymers produced from the silane sulfide modifiers of the invention are elastomer vulcanised polymer compositions (Table 9 and in Table 9 and 10). It has relatively high (or elevated) tan δ value at -10 ° C. and relatively low tire heat as compared to 10) (see Examples 1A and 2A). The exemplary vulcanized composition 3A obtained with the silane sulfide modifier M3 of the present invention based on the silane sulfide modified polymer 3 has an exotherm of 88.4 ° C. and a tan δ value at −10 ° C. of 0.571 Vulcanizing compositions 1A and 2A, which are both based on non-modified polymers 1 and 2 and modified by other modifiers M1 or modifiers M1 and M2, respectively, compare 90.6 ° C. and 95.5 ° C. respectively High exotherm value, and tan δ value at relatively low -10 ° C. of 0.564 and 0.548.

式中、
Ｍはケイ素またはスズであり、
ｘは１、２、および３から選択される整数であり、
ｙは０、１、および２から選択される整数であって、ｘ＋ｙ＝３であり、
ｓは２、３、および４から選択される整数であり、
ｔは０、１、および２から選択される整数であり、
ｕは０、１、および２から選択される整数であって、ｓ＋ｔ＋ｕ＝４であり、
Ｒ ¹ は独立して、水素および（Ｃ ₁ −Ｃ ₆ ）アルキルから選択され、
Ｒ ² は独立して、（Ｃ ₁ −Ｃ ₁₆ ）アルキル、（Ｃ ₇ −Ｃ ₁₆ ）アルキルアリール、および（Ｃ ₇ −Ｃ ₁₆ ）アリールアルキルから選択され、
Ｒ ³ は少なくとも二価であり、独立して、（Ｃ ₁ −Ｃ ₁₆ ）アルキル、（Ｃ ₈ −Ｃ ₁₆ ）アルキルアリールアルキル、（Ｃ ₇ −Ｃ ₁₆ ）アリールアルキル、および（Ｃ ₇ −Ｃ ₁₆ ）アルキルアリールから選択され、各基は以下の基：第三級アミン基、シリル基、（Ｃ ₇ −Ｃ ₁₈ ）アラルキル基、および（Ｃ ₆ −Ｃ ₁₈ ）アリール基のうちの１つ以上で置換されていてもよく、
Ｒ ⁴ は独立して、（Ｃ ₁ −Ｃ ₁₆ ）アルキルおよび（Ｃ ₇ −Ｃ ₁₆ ）アルキルアリールから選択され、
Ｘは独立して、塩化物、臭化物、および−ＯＲ ⁵ から選択され、式中、Ｒ ⁵ は（Ｃ ₁ −Ｃ ₁₆ ）アルキルおよび（Ｃ ₇ −Ｃ ₁₆ ）アリールアルキルから選択される、シランスルフィド変性剤。
［２］
Ｒ ³ は二価の（Ｃ ₁ −Ｃ ₁₆ ）アルキルである、項目１に記載のシランスルフィド変性剤。
［３］
Ｘは塩化物、臭化物、および−ＯＲ ⁵ から選択され、式中、Ｒ ⁵ は（Ｃ ₁ −Ｃ ₁₆ ）アルキルから選択される、項目１または２に記載のシランスルフィド変性剤。
［４］
Ｒ ² およびＲ ⁴ は独立して、（Ｃ ₁ −Ｃ ₁₆ ）アルキルから選択される、項目１〜３のいずれか１項に記載のシランスルフィド変性剤。
［５］
Ｒ ¹ 、Ｒ ² 、Ｒ ⁴ 、およびＲ ⁵ は独立して、（Ｃ ₁ −Ｃ ₄ ）アルキルから選択される、項目１〜４のいずれか１項に記載のシランスルフィド変性剤。
［６］
ｓおよびｔがそれぞれ２であり、ｕが０であるか、あるいはｓは３であり、ｔは１であり、ｕは０である、項目１〜５のいずれか１項に記載のシランスルフィド変性剤。
［７］
ｘは２であり、ｙが１であるか、あるいはｘは１であり、ｙは２である、項目１〜６のいずれか１項に記載のシランスルフィド変性剤。
［８］
以下の式５または式６を有し、

式中、
Ｍはケイ素原子またはスズ原子であり、
Ｒ ³ は少なくとも二価であり、（Ｃ ₈ −Ｃ ₁₆ ）アルキルアリールアルキル、（Ｃ ₇ −Ｃ ₁₆ ）アリールアルキル、（Ｃ ₇ −Ｃ ₁₆ ）アルキルアリール、または（Ｃ ₁ −Ｃ ₁₆ ）アルキルであり、各基は以下の基、第三級アミン基、シリル基、（Ｃ ₇ −Ｃ ₁₈ ）アラルキル基、および（Ｃ ₆ −Ｃ ₁₈ ）アリール基のうちの１つ以上で置換されていてもよく、
Ｒ ¹ 、Ｒ ¹² 、およびＲ ¹⁶ はそれぞれ独立して、水素原子および（Ｃ ₁ −Ｃ ₄ ）アルキルから選択され、
Ｒ ² 、Ｒ ¹³ 、およびＲ ¹⁵ はそれぞれ独立して、（Ｃ ₁ −Ｃ ₁₆ ）アルキル、（Ｃ ₇ −Ｃ ₁₆ ）アルキルアリール、および（Ｃ ₇ −Ｃ ₁₆ ）アリールアルキルから選択され、
Ｒ ⁴ およびＲ ¹⁴ はそれぞれ独立して、（Ｃ ₁ −Ｃ ₁₆ ）アルキルおよび（Ｃ ₇ −Ｃ ₁₆ ）アルキルアリールから選択され、
ｂ、ｄ、およびｆはそれぞれ独立して、０、１、および２の整数から選択され、ａ、ｃ、およびｅはそれぞれ独立して、１、２、および３の整数から選択され、ａ＋ｂ＝３であり、ｃ＋ｄ＝３であり、ならびにｅ＋ｆ＝３である、項目１に記載のシランスルフィド変性剤。
［９］
Ｒ ³ は（Ｃ ₁ −Ｃ ₁₆ ）の二価のアルキル基または（Ｃ ₈ −Ｃ ₁₆ ）の二価のアルキルアリールアルキル基である、項目８に記載のシランスルフィド変性剤。
［１０］
Ｒ ³ は−ＣＨ ₂ −、−（ＣＨ ₂ ） ₂ −、−（ＣＨ ₂ ） ₃ −、−（ＣＨ ₂ ） ₄ −、−ＣＨ ₂ −Ｃ ₆ Ｈ ₄ −ＣＨ ₂ −、および−Ｃ ₆ Ｈ ₄ −Ｃ（ＣＨ ₃ ） ₂ −Ｃ ₆ Ｈ ₄ −から選択される、項目８または９に記載のシランスルフィド変性剤。
［１１］
Ｒ ² 、Ｒ ⁴ 、Ｒ ¹³ 、およびＲ ¹⁵ がそれぞれ独立して、（Ｃ ₁ −Ｃ ₁₆ ）アルキルから選択される、項目８〜１０のいずれか１項に記載のシランスルフィド変性剤。
［１２］
Ｍはケイ素原子であり、ａ、ｃ、およびｅはそれぞれ２および３から選択される整数であり、ｂ、ｄ、およびｅはそれぞれ０および１から選択される整数である、項目８〜１１のいずれか１項に記載のシランスルフィド変性剤。
［１３］
項目１〜１２のいずれか１項に規定される式１、式５、または式６のシランスルフィド変性剤を製造する方法であって、
（ｉ）
（ｉａ）以下の式２の化合物

（式中、Ｒ ¹ 、Ｒ ² 、Ｒ ³ 、ｘ、およびｙは項目１に規定されるとおりである）、および
（ｉｂ）以下の式３ａおよび式３ｂから選択されるアミン化合物

（式中、Ｒ ⁵ 、Ｒ ⁶ 、Ｒ ⁷ 、Ｒ ⁸ 、Ｒ ⁹ 、Ｒ ¹⁰ 、およびＲ ¹¹ はそれぞれ独立して、水素、（Ｃ ₁ −Ｃ ₁₆ ）アルキル、（Ｃ ₇ −Ｃ ₁₆ ）アルキルアリール、（Ｃ ₇ −Ｃ ₁₆ ）アリールアルキル、および（Ｃ ₆ −Ｃ ₁₆ ）アリールから選択され、ｖは１〜１０から選択される整数である）を組み合わせるステップと、
（ｉｉ）ステップ（ｉ）の結果として得られる混合物を以下の式４の化合物

（式中、Ｍはケイ素またはスズであり、ｕは２、３、および４から選択される整数であり、Ｒ ⁴ 、Ｘ、およびｔは項目１に規定されるとおりであり、ｔ＋ｕ＝４である）と、
溶媒中にて反応させるステップと、
（ｉｉｉ）任意に、ステップ（ｉｉ）にて得られた式１、式５、または式６のシランスルフィド変性剤を単離するステップと、を含む、方法。
［１４］
項目１〜１２のいずれか１項に規定される、式１、式５、または式６のシランスルフィド変性剤を製造する方法であって、
（ｉ）上に規定される式２の化合物をアルカリ金属ヒドリドと溶媒中にて反応させるステップと、
（ｉｉ）ステップ（ｉ）の結果として得られる反応生成物を、上に規定される式４の化合物と溶媒中にて反応させるステップと、
（ｉｉｉ）任意に、ステップ（ｉｉ）にて得られる式１、式５、または式６のシランスルフィド変性剤を単離するステップと、を含む、方法。
［１５］
ステップ（ｉｉ）で得られる式１、式５、または式６の前記シランスルフィド変性剤が、ろ過、前記溶媒の蒸発、または蒸留によってステップ（ｉｉｉ）で単離される、項目１３または１４に記載の方法。
［１６］
ｉ）リビングアニオンエラストマーポリマー、および
ｉｉ）項目１〜１２のいずれか１項に規定される、式１、式５、または式６で表されるシランスルフィド変性剤、を反応させることで得られる、シランスルフィド変性エラストマー高分子化合物。
［１７］
以下の式Ｐ１で表され、

式中、
Ｐは以下のモノマー基、ブタジエン、イソプレン、スチレン、およびアルファ−メチルスチレン、の少なくとも１つに由来するモノマー単位を含むポリマー鎖であり、１高分子あたりのモノマー単位数が１０〜５０．０００、好ましくは２０〜４０．０００の範囲内であり、Ｍはケイ素原子またはスズ原子であり、
Ｘは１、２、および３から選択される整数であり、ｙは０、１、および２から選択される整数であり、ｒは１、２、および３から選択される整数であり、ｘ＋ｙ＋ｒ＝３であり、
Ｓは２、３、および４から選択される整数であり、ｔは０、１、および２から選択される整数であり、ｕは０、１、および２から選択される整数であり、ｓ＋ｔ＋ｕ＝４であり、
Ｒ ¹ は独立して、水素原子および（Ｃ ₁ −Ｃ ₆ ）アルキルから選択され、
Ｒ ² は独立して、（Ｃ ₁ −Ｃ ₁₆ ）アルキル、（Ｃ ₇ −Ｃ ₁₆ ）アルキルアリール、および（Ｃ ₇ −Ｃ ₁₆ ）アリールアルキルから選択され、
Ｒ ³ は少なくとも二価であり、独立して、（Ｃ ₁ −Ｃ ₁₆ ）アルキル、（Ｃ ₈ −Ｃ ₁₆ ）アルキルアリールアルキル、（Ｃ ₇ −Ｃ ₁₆ ）アリールアルキル、および（Ｃ ₇ −Ｃ ₁₆ ）アルキルアリールから選択され、各基は以下の基：第三級アミン基、シリル基、（Ｃ ₇ −Ｃ ₁₈ ）アラルキル基、および（Ｃ ₆ −Ｃ ₁₈ ）アリール基のうちの１つ以上で置換され得て、
Ｒ ⁴ は独立して、（Ｃ ₁ −Ｃ ₁₆ ）アルキルおよび（Ｃ ₇ −Ｃ ₁₆ ）アルキルアリールから選択され、
Ｘは独立して、塩化物、臭化物、および−ＯＲ ⁵ から選択され、式中、Ｒ ⁵ は（Ｃ ₁ −Ｃ ₁₆ ）アルキルおよび（Ｃ ₇ −Ｃ ₁₆ ）アリールアルキルから選択される、項目１６に記載のシランスルフィド変性エラストマー高分子化合物。
［１８］
Ｒ ³ が二価の（Ｃ ₁ −Ｃ ₁₆ ）アルキルである、項目１７に記載のシランスルフィド変性エラストマー高分子化合物。
［１９］
Ｘは塩化物、臭化物、および−ＯＲ ⁵ から選択され、式中、Ｒ ⁵ は（Ｃ ₁ −Ｃ ₁₆ ）アルキルから選択される、項目１７または１８に記載のシランスルフィド変性エラストマー高分子化合物。
［２０］
Ｒ ² およびＲ ⁴ は独立して、（Ｃ ₁ −Ｃ ₁₆ ）アルキルから選択される、項目１７〜１９のいずれか１項に記載のシランスルフィド変性エラストマー高分子化合物。
［２１］
Ｒ ¹ 、Ｒ ² 、Ｒ ⁴ 、およびＲ ⁵ は独立して、（Ｃ ₁ −Ｃ ₄ ）アルキルから選択される、項目１７〜２０のいずれか１項に記載のシランスルフィド変性エラストマー高分子化合物。
［２２］
ｓおよびｔはそれぞれ２であり、ｕは０であるか、あるいは、ｓは３であり、ｔは１であり、ｕは０である、項目１７〜２１のいずれか１項に記載のシランスルフィド変性エラストマー高分子化合物。
［２３］
ｒは１であり、ｘは１であり、ｙは１であるか、あるいは、ｒは１であり、ｘは０であり、ｙは２である、項目１７〜２２のいずれか１項に記載のシランスルフィド変性エラストマー高分子化合物。
［２４］
項目１６〜２３のいずれか１項に規定される前記シランスルフィド変性エラストマー高分子化合物を製造する方法であって、
（Ａ）重合開始剤を、ブタジエン、スチレン、イソプレン、アルファメチル−スチレン、およびその組み合わせから選択されるモノマーを含む１つ以上のモノマー種と重合溶媒中にて反応させて、反応混合物Ａを形成するステップと、
（Ｂ）任意に、反応混合物Ａを少なくとも１つのカップリング剤と反応させて反応混合物Ｂを形成するステップと、
（Ｃ）前記反応混合物ＡまたはＢを、項目１〜１２のいずれか１項で規定される、式１、式５、または式６のシランスルフィド変性剤の少なくとも１つと反応させて、シランスルフィド変性高分子化合物を製造するステップと、
（Ｄ）任意に、ステップ（Ｃ）で得られた前記反応混合物をさらなる変性剤と反応させるステップと、を含む、方法。
［２５］
ステップ（Ｂ）に用いられる前記少なくとも１つのカップリング剤は、ＳｎＣｌ ₄ 、（Ｒ ₁ ） ₃ ＳｎＣｌ、（Ｒ ₁ ） ₂ ＳｎＣｌ ₂ 、Ｒ ₁ ＳｎＣｌ ₃ 、ＳｉＣｌ ₄ 、（Ｒ ₁ ） ₃ ＳｉＣｌ、（Ｒ ₁ ） ₂ ＳｉＣｌ ₂ 、Ｒ ₁ ＳｉＣｌ ₃ 、Ｃｌ ₃ Ｓｉ−ＳｉＣｌ ₃ 、Ｃｌ ₃ Ｓｉ−Ｏ−ＳｉＣｌ ₃ 、Ｃｌ ₃ Ｓｎ−ＳｎＣｌ ₃ 、Ｃｌ ₃ Ｓｎ−Ｏ−ＳｎＣｌ ₃ （式中、Ｒ ₁ は上に規定されるとおりである）、Ｓｎ（ＯＭｅ） ₄ 、Ｓｉ（ＯＭｅ） ₄ 、Ｓｎ（ＯＥｔ） ₄ 、およびＳｉ（ＯＥｔ） ₄ からなる群より選択される、項目２４に記載の方法。
［２６］
ステップ（Ｄ）にて用いられる前記さらなる変性剤は以下の式７で表され、

式中、
Ｍ ¹ はケイ素またはスズであり、ｘは１、２、および３から選択される整数であり、ｙは０、１、および２から選択される整数であり、ｘ＋ｙ＝３であり、Ｒは独立して、（Ｃ ₁ −Ｃ ₁₆ ）アルキルから選択され、Ｒ’は（Ｃ ₁ −Ｃ ₁₆ ）アルキル、（Ｃ ₈ −Ｃ ₁₆ ）アルキルアリールアルキル、（Ｃ ₇ −Ｃ ₁₆ ）アリールアルキル、および（Ｃ ₇ −Ｃ ₁₆ ）アルキルアリールである、項目２４または２５に記載の方法。
［２７］
項目１〜１２のいずれか１項に規定されるシランスルフィド変性高分子化合物を少なくとも１つ、および、前記変性高分子化合物を製造するのに用いられる重合処理に添加されるかその結果として得られる成分ならびに前記重合処理から溶媒を除去した後に残留する成分から選択される１つ以上のさらなる成分を含む、ポリマー組成物。
［２８］
少なくとも１つの充填剤を含む、項目２７に記載のポリマー組成物。
［２９］
前記充填剤が、カーボンブラック、シリカ、カーボン−シリカ二相充填剤、粘土、炭酸カルシウム、炭酸マグネシウム、リグニン、およびガラス粒子から１つ以上選択される、項目２８に記載のポリマー組成物。
［３０］
前記充填剤はシリカを含む、項目２９に記載のポリマー組成物。
［３１］
前記充填剤はカーボンブラックを含む、項目２９または３０に記載のポリマー組成物。
［３２］
加硫剤を含む、項目２７〜３１のいずれか１項に記載のポリマー組成物。
［３３］
ポリブタジエン、ブタジエン−スチレンコポリマー、ブタジエン−イソプレンコポリマー、ポリイソプレン、およびブタジエン−スチレン−イソプレンターポリマーからなる群より選択される少なくとも１つのポリマーを含む、項目２７〜３２のいずれか１項に記載のポリマー組成物。
［３４］
少なくとも以下の
１）少なくとも１つの加硫剤、および
２）項目２７〜３３のいずれか１項に規定されるポリマー組成物、の反応生成物を含む、加硫ポリマー組成物。
［３５］
加硫ポリマー組成物を製造する方法であって、少なくとも以下の成分
１）少なくとも１つの加硫剤、および
２）項目２７〜３３のいずれか１項に規定される前記ポリマー組成物、を反応させることを含む、方法。
［３６］
項目３５に規定される前記加硫ポリマー組成物から形成される少なくとも１つの成分を含む、物品。
［３７］
タイヤ、タイヤトレッド、タイヤ側壁、タイヤカーカス、ベルト、ホース、制振体、および履物部品からなる群より選択される、項目３６に記載の物品。
One particular application of modified elastomeric polymers is in the preparation of elastomeric polymer compositions, which are also specifically used in tire treads, and can have one or more of the following important properties: low viscosity during manufacture, Low rolling resistance, relatively reduced tire heat, improved wet grip, improved ice skid. Hereinafter, examples of embodiments of the present invention will be listed.
[1]
It is a silane sulfide modifier represented by the following formula 1,

During the ceremony
M is silicon or tin,
x is an integer selected from 1, 2 and 3 and
y is an integer selected from 0, 1, and 2 and x + y = 3,
s is an integer selected from 2, 3 and 4 and
t is an integer selected from 0, 1 and 2;
u is an integer selected from 0, 1 and 2 and s + t + u = 4,
R ¹ is independently selected from hydrogen and (C ₁ -C ₆ ) alkyl,
R ² is independently selected from (C ₁ -C ₁₆ ) alkyl, (C ₇ -C ₁₆ ) alkylaryl, and (C ₇ -C ₁₆ ) arylalkyl,
R ³ is at least bivalent and is independently (C ₁ -C ₁₆ ) alkyl, (C ₈ -C ₁₆ ) alkylarylalkyl, (C ₇ -C ₁₆ ) arylalkyl, and (C ₇ -C ₁₆₎ ) Alkylaryl, wherein each group is one or more of the following groups: tertiary amine group, silyl group, (C ₇ -C ₁₈ ) aralkyl group, and (C ₆ -C ₁₈ ) aryl group It may be substituted,
R ⁴ is independently selected from (C ₁ -C ₁₆ ) alkyl and (C ₇ -C ₁₆ ) alkylaryl;
X is independently selected from chloride, bromide, and -OR ⁵ , wherein R ⁵ is a silane sulfide selected from (C ₁ -C ₁₆ ) alkyl and (C ₇ -C ₁₆ ) arylalkyl Modifier.
[2]
The silane sulfide modifier according to claim 1, wherein R ³ is divalent (C ₁ -C ₁₆ ) alkyl.
[3]
X is chloride, is selected bromide, and -OR ^5, wherein, R ⁵ is selected from (C ₁ -C ₁₆₎ alkyl, Shiransurufido modifier according to claim 1 or 2.
[4]
The silane sulfide modifier according to any one of items 1 to 3, wherein R ² and R ⁴ are independently selected from (C ₁ -C ₁₆ ) alkyl.
[5]
R ^1, R ^2, R ^4, and R ⁵ are independently, (C ₁ -C ₄₎ is selected from alkyl, Shiransurufido modifier according to any one of claims 1 to 4.
[6]
The silane sulfide-modified according to any one of items 1 to 5, wherein s and t are 2 and u is 0 or s is 3 and t is 1 and u is 0. Agent.
[7]
The silane sulfide modifier according to any one of Items 1 to 6, wherein x is 2 and y is 1 or x is 1 and y is 2.
[8]
Have the following Equation 5 or Equation 6,

During the ceremony
M is a silicon atom or a tin atom,
R ³ is at least bivalent and is (C ₈ -C ₁₆ ) alkylarylalkyl, (C ₇ -C ₁₆ ) arylalkyl, (C ₇ -C ₁₆ ) alkylaryl, or (C ₁ -C ₁₆ ) alkyl And each group may be substituted with one or more of the following groups: tertiary amine group, silyl group, (C ₇ -C ₁₈ ) aralkyl group, and (C ₆ -C ₁₈ ) aryl group Often,
R ¹ , R ¹² and R ¹⁶ are each independently selected from hydrogen atom and (C ₁ -C ₄ ) alkyl;
R ² , R ¹³ and R ¹⁵ are each independently selected from (C ₁ -C ₁₆ ) alkyl, (C ₇ -C ₁₆ ) alkylaryl and (C ₇ -C ₁₆ ) arylalkyl;
R ⁴ and R ¹⁴ are each independently selected from (C ₁ -C ₁₆ ) alkyl and (C ₇ -C ₁₆ ) alkylaryl;
b, d and f are each independently selected from the integers of 0, 1 and 2; a, c and e are each independently selected from the integers of 1, 2 and 3; a + b = 3. The silane sulfide modifier according to item 1, which is 3 and c + d = 3 and e + f = 3.
[9]
9. The silane sulfide modifier according to item 8, wherein R ³ is a (C ₁ -C ₁₆ ) divalent alkyl group or a (C ₈ -C ₁₆ ) divalent alkylarylalkyl group.
[10]
R ³ is —CH ₂ —, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, —CH ₂ —C ₆ H ₄ —CH ₂ —, or —C ₆ H _{4 -C (CH 3) 2 -C} 6 H 4 - is selected from, Shiransurufido denaturing agent according to claim 8 or 9.
[11]
11. The silane sulfide modifier according to any one of items 8 to 10, wherein R ² , R ⁴ , R ¹³ and R ¹⁵ are each independently selected from (C ₁ -C ₁₆ ) alkyl.
[12]
M is a silicon atom, a, c, and e are integers selected from 2 and 3, respectively, b, d, and e are integers selected from 0 and 1, respectively The silane sulfide modifier according to any one of the above.
[13]
A method for producing a silane sulfide modifying agent of formula 1, formula 5, or formula 6 as defined in any one of items 1 to 12,
(I)
(Ia) compounds of formula 2 below

Wherein R ¹ , R ² , R ³ , x and y are as defined in item 1), and
(Ib) an amine compound selected from the following Formula 3a and Formula 3b

(Wherein, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are each independently hydrogen, (C ₁ -C ₁₆ ) alkyl, (C ₇ -C ₁₆ ) alkyl Combining aryl, (C ₇ -C ₁₆ ) arylalkyl, and (C ₆ -C ₁₆ ) aryl, wherein v is an integer selected from 1 to 10;
(Ii) the resulting mixture of step (i) is a compound of formula 4

(Wherein, M is silicon or tin, u is an integer selected from 2, 3 and 4; R ⁴ , X and t are as defined in item 1, and t + u = 4) If there,
Reacting in a solvent;
(Iii) optionally isolating the silane sulfide modifier of formula 1, 5 or 6 obtained in step (ii).
[14]
A method of producing the silane sulfide modifying agent of Formula 1, Formula 5, or Formula 6, as defined in any one of Items 1 to 12,
(I) reacting the compound of formula 2 as defined above with an alkali metal hydride in a solvent;
(Ii) reacting the resulting reaction product of step (i) with a compound of formula 4 as defined above in a solvent;
(Iii) optionally isolating the silane sulfide modifier of formula 1, 5 or 6 obtained in step (ii).
[15]
15. The silane sulfide modifying agent of formula 1, 5 or 6 obtained in step (ii) is isolated in step (iii) by filtration, evaporation of the solvent or distillation Method.
[16]
i) living anionic elastomeric polymers, and
ii) A silane sulfide-modified elastomeric polymer compound obtained by reacting the silane sulfide modifier represented by Formula 1, Formula 5, or Formula 6 as defined in any one of Items 1 to 12.
[17]
It is expressed by the following equation P1,

During the ceremony
P is a polymer chain containing monomer units derived from at least one of the following monomer groups, butadiene, isoprene, styrene, and alpha-methylstyrene, and the number of monomer units per one polymer is 10 to 50.000, Preferably, it is in the range of 20 to 40.000, and M is a silicon atom or a tin atom,
X is an integer selected from 1, 2 and 3; y is an integer selected from 0, 1 and 2; r is an integer selected from 1, 2 and 3; x + y + r = 3 and
S is an integer selected from 2, 3 and 4; t is an integer selected from 0, 1 and 2; u is an integer selected from 0, 1 and 2; s + t + u = 4 and
R ¹ is independently selected from hydrogen atom and (C ₁ -C ₆ ) alkyl,
R ² is independently selected from (C ₁ -C ₁₆ ) alkyl, (C ₇ -C ₁₆ ) alkylaryl, and (C ₇ -C ₁₆ ) arylalkyl,
R ³ is at least bivalent and is independently (C ₁ -C ₁₆ ) alkyl, (C ₈ -C ₁₆ ) alkylarylalkyl, (C ₇ -C ₁₆ ) arylalkyl, and (C ₇ -C ₁₆₎ ) Alkylaryl, wherein each group is one or more of the following groups: tertiary amine group, silyl group, (C ₇ -C ₁₈ ) aralkyl group, and (C ₆ -C ₁₈ ) aryl group Can be replaced,
R ⁴ is independently selected from (C ₁ -C ₁₆ ) alkyl and (C ₇ -C ₁₆ ) alkylaryl;
X is independently chloride, bromide, and is selected from -OR ^5, wherein, R ⁵ is selected from (C ₁ -C ₁₆₎ alkyl and (C ₇ -C ₁₆₎ arylalkyl, item 16 The silane sulfide modified | denatured elastomeric high molecular compound as described in-.
[18]
The silane sulfide-modified elastomeric polymer according to item 17, wherein R ³ is divalent (C ₁ -C ₁₆ ) alkyl.
[19]
X is chloride, bromide, and is selected from -OR ^5, wherein, R ⁵ is (C ₁ -C ₁₆₎ is selected from alkyl, Shiransurufido modified elastomer polymer compound according to claim 17 or 18.
[20]
20. The silane sulfide modified elastomeric high molecular compound according to any one of items 17 to 19, wherein R ² and R ⁴ are independently selected from (C ₁ -C ₁₆ ) alkyl.
[21]
The silane sulfide-modified elastomeric polymer compound according to any one of items 17 to 20, wherein R ¹ , R ² , R ⁴ and R ⁵ are independently selected from (C ₁ -C ₄ ) alkyl.
[22]
The silane sulfide according to any one of items 17 to 21, wherein s and t are each 2 and u is 0 or s is 3 and t is 1 and u is 0. Modified elastomeric polymer compound.
[23]
25. The method according to any one of items 17 to 22, wherein r is 1 and x is 1 and y is 1 or r is 1 and x is 0 and y is 2 Silane sulfide modified elastomeric polymer compound.
[24]
26. A method of producing the silane sulfide-modified elastomer polymer compound as defined in any one of items 16 to 23, wherein
(A) A polymerization initiator is reacted in the polymerization solvent with one or more monomer species comprising monomers selected from butadiene, styrene, isoprene, alpha methyl-styrene, and combinations thereof to form a reaction mixture A Step to
(B) optionally reacting the reaction mixture A with at least one coupling agent to form a reaction mixture B;
(C) Reacting the reaction mixture A or B with at least one of the silane sulfide modifiers of Formula 1, Formula 5, or Formula 6, as defined in any one of items 1 to 12, to modify the silane sulfide Producing a polymer compound;
(D) optionally reacting the reaction mixture obtained in step (C) with a further denaturing agent.
[25]
The at least one coupling agent used in step (B) is SnCl ₄ , (R ₁ ) ₃ SnCl, (R ₁ ) ₂ SnCl ₂ , R ₁ SnCl ₃ , SiCl ₄ , (R ₁ ) ₃ SiCl, ( R ₁ ) ₂ SiCl ₂ , R ₁ SiCl ₃ , Cl ₃ Si-SiCl ₃ , Cl ₃ Si-O-SiCl ₃ , Cl ₃ Sn-SnCl ₃ , Cl ₃ Sn-O-SnCl ₃ (wherein, R ₁ is 25. A method according to item 24, selected from the group consisting of : Sn (OMe) ₄ , Si (OMe) ₄ , Sn (OEt) ₄ , and Si (OEt) ₄ as defined above .
[26]
Said further modifier used in step (D) is represented by the following formula 7

During the ceremony
M ¹ is silicon or tin, x is an integer selected from 1, 2 and 3, y is an integer selected from 0, 1 and 2 and x + y = 3, R is independent Are selected from (C ₁ -C ₁₆ ) alkyl, R ′ is (C ₁ -C ₁₆ ) alkyl, (C ₈ -C ₁₆ ) alkylarylalkyl, (C ₇ -C ₁₆ ) arylalkyl, and The method according to item 24 or 25, which is C ₇ -C ₁₆ ) alkylaryl.
[27]
Item 11. At least one silane sulfide modified polymer compound as defined in any one of items 1 to 12 and added to or obtained as a result of polymerization treatment used for producing the modified polymer compound A polymer composition comprising an ingredient and one or more further ingredients selected from ingredients remaining after removing the solvent from the polymerization process.
[28]
29. Polymer composition according to item 27, comprising at least one filler.
[29]
29. The polymer composition according to item 28, wherein the filler is one or more selected from carbon black, silica, carbon-silica dual phase filler, clay, calcium carbonate, magnesium carbonate, lignin and glass particles.
[30]
30. The polymer composition according to item 29, wherein the filler comprises silica.
[31]
30. A polymer composition according to item 29 or 30, wherein the filler comprises carbon black.
[32]
32. A polymer composition according to any one of items 27-31, comprising a vulcanizing agent.
[33]
32. The polymer according to any one of items 27 to 32, comprising at least one polymer selected from the group consisting of polybutadiene, butadiene-styrene copolymer, butadiene-isoprene copolymer, polyisoprene and butadiene-styrene-isoprene terpolymer Composition.
[34]
At least
1) at least one vulcanizing agent, and
2) A vulcanized polymer composition comprising the reaction product of the polymer composition as defined in any one of items 27-33.
[35]
A method of producing a vulcanized polymer composition, comprising at least the following components:
1) at least one vulcanizing agent, and
2) A method comprising reacting the polymer composition as defined in any one of items 27-33.
[36]
An article comprising at least one component formed from said vulcanized polymer composition as defined in item 35.
[37]
37. An article according to item 36, selected from the group consisting of a tire, a tire tread, a tire sidewall, a tire carcass, a belt, a hose, a damping body, and a footwear part.

Claims (19)

i) a living anionic elastomeric polymer,
ii) A silane sulfide-modified elastomeric polymer compound containing a reaction product with a silane sulfide modifier represented by the following formula 5 or formula 6.

During the ceremony
M is a silicon atom or a tin atom,
R ³ is at least bivalent and is (C ₈ -C ₁₆ ) alkylarylalkyl, (C ₇ -C ₁₆ ) arylalkyl, (C ₇ -C ₁₆ ) alkylaryl, or (C ₁ -C ₁₆ ) alkyl And each group may be substituted with one or more of the following groups: tertiary amine group, silyl group, (C ₇ -C ₁₈ ) aralkyl group, and (C ₆ -C ₁₈ ) aryl group Often,
R ¹ , R ¹² and R ¹⁶ are each independently selected from ( C ₁ -C ₄ ) alkyl;
R ² , R ¹³ and R ¹⁵ are each independently selected from (C ₁ -C ₁₆ ) alkyl, (C ₇ -C ₁₆ ) alkylaryl and (C ₇ -C ₁₆ ) arylalkyl;
R ⁴ and R ¹⁴ are each independently selected from (C ₁ -C ₁₆ ) alkyl and (C ₇ -C ₁₆ ) alkylaryl;
b, d and f are each independently selected from the integers of 0, 1 and 2; a, c and e are each independently selected from the integers of 1, 2 and 3; a + b = 3, c + d = 3, and e + f = 3. The silane sulfide modified elastomeric polymer compound according to claim 1, wherein R ³ is a (C ₁ -C ₁₆ ) divalent alkyl group or a (C ₈ -C ₁₆ ) divalent alkylarylalkyl group. R ³ is —CH ₂ —, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, —CH ₂ —C ₆ H ₄ —CH ₂ —, or —C ₆ H _{4 -C (CH 3) 2 -C} 6 H 4 - is selected from claim 1 or Shiransurufido modified elastomer polymer compound according to 2. The silane sulfide modified elastomer polymer according to any one of claims 1 to 3, wherein R ² , R ⁴ , R ¹³ and R ¹⁵ are each independently selected from (C ₁ -C ₁₆ ) alkyl. Compound.   M is a silicon atom, a, c and e are integers selected from 2 and 3 respectively, b, d and f are integers selected from 0 and 1 respectively The silane sulfide modified | denatured elastomeric polymer compound of any one of these. A method for producing the silane sulfide-modified elastomer polymer compound as defined in any one of claims 1 to 5 , wherein
(A) An anionic polymerization initiator is reacted in a polymerization solvent with one or more monomer species comprising monomers selected from butadiene, styrene, isoprene, alpha methyl-styrene, and combinations thereof to form a reaction mixture A Forming steps,
(B) optionally reacting the reaction mixture A with at least one coupling agent to form a reaction mixture B;
(C) A silane sulfide modified polymer, wherein the reaction mixture A or B is reacted with at least one of the silane sulfide modifiers of the formulas 5 or 6 as defined in any one of claims 1 to 5 Producing the compound;
(D) optionally reacting the reaction mixture obtained in step (C) with a further denaturing agent. The at least one coupling agent used in step (B) is SnCl ₄ , (R ₁ ) ₃ SnCl, (R ₁ ) ₂ SnCl ₂ , R ₁ SnCl ₃ , SiCl ₄ , (R ₁ ) ₃ SiCl, ( R ₁ ) ₂ SiCl ₂ , R ₁ SiCl ₃ , Cl ₃ Si-SiCl ₃ , Cl ₃ Si-O-SiCl ₃ , Cl ₃ Sn-SnCl ₃ , Cl ₃ Sn-O-SnCl ₃ (wherein, R ₁ is 7. The method according to claim 6 , wherein the at least one selected from the group consisting of (C ₁ -C ₄ ) alkyl, Sn (OMe) ₄ , Si (OMe) ₄ , Sn (OEt) ₄ and Si (OEt) ₄ . Method. Said further modifier used in step (D) is represented by the following formula 7

During the ceremony
M ¹ is silicon or tin, x is an integer selected from 1, 2 and 3, y is an integer selected from 0, 1 and 2 and x + y = 3, R is independent Are selected from (C ₁ -C ₁₆ ) alkyl, R ′ is (C ₁ -C ₁₆ ) alkyl, (C ₈ -C ₁₆ ) alkylarylalkyl, (C ₇ -C ₁₆ ) arylalkyl, and a C ₇ -C ₁₆₎ alkylaryl, the method according to claim 6 or 7. 6. At least one silane sulfide modified polymer compound as defined in any one of claims 1 to 5 and added to or obtained as a result of the polymerization process used to produce said modified polymer compound A polymer composition comprising one or more additional components selected from the components to be removed and the components remaining after removing the solvent from the polymerization process. 10. The polymer composition of claim 9 , comprising at least one filler. 11. The polymer composition according to claim 10 , wherein the filler is one or more selected from carbon black, silica, carbon-silica biphasic filler, clay, calcium carbonate, magnesium carbonate, lignin and glass particles. The polymer composition of claim 11 , wherein the filler comprises silica. 13. The polymer composition of claim 11 or 12 , wherein the filler comprises carbon black. The polymer composition according to any one of claims 9 to 13 , comprising a vulcanizing agent. 15. A composition according to any one of claims 9 to 14 comprising at least one polymer selected from the group consisting of polybutadiene, butadiene-styrene copolymer, butadiene-isoprene copolymer, polyisoprene and butadiene-styrene-isoprene terpolymer. Polymer composition. A vulcanized polymer composition comprising the reaction product of at least the following 1) at least one vulcanizing agent, and 2) the polymer composition as defined in any one of claims 9 to 15 . A process for producing a vulcanized polymer composition, comprising reacting at least one of the following components 1) at least one vulcanizing agent, and 2) the polymer composition as defined in any one of claims 9 to 15. Method, including letting it happen. An article comprising at least one component formed from said vulcanized polymer composition as defined in claim 16 . The article of claim 18 , wherein the article is selected from the group consisting of a tire, a tire tread, a tire sidewall, a tire carcass, a belt, a hose, a damping body, and an article of footwear.