Production method of modified conjugated diene rubber, modified conjugated diene rubber and rubber c

专利摘要:
Production method of modified conjugated diene rubber, modified conjugated diene rubber and rubber composition. It is a method of producing a conjugated diene rubber capable of being used as a starting material for a particulate rubber that can be used in applications such as tire treads and can increase fuel efficiency. This method of producing a conjugated diene rubber comprises (a) a step of reacting a first alkoxysilane compound which has in a molecule at least one onion convertible group by an onion generator and at least one alkoxysilyl group which has at least two alkoxy groups having a conjugated diene polymer having an alkali metal or alkaline earth metal active terminal and obtained by polymerizing a conjugated diene compound and an aromatic vinyl compound to obtain a modified conjugated diene polymer having the onion convertible group and alkoxy silyl group, and (b) a step of mixing the resulting modified conjugated diene polymer with the onion generator and a second alkoxy silane compound having on one molecule at least one alkoxy silyl group and at least one onion convertible group by the onion generator.
公开号:BR112012009465B1
申请号:R112012009465-3
申请日:2010-10-21
公开日:2019-11-05
发明作者:Hasegawa Kenji；Shibata Masahiro；Tanaka Ryouji；Nakamura Takahiro；Tadaki Toshihiro
申请人:Jsr Corp；
IPC主号:

专利说明:

METHOD OF PRODUCTION OF MODIFIED CONJUGATED DIENO RUBBER, MODIFIED CONJUGATED DIENO RUBBER AND RUBBER COMPOSITION
Technique field
The present invention relates to a method of producing a modified conjugated diene rubber, a modified conjugated diene rubber and a rubber composition. More particularly, the present invention relates to a method of producing a modified conjugated diene rubber that has an excellent shape retention performance and that can produce a crosslinked rubber that exhibits excellent tensile strength, wear resistance (i.e. , abrasion resistance) and wet slip resistance and excellent low hysteresis loss behavior; to a modified conjugated diene rubber obtained by the production method; a rubber composition containing the modified conjugated diene rubber; and a crosslinked rubber composition (vulcanized rubber composition) obtained by crosslinking (e.g., vulcanizing) the rubber composition.
Prior art
The conjugated diene rubbers (for example, styrene-butadiene copolymer) obtained by means of emulsion polymerization methods are known as rubbers for automotive tire applications. A variety of conjugated diene rubbers that can achieve excellent fuel efficiency performance have been introduced in recent years amid expectations for improved automotive fuel efficiency.
As an example, a diolefin (co) polymer rubber conjugated with the following characteristics (1) to
Petition 870190089753, of 10/09/2019, p. 6/97
2/86 (3) has been proposed: (1) it consists of a (co) polymer rubber of a conjugated diolefin or a conjugated diolefin and an aromatic vinyl compound; (2) has a primary amino group and an alkoxy-silyl group attached to the (co) polymer chain; and (3) at least one bifunctional monomer is copolymerized in the (co) polymer chain, and / or, at least part of the (co) polymer chain is coupled with at least one bifunctional coupling agent (see patent reference 1 ).
In another example, a modified diene polymer rubber is proposed that is obtained by step 1 of obtaining an active polymer that has an alkali metal terminal by polymerizing a conjugated diene monomer or a conjugated diene monomer and a aromatic vinyl monomer in a hydrocarbon solvent in the presence of an alkali metal catalyst, and step 2 of obtaining a modified polymer rubber by reacting the active polymer with a compound that has a specific formula (see patent reference 2 ).
A method has also been proposed for the production of a modified polymer that has an increased interaction with silica and carbon black and that can provide improved wear resistance and failure characteristics and improved low heat build-up performance. This method proceeds through a primary modification reaction, in which a hydrocarbyloxy silane compound is reacted with the active site of a polymer that has an active organometal site in the molecule, and through a subsequent secondary modification reaction, in which a hydrocarbyloxy-silane compound is reacted through a condensation reaction between the hydrocarbyloxy-silyl groups (see patent reference 3).
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3/86 [Related technique references] [Patent reference list]
Reference of patent 1: Request in Patent Japanese open to inspection public at the. 2004-18795 Reference of patent 2: Request in Patent Japanese open to inspection public at the. 2005-290355 Patent reference 3: WO 03/048216 TO 1
Summary of the invention [Problems to be solved by the invention]
As noted above, a variety of conjugated diene rubbers have been introduced that can achieve excellent automotive fuel efficiency performance. However, improvements in automotive fuel efficiency are anticipated in
view of considerations economic, t ais how increase excessive of prices gives gasoline and in views in environmental considerations what begin with at emissions in
carbon dioxide. An object of the present invention, therefore, is to provide a method of producing a modified conjugated diene rubber capable of being used as a starting material for a crosslinked rubber that can be used in applications such as automotive tires, and which can increase fuel efficiency, for example, in automobiles.
[Way to solve problems]
As a consequence of intensive investigations to solve the problems described above, the inventors found that properties, such as excellent low hysteresis loss behavior, are conferred using an onium generator and two special types of compounds. alkoxy-silane in addition to a conjugated diene polymer that has an active alkali metal terminal, and which, as a consequence, can be
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4/86 produced a modified conjugated diene rubber that has the ability to provide excellent fuel efficiency when used, for example, in automotive tires. The present invention was achieved based on these researches.
Thus, the present invention provides the following [1] to [10].
[1] A method of producing a modified conjugated diene rubber, comprising:
(a) a step of reacting a first alkoxy-silane compound that has at least one convertible to an onium group in one molecule by means of an onium generator and at least one alkoxy-silyl group that has at least two alkoxy groups, with a conjugated diene polymer that has an active alkali metal or alkaline earth metal terminal and obtained by polymerizing a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound, to obtain, thus, a polymer of modified conjugated diene which has the onion convertible group and the alkoxy-silyl group; and (b) a step of mixing the modified conjugated diene polymer obtained in step (a) with the onium generator and a second alkoxy-silane compound that has at least one alkoxy-silyl group and at least one group in one molecule. convertible to onio by the onio generator.
[2] The production method of a conjugated diene rubber modified according to [1], in which the onion convertible group in the first alkoxy silane compound is at least one type selected from the group consisting of nitrogenous groups obtained by replacing two hydrogen atoms in a primary amine with two protecting groups, nitrogenous groups obtained by replacing a hydrogen atom
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5/86 on a secondary amine by a protecting group, tertiary amino groups, imino groups, pyridyl groups, phosphorus-containing groups obtained by replacing two hydrogen atoms of a primary phosphine with two protecting groups, phosphorus-containing groups obtained by means of the substitution of a hydrogen atom of a secondary phosphine with a protecting group, tertiary phosphine groups, and sulfur-containing groups obtained by replacing a hydrogen atom in a thiol with a protecting group.
[3] The production method of a modified conjugated diene rubber, according to [1] or [2], in which the onium generator is at least one type selected from the group consisting of silicon halide compounds , tin halide compounds, aluminum halide compounds, titanium halide compounds, zirconium halide compounds, germanium halide compounds, gallium halide compounds, zinc halide compounds, sulfate esters, phosphate esters , carboxylic acids and sulfonic acids.
[4] The production method of a modified conjugated diene rubber, according to any one of [1] to [3], in which the onion convertible group in the second alkoxysilane compound is at least one type selected from from the group consisting of primary amino groups, secondary amino groups, tertiary amino groups, imino groups, pyridyl groups, primary phosphine groups, secondary phosphine groups, tertiary phosphine groups and thiol groups.
[5] The method of producing a modified conjugated diene rubber, according to any one of [1] to [4], which further comprises:
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6/86 (c) a step of putting a mixture obtained in step (b) in contact with water.
[6] The method of producing a modified conjugated diene rubber, according to any one of [1] to [5], wherein the modified conjugated diene rubber contains the modified conjugated diene polymer mentioned above, the second compound of alkoxy-silane mentioned above and a condensation and hydrolysis product from the modified conjugated diene polymer and the second alkoxy-silane compound, and have onium structures formed by these three materials.
[7] A modified conjugated diene rubber obtained by the production method of a modified conjugated diene rubber according to any one of [1] to [6].
[8] A rubber composition comprising the conjugated diene rubber modified according to [7], a silica and / or a carbon black and a crosslinking agent.
[9] A cross-linked rubber composition obtained by cross-linking the rubber composition according to [8].
[10] A tire comprising the crosslinked rubber composition according to [9].
[Effects of the invention]
The production method of the present invention can provide a modified conjugated diene rubber that can produce a crosslinked rubber composition that exhibits excellent low hysteresis loss behavior. At the same time, the production method of the present invention can provide a modified conjugated diene rubber that exhibits excellent shape retention and can provide a modified conjugated diene rubber
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7/86 which can produce a crosslinked rubber that exhibits excellent tensile strength, wear resistance and wet slip resistance.
The crosslinked rubber composition produced using this modified conjugated diene rubber can be used, for example, for automotive tires, and can increase fuel efficiency, for example, for automobiles.
Modalities for carrying out the invention
The method of the present invention for the production of a modified conjugated diene rubber comprises (a) a step of reacting a first alkoxy silane compound that has at least one convertible to an onio group by an onium generator and at least one molecule. an alkoxysilyl group that has at least two alkoxy groups, with a conjugated diene polymer that has an active alkali metal or alkaline earth metal terminal and obtained by polymerizing a conjugated diene compound or a conjugated diene compound and a compound aromatic vinyl, to obtain, thus, a modified conjugated diene polymer that has the onion convertible group and the alkoxy-silyl group; and (b) a step of mixing the modified conjugated diene polymer obtained in step (a) with the onium generator and a second alkoxysilane compound that has at least one alkoxysilyl group and at least one onion convertible group in one molecule. onium generator.
[1] The method of producing a modified conjugated diene rubber is as follows.
[Step (a)] stage to react one firstStep (a) is compound of alkoxy-silane that have in a molecule at least a group convertible on onium for one onio generator and the
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8/86 minus an alkoxy-silyl group that has at least two alkoxy groups, with a conjugated diene polymer that has an active alkali metal or alkaline earth metal terminus and obtained through the polymerization of a conjugated diene compound or a compound of conjugated diene and an aromatic vinyl compound, to obtain, thus, a modified conjugated diene polymer that has the onion convertible group and the alkoxy-silyl group.
The conjugated diene polymer that has an active alkali metal or alkaline earth metal terminal consists, for example, of an anionic polymer obtained by the homopolymerization of a conjugated diene compound or by the copolymerization of a conjugated diene compound and an aromatic vinyl compound .
The method for producing the conjugated diene polymer should perform an anionic polymerization mediated by an alkali metal or alkaline earth metal (also mentioned below as the polymerization initiator ”) as noted above, but is not otherwise particularly limited. For example, the polymerization method may consist of a solution polymerization method, gas phase polymerization method or volume polymerization method. Among these methods, solution polymerization methods are particularly preferred. The polymerization regime can be batch or continuous. The metal at the active site present in the conjugated diene polymer molecule is an alkali metal or alkaline earth metal. Among these, lithium, sodium, potassium, magnesium and barium are preferred and lithium is particularly preferred. All of these alkali metals and alkaline earth metals have the same functionality in terms of enabling the production of a conjugated diene polymer that has an active metal terminal that is reactive
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9/86 with the first alkoxy silane compound and those species not explored in the examples below can also be used in the present invention.
In addition, it is also effective to incorporate a monomer containing a functional group and activate the functional group in the polymer with the use of an alkali metal type initiator. For example, an active site can be generated effectively by lithionizing the functional group portion of a copolymer that contains the isobutylene unit, para-methylstyrene unit and parahalomethylstyrene unit.
The following compounds, for example, are suitably used as the conjugated diene monomer:
1.3- butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 3- methyl-1,3-pentadiene, 2-chloro-1,3-butadiene, and so on. One of these can be used or two or more can be used in combination. Among these compounds, the use of 1,3-butadiene, isoprene or 2,3-dimethyl-1,3-butadiene is particularly suitable. These conjugated diene monomers have the same functionality in terms of enabling the production of a conjugated diene polymer that has an active metal terminal that is reactive with the first alkoxy silane compound, and those species not explored in the examples below can also be used in the present invention.
Suitable aromatic vinyl compounds are, for example, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene,
2.4- diisopropylstyrene, 4-tert-butylstyrene, 5-t-butyl2-methylstyrene, vinylethylbenzene, divinylbenzene, trivinylbenzene, divinylnaphthalene, tert-butoxy-styrene,
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10/86 vinylbenzyldimethylamine, (4-vinylbenzyl) dimethylaminoethyl ether, N, N-dimethylaminoethylstyrene, N, Ndimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-styrene-butyl-styrene-butyl , vinylxylene, vinylnaphthalene, vinyltoluene, vinylpyridine, diphenylethylene, diphenylethylene that contains a tertiary amino group, and so on. One of these can be used or two or more can be used in combination. Styrene is particularly preferred among these compounds. These aromatic vinyl compounds have the same functionality in terms of enabling the production of a conjugated diene polymer that has an active metal terminus that is reactive with the first alkoxy silane compound, and those species not explored in the examples below can also be used in the present invention.
When a copolymerization is carried out using a conjugated diene monomer and an aromatic vinyl compound, 1,3-butadiene and styrene are preferably used, respectively. These monomers are easy to acquire and are excellent in terms of having a high live activity in anionic polymerization. When a solution polymerization method is employed, the concentration of monomer in the solvent, when viewed from the perspective of maintaining a balance between productivity and ease of polymerization control, is preferably 5 to 50%, in mass, and more preferably it is 10 to 30% by mass. When a copolymerization is performed using a conjugated diene monomer and an aromatic vinyl compound, the content of aromatic vinyl compound in the charged monomer mixture - when viewed from the perspective of maintaining a balance between wet slip resistance and the behavior of
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11/86 low hysteresis loss of the resulting cross-linked rubber composition - is preferably 3 to 55% by weight, and more preferably 5 to 50% by weight.
The compound used as the alkali metal or alkaline earth metal initiator can be exemplified by alkyl lithium, alkylene dilithium, lithium alkyleneimide, lithium dialkylamide, phenyl lithium, stilbene-lithium, lithium naphthalene, sodium naphthalene, potassium naphthalene , n-butylmagnesium, n-hexyl magnesium, calcium ethoxy, calcium stearate, strontium t-butoxy, barium ethoxy, barium isopropoxy, barium ethylmercapto, barium t-butoxy, barium phenoxy, barium diethylamino, barium stearate, barium cetyl, biphenyl sodium, potassium-tetrahydrofuran complex, diethyl-ethane potassium complex, the sodium salt of α-methylstyrene tetramer, and so on. Among these compounds, organolithium compounds, such as alkyl lithiums, and lithium amide compounds, such as lithium alkyleneimides, and so on, are preferred examples. When the first (i.e., organolithium compound) is used, a conjugated diene polymer is obtained which has a hydrocarbyl group at the polymerization initiation terminal and an active polymerization site at the other terminal. When the latter (i.e., lithium amide compound) is used, a conjugated diene polymer is obtained which has a nitrogenous group at the polymerization initiation terminal and an active polymerization site at the other terminal. All of these alkali metal initiators and alkaline earth metal initiators have the same functionality in terms of enabling the production of a conjugated diene polymer that has an active metal terminal that is reactive with the first alkoxy silane compound, and those species no
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12/86 explored in the examples below can also be used in the present invention.
The organolithium compound preferably has a C1-20 hydrocarbyl group (i.e., a hydrocarbyl group having 1 to 20 carbon atoms). For example, methyl lithium, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyllithium, sec-butyl lithium, tert-octyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl -lithium, 2-butylphenyl-lithium, 4-phenyl-butyl-lithium, cyclohexyl-lithium, the reaction product of diisopropenylbenzene with butyl-lithium, t-butyl-lithium, n-hexyl-lithium, benzyl-lithium, phenyl- lithium, stylbene-lithium,
1,4-dilithiobutane, 1,3,5-trilithiobenzene, the reaction product of n-butyllithium with 1,3-butadiene and divinylbenzene, the reaction product of n-butyllithium and a polyacetylene compound, 4 -cyclopentyl-lithium, 1,2dilithomethane, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane and 1,3,5-trilithiobenzene. N-butyl lithium and secbutyl lithium are preferred among the above.
The lithium amide compound can be exemplified by lithium hexamethyleneimide, lithium pyrrolidide, lithium piperidide, lithium heptamethyleneimide, lithium dodecamethyleneimide, lithium morphide, lithium dimethylamide, lithium diethylamide, lithium dibutylamide, dipropylamide, dipropylamide, dipropylamide lithium diisopropylamide, lithium diheptylamide, lithium dihexylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium N-methylpiperazide, lithium ethylpropylamide, lithium ethylbutylamide, lithium ethylbenzylamide, lithium methylphenethylamide, 3 [N, N-bis (trimethylsilyl)] - 1-propyl lithium, 3- [N, Nbis (trimethylsilyl)] - 2-methyl-1-propyl-lithium, 3- [ N, Nbis (trimethylsilyl)] - 2,2-dimethyl-1-propyl-lithium, 4- [N, Nbis (trimethylsilyl)] - 1-butyl-lithium, 5- [N, NPetition 870190089753, of 10/09 / 2019, p. 17/97
13/86 bis (trimethylsilyl)] - 1-pentyl-lithium, 8- [N, Nbis (trimethylsilyl)] - 1-octyl-lithium, 3- (2,2,5,5-tetramethyl-
2,5-disyl-1-azacyclopentane) -1-propyl-lithium, 2-methyl-3- (2,2,5,5-tetramethyl-2,5-disyl-1-azacyclopentane) -1propyl-lithium, 2 , 2-dimethyl-3- (2,2,5,5-tetramethyl-2,5disyl-1-azacyclopentane) -1-propyl-lithium, 4- (2,2,5,5tetramethyl-2,5-disyl- 1-azacyclopentane) -1-butyl lithium and
6- (2,2,5,5-tetramethyl-2,5-disyl-1-azacyclopentane) -1hexyl-lithium. Among the above, cyclic lithium amides, such as lithium hexamethyleneimide, lithium pyrrolidide, lithium piperidide, lithium heptamethyleneimide, lithium dodecamethyleneimide, and so on, are preferred for their polymerization initiation activity and their interaction with carbon black and silica. Among these, lithium hexamethyleneimide,
lithium pyrrolidide and piperidide in lithium are particularly preferred. These compounds amide in lithium are often prepared by middle of use in a compound
of lithium and a secondary amine in advance, and are used in polymerization, but can also be prepared in the polymerization system (in situ). The amount of use of this polymerization initiator is preferably selected from the range of 0.2 to 20 millimols per 100 g of monomer.
In a specific method for the production of a conjugated diene polymer by means of anionic polymerization using a lithium compound, as described above, as the polymerization initiator, for example, the diene monomer, or the diene monomer and composed of aromatic vinyl, is subjected to anionic polymerization, possibly in the presence of a randomization element, in an organic solvent inert to the reaction, for
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14/86 example, a hydrocarbon solvent, such as an aliphatic, alicyclic or aromatic hydrocarbon compound, using the aforementioned lithium compound as the polymerization initiator. The desired conjugated diene polymer can be obtained using this method.
The hydrocarbon solvent mentioned above is preferably from 3 to 8 carbons, and can be exemplified by propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1- butene, isobutene, trans-2-butene, cis-2butene, 1-pentine, 2-pentine, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene, heptane, cyclopentane, methylcyclopentane, methylcyclohexane, 1- pentene, 2pentene, cyclohexene, and so on. A single of these can be used or a mixture of two or more can be used.
The randomization element that is used on an optional basis is a compound that works to control the microstructure of the conjugated diene polymer, for example, to increase the vinyl bonds (ie, 1,2 bond) in the butadiene portion in a copolymer of butadiene-styrene or to increase the vinyl bonds (i.e., 1,2-bond and 3,4-bond) in an isoprene polymer, or to control the component distribution of the monomer units in the conjugated diene polymer, for example , to randomize the butadiene units and styrene units in a butadiene styrene copolymer. There are no particular limitations on this element of randomization and any element of randomization can be used, selected as appropriate from the compounds known so far, generally known as a randomization element. The examples
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Specific 15/86 are tertiary ethers and amines, such as dimethoxy-benzene, tetrahydrofuran, dimethoxy-ethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, 2,2-di (tetrahydrofuryl) propane, 2- (2 -ethoxy-ethoxy) 2-methylpropane, triethylamine, pyridine, N-methylmorpholine, N, N, N ', N'-tetramethylethylenediamine, 1,2-dipiperidinoethane, ethylene glycol dibutyl ether, ethylene glycol dimethyl ether, diethyl ether, dioxane, trimethylamine, quinuclidine, potassium tamylate, potassium t-butylate, triphenylphosphine, tetrahydropyran, dibutyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, diphenyl ether, anisol, tripropylamine, tributylamine, N, quinoline and N, ethylamine onwards. A single of these randomization elements can be used on its own or a combination of two or more can be used.
A potassium compound can be added in combination with the polymerization initiator when an increase in the reactivity of the aforementioned polymerization initiator is required, when a random arrangement of the aromatic vinyl compound inserted in the polymer is required or when a single unit chain / long chain of aromatic vinyl compound should be provided. The potassium compound added in combination with the polymerization initiator can be exemplified by potassium alkoxides as represented by potassium isopropoxide, potassium t-butoxide, potassium t-amyloxide, potassium n-heptoxide, potassium benzyloxide and potassium; potassium phenoxide; the potassium salt of, for example, isovalerianic acid, caprylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, benzoic acid, phthalic acid, 2-ethylhexanoic acid, and so on; the potassium salts of
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16/86 organo-sulfonic acids, such as dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, and so on; and the potassium salts of organophosphite ester moieties, such as diethyl phosphite, diisopropyl phosphite, diphenyl phosphite, dibutyl phosphite, dilauroyl phosphite, and so on.
These potassium compounds are preferably added in 0.005 to 0.5 mol per 1 gram of equivalent atom of the alkali metal or alkaline earth metal in the polymerization initiator. When this amount is less than 0.005 mol, the addition of the potassium compound has no effect on the reactivity optimized by the polymerization initiator, the randomization of the aromatic vinyl compound or generation of a single unit chain / long chain of the aromatic vinyl compound . When this amount is above 0.5 mol, on the other hand, the polymerization activity is reduced and the productivity is then substantially reduced, and in combination with these, the modification efficiency in the modification reaction with the first compound of alkoxy-silane can be reduced.
The temperature in this polymerization reaction is preferably from -20 to 150 ° C, and more preferably, from 0 to 120 ° C. The polymerization reaction can be carried out under the pressure spontaneously generated, but as a general matter, the process is preferably carried out at a pressure sufficient to substantially maintain the monomer in the liquid phase. Thus, the pressure will also depend on the substance (s) that is polymerized, the polymerization medium used and the polymerization temperature and, as desired, a pressure that is greater than the spontaneously generated pressure can be used. Such pressure is obtained through a suitable method, for example,
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17/86 by pressurizing the reactor with a gas that is inert to the polymerization reaction.
All starting materials provided for this polymerization, such as the polymerization initiator, solvent, monomer, and so on, are desirably used in this polymerization after removing substances that can poison or inhibit the reaction, such as water, oxygen, carbon dioxide, protic compounds, and so on, from the starting materials. When the polymer obtained consists of an elastomer, the glass transition temperature (Tg) of the polymer or copolymer obtained, as determined by the differential calorimetric analysis, is preferably from -90 ° C to 0 ° C. It is difficult to obtain a polymer that has a glass transition temperature of less than -90 ° C. When the glass transition temperature exceeds 0 ° C, the viscosity in the room temperature region is too high and handling can be very problematic.
The alkoxy-silyl group in the first alkoxy-silane compound has at least two alkoxy groups based on a consideration of reactivity with the conjugated diene polymer which has an active alkali metal or alkaline earth metal terminus. Suitable examples of the alkoxy group are alkoxy groups that have a C1-20 alkyl group or an aryl group. When two or more alkoxy groups are present, they may be the same or may differ from each other.
Regarding the convertible to onio group in the first alkoxy silane compound, this molecule should contain at least one group consisting of a protected group that is protected from the active terminals of alkali metal or alkaline earth metal of the diene polymer
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18/86 combined and that, after deprotection, can be converted into onium by means of the action of an onium generator. This onion-convertible group can be exemplified by nitrogenous groups obtained by replacing two hydrogen atoms in a primary amine with two protecting groups, nitrogenic groups obtained by replacing a hydrogen atom in a secondary amine with a protecting group , tertiary amino groups, imino groups, pyridyl groups, phosphorus-containing groups obtained by replacing two hydrogen atoms in a primary phosphine with two protecting groups, phosphorus-containing groups obtained by replacing a hydrogen atom in a secondary phosphine by a protecting group, tertiary phosphine groups, and sulfur-containing groups obtained by replacing a hydrogen atom in a thiol with a protecting group. A single of these first alkoxy silane compounds can be used on its own (i.e., alone) or two or more can be used in combination.
The following are examples of compounds that have an alkoxy-silyl group and a nitrogenous group obtained by replacing two hydrogen atoms in a primary amine with two protecting groups, a nitrogenous group obtained by substituting a hydrogen atom in a secondary amine with a protecting group, or a tertiary amino group: N, Nbis (trimethylsilyl) aminopropylmethyldimethoxy-silane, N, Nbis (trimethylsilyl) aminopropyltrimethoxy-silane, N, Nbis (trimethylsilyl) aminopropyltriethoxy-silane, N, Nylsyl) aminopropylmethyldietoxy silane, N, Nbis (trimethylsilyl) aminoethyltrimethoxy silane, N, Nbis (trimethylsilyl) aminoethyltriethoxy silane, N, N
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19/86 bis (trimethylsilyl) aminoethylmethyldimethoxy-silane, N, Nbis (trimethylsilyl) aminoethylmethyldiethoxy-silane, N, Nbis (triethylsilyl) aminopropylmethyldimethoxy-silane, N, Nbis (triethylsilyl) aminopropyltriethyl-triethyl-triethyl-silane, triloxy-silane, N , N, Nbis (triethylsilyl) aminopropylmethyldietoxy-silane, N, Nbis (triethylsilyl) aminoethyltrimethoxy-silane, N, Nbis (triethylsilyl) aminoethyltriethoxy-silane, N, Nbis (triethylsilyl) aminoethylmethyl-methylethylethyl-ethylene, silane, N , N, N ', N'tris (trimethylsilyl) -N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N, N', N'-tris (trimethylsilyl) -N- (2-aminoethyl) -3aminopropylmethyldietoxy-silane, N, N ', N'-tris (trimethylsilyl) N- (2-aminoethyl) -3-aminopropyltrimethoxy-silane, N, N', N'tris (trimethylsilyl) -N- (2-aminoethyl) -3aminopropylmethyldimethoxy-silane, 1- (3-triethoxysilylpropyl) -2,2,5,5-tetramethyl-1-aza-2,5disylacyclopentane, 1- (3-trimethoxy-silylpropyl) -2,2,5,5tetramethyl-1-aza-2, 5-disylacyclopentane, 1- (3-methylldiethoxy-silylpro pil) -2,2,5,5-tetramethyl-1-aza-2,5disylacyclopentane, 1- (3-methyldimethoxy-silylpropyl) 2,2,5,5-tetramethyl-1-aza-2,5-disylacyclopentane, 1trimethylsilyl-2,2-dimethoxy-1-aza-2-silacyclopentane, N- [3 (trimethoxy-silyl) propyl] -N, N'-diethyl-N'-trimethylsilyl-ethane-
1,2-diamine, N- [3- (triethoxy-silyl) propyl] -N, N'-diethyl-N'-trimethylsilyl-ethane-1,2-diamine, N- [3- (methyldimethoxysylyl) propyl] - N, N'-diethyl-N'-trimethylsilyl-ethane-1,2diamine, N- [3- (methyldimethoxy-silyl) propyl] -N, N'-diethyl-N'trimethylsilyl-p-phenylenediamine, N- [3 - (triethoxysilyl) propyl] -N, N'-diethyl-N'-trimethylsilyl-pphenylenediamine, 3- [3- (trimethylsilylethylamino) -1pyrrolidinyl) propylmethyldiethoxy-silane, 3- [3Petition 870190089753, from 10/09/2019, page . 24/97
20/86 (trimethylsilylpropylamino) -1pyrrolidinyl) propyltriethoxysilane, N- (3- (diethoxymethylsilyl) propyl] -N-ethyl-N'- (2-ethoxy-ethyl) -N'trimethylsilylethane-1,2-diamine, N- [ 3- (tripropoxysilyl) propyl] -N-propyl-N'- (2-ethoxy-ethyl) -N'-triethylsilyl-pphenylenediamine, N- [2- (diethoxy-methylsilyl) -1-methylethyl] -Netyl-N ' - (2-diethylaminoethyl) -N'-triethylsilylethane-1,2diamine, N- [3- (triethoxy-silyl) propyl] -N-ethyl-N'- (2 diethylaminoethyl) -N'-triethylsilylethane-1,2- diamine, 3- (4trimethylsilyl-1-piperazine) propylmethyldimethoxy-silane, 3 (4-trimethylsilyl-1-piperazine) propyltriethoxy-silane, 3- (4trimethylsilyl-1-piperazine) propyltributoxy-silane, 3- (4trimethylsiline-pylazine ) propylmethyldiethoxy-silane, 3 (4-trimethylsilyl-1-piperazine) propyltrimethoxy-silane, 3 (3-trimethylsilyl-1-imidazolidinyl) propylethylethoxy-silane, 3- (3-trimethylsilyl-1imidazolidinyl) propyltriethyl-3-silane, 3- -hexa-hydropyrimidinyl) propylmethyldimethoxy-silane, 3- (3-trimethylsilyl-1-hexahydropyrimidinyl) propyltriethoxysil year, 4- (4-trimethylsilyl-1-piperazinyl) butyltriethoxysilane, N- [2- (trimethoxy-silyl) ethyl] -N, N ', N'-trimethylethane-
1.2- diamine, N- [2- (dimethoxy-methylsilyl) ethyl] -N-ethyl-N ', N'-dimethylethane-1,2-diamine, N- [3- (trimethoxy-silyl) propyl] N, N ', N'-trimethylpropane-1,3-diamine, N- [3- (dimethoxymethylsilyl) propyl] -N-ethyl-N', N'-dimethylpropane-1,3-diamine, N- [3- (triethoxy- silyl) propyl] -N, N ', N'-triethyl-2-methylpropane-
1.3- diamine, N- [3- (dimethoxymethylsilyl) propyl] -2, N, N ', N'- tetramethylpropane-1,3-diamine, N- (2-dimethylaminoethyl) -N' [2- (trimethoxy -silyl) ethyl] -N, N'-dimethylethane-1,2-diamine, N [2- (diethoxy-propylsilyl) ethyl] -N '- (3-ethoxy-propyl) -N, N'dimethylethane-1, 2-diamine, N- [2- (trimethoxy-silyl) ethyl] -N'Petition 870190089753, from 10/09/2019, p. 25/97
21/86 methoxy-methyl-N, N'-dimethylethane-1,2-diamine,
N- [2 (trimethoxy-silyl) ethyl] -N, N'-dimethyl-N'- (2-trimethylsilylethyl) ethane-1,2-diamine,
N- [2- (triethoxysilyl) ethyl] -N, N'-diethyl-N'- (2-dibutylmethoxy-silylethyl) ethane1,2-diamine, methylpiperazine, methylpiperazine, methylpiperazine, methylpiperazine, methylpiperazine, methylimidazolidine, methylimidazolidine, methylimidazolidine hydropyrimidine,
1- [3- (triethoxy-silyl) propyl] -41- [3- (diethoxy-ethylsilyl) propyl] -41- [3- (trimethoxy-silyl) propyl] -41- [3- (diethoxy-methylsilyl) propyl ] -41- [3- (dimethoxy-methylsilyl) propyl] -41- [3- (trimethoxy-silyl) propyl] -31- [3- (diethoxy-ethylsilyl) propyl] -31- [3- (triethoxy-silyl ) propyl] -3-methyl1- [3- (dimethoxy-methylsilyl) propyl] -3methyl-hexahydropyrimidine, 3- [3- (tributoxy-silyl) propyl] 1-methyl-1,2,3,4-tetra -hydropyrimidine,
3- [3- (dimethoxymethylsilyl) propyl] -1-ethyl-1,2,3,4-tetrahydropyrimidine,
1- (2-ethoxy-ethyl) -3- [3- (trimethoxysilyl) propyl] imidazolidine,
2- {3- [3- (trimethoxysilyl) propyl] tetrahydropyrimidin-1-yl} ethyldimethylamine,
2- (trimethoxy-silyl) -1,3-dimethylimidazolidine, 2- (diethoxyethylsilyl) -1,3-diethylimidazolidine,
1,4-diethylpiperazine, dimethylpiperazine, hydropyrimidine, hydropyrimidine,
2- (triethoxy-silyl) 2- (dimethoxy-methylsilyl) -1,45- (triethoxy-silyl) -1,3-dipropyl-hexa5- (diethoxy-ethylsilyl) -1,3-diethyl-hexa2- [3- (2-dimethylaminoethyl) -2 (ethyldimethoxy-silyl) imidazolidin-1-yl] ethyldimethylamine, 5 (trimethoxy-silyl) -1,3-bis (2-methoxy-ethyl) hexahydropyrimidine,
5- (ethyldimethoxy-silyl) -1,3-bistrimethylsilyl-hexahydropyrimidine,
2- (3-dietoxyethylsilylpropyl) -1,3-diethylimidazolidine,
2- (3-triethoxysilylpropyl) -1,4-diethylpiperazine,
2- (3-dimethoxymethylsilylpropyl) -1,4-dimethylpiperazine,
5- (3-triethoxyPetition 870190089753, of 9/10/2019, page 26/97
22/86 silylpropyl) -1,3-dipropyl-hexahydropyrimidine, 5- (3diethoxy-ethylsilylpropyl) -1,3-diethyl-hexahydropyrimidine,
2- [3- (2-dimethylaminoethyl) -2- (3-ethyldimethoxysilylpropyl) imidazolidin-1-yl] ethyldimethylamine, 5- (3-methoxy-silylpropyl) -1,3-bis (2-methoxy-ethyl) hexahydropyrimidine, 5- (3-etildimetóxi-silylpropyl) -1,3-bis (2 trimethylsilylethyl) hexahydropyrimidine, 3dimetilaminopropiltrimetóxi silane, silane 3dietilaminopropiltrimetóxi, 3dimetilaminopropiltrietóxi silane, 3dietilaminopropiltrietóxi silane, silane 3etilmetilaminopropiltrimetóxi, 3etilmetilaminopropiltrietóxi silane, silane 3dimetilaminopropilmetildimetóxi, 3dietilaminopropilmetildimetóxi silane, 3dimetilaminopropiletildimetóxi silane, silane 3dietilaminopropiletildimetóxi, 3dimetilaminopropildimetilmetóxi silane, silane 3dimetilaminopropildietilmetóxi, 3dietilaminopropildimetilmetóxi silane, silane 3dietilaminopropildietilmetóxi, 3etilmetilaminopropilmetildimetóxi silane, 3-methyl-3etilaminopropiletildimetóxi silane, 3dimetilaminopropilmetildietóxi silane, silane 3dietilaminopropilmetildietóxi, 3dimetilaminopropiletildiet xi silane, 3dietilaminopropiletildietóxi silane, silane 3dimetilaminopropildimetiletóxi, 3dimetilaminopropildietiletóxi silane, silane 3dietilaminopropildimetiletóxi, 3dietilaminopropildietiletóxi silane, silane 3etilmetilaminopropilmetildietóxi, 3etilmetilaminopropiletildietóxi silane, 3-di (metóxiPetição 870 190 089 753 of 10.9.2019, p. 27/97
23/86 methyl) aminopropyltrimethoxy silane,
3-di (methoxyethyl) aminopropyltrimethoxy silane,
3-di (methoxymethyl) aminopropyltriethoxy-silane,
3-di (methoxyethyl) aminopropyltriethoxy silane,
3-di (ethoxyethyl) aminopropyltrimethoxy-silane, methyl) aminopropyltrimethoxy-silane, ethyl) aminopropyltriethoxy-silane, methyl) aminopropyltriethoxy-silane, di (trimethylsilyl) aminopropyltrimethoxy-silane, di (trimethylsilyl) aminopropyltriethylethylethylethylethylethylethylethylethyltriethylethyltriethylene) butyldimethylsilyl) aminopropyltriethoxy silane,
3-di (ethoxy3-di (ethoxy3-di (ethoxy333-di (t3-di (t3di (trimethylsilyl) aminopropylmethyldimethoxy-silane, di (trimethylsilyl) aminopropylmethyldietoxy-silane, butyldimethylsilyl) aminopropylmethyldiethylethylethylsilane, butyl) trimethylsilyl) aminopropildimetilmetóxi silane, di (trimethylsilyl) aminopropildimetiletóxi silane, butyldimethylsilyl) aminopropildimetilmetóxi silane, butyldimethylsilyl) aminopropildimetiletóxi silane, morfolinopropiltrimetóxi silane, morfolinopropiltrietóxi silane, morfolinopropilmetildimetóxi silane, morfolinopropiletildimetóxi silane, morfolinopropilmetildietóxi silane, morfolinopropiletildietóxi silane, piperidinopropyltrimethoxy-silane, piperidinopropyltriethoxy-silane, piperidinopropylmethyldimethoxy-silane, piperidinopropylethyldimethoxy-silane, piperidinopropylmethyldietoxy-silane, piperidinopropylethylethoxy-silane, silyl) propylamine] trimethyl]
33-di (t3-di (t333-di (t3-di (t333333333333bis [3- (trietoxibis [3- (trimethoxyPetition 870190089753, from 10/09/2019, page 28/97
24/86 silyl) propyl] trimethylsilylamine. Preferred are the following: N, N-bis (triethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldietoxysilane, N, N-bis (trimethylsilyl) aminopropyltriethoxy (3-triethoxy-silylpropyl) -2,2,5,5-tetramethyl-1-aza-2,5disylacyclopentane, N, N ', N'-tris (trimethylsilyl) -N- (2aminoethyl) -3-aminopropyltriethoxy-silane , 1-trimethylsilyl2,2-dimethoxy-1-aza-2-silacyclopentane, N- [3- (trimethoxysilyl) propyl] -N, N'-diethyl-N'-trimethylsilyl ethane-1,2-diamine, N- [3 - (triethoxy-silyl) propyl] -N, N'-diethyl-N'trimethylsilylethane-1,2-diamine, 3- (4-trimethylsilyl-1piperazine) propyltriethoxy-silane, N- [2- (trimethoxysilyl) ethyl] - N, N ', N'-trimethylethane-1,2-diamine, 1- [3 (triethoxy-silyl) propyl] -4-methylpiperazine, 2- (trimethoxysilyl) -1,3-dimethylimidazolidine, 2- (3-trimethoxysilylpropyl ) -1,3-dimethylimidazolidine, 3dimethylaminopropyltrimethoxy-silane, 3diethylaminopropyltrimethoxy-silane, 3dimethylaminopropyltriethoxy-silane, 3diethylamino propyltriethoxy-silane, bis [3- (triethoxysilyl) propyl] trimethylsilylamine and bis [3- (trimethoxysilyl) propyl] trimethylsilylamine.
Compounds having an alkoxy-silyl group and an imino group or pyridyl group can be exemplified by
N- (1,3-dimethylbutylenene) -3- (triethoxy-silyl) -1propanamine, N- (1,3-methylethylidene) -3- (triethoxy-silyl) -1propanamine, N-ethylidene-3- (triethoxy-silyl) ) -1-propanamine, N- (1-methylpropylidene) -3- (triethoxy-silyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (triethoxy-silyl) -1propanamine and N- (cyclohexylidene) -3- (triethoxy-silyl) -1propanamine, and trimethoxy-silyl compounds, compounds
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25/86 of methyldiethoxy-silyl and ethyldimethoxy-silyl compounds that correspond to these triethoxy-silyl compounds, as well as N- (3-trimethoxy-silylpropyl) -4,5-dihydroimidazole, N- (3-triethoxy-silylpropyl) -4,5-dihydroimidazole, N- (3-trimethoxy-silylpropyl) -4,5-imidazole,
N- (3-triethoxy-silylpropyl) -4,5-imidazole, 3hexamethyleneiminopropyltrimethoxy-silane, 3hexamethyleneiminopropyltriethoxy-silane, 3hexamethyleneiminopropylmethyldimethoxyethyl-ethylamethyl-ethylamethyl-ethylene-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl-ethyl Preferred are as follows: N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (triethoxysylyl) -1-propanamine and N- (3-trimethoxy -silylpropyl) -4,5-dihydroimidazole, N- (3-triethoxy-silylpropyl) -4,5-dihydroimidazole, N- (3-trimethoxy-silylpropyl) -4,5-imidazole, N- (3-triethoxy- silylpropyl) -4,5-imidazole.
The following are examples of compounds that have an alkoxy-silyl group and a group containing phosphorus obtained by replacing two hydrogen atoms of a primary phosphine with two protecting groups, a group containing phosphorus obtained by substituting an atom of hydrogen from a secondary phosphine by a protecting group, a tertiary phosphine group or a sulfur-containing group obtained by replacing a hydrogen atom in a thiol with a protecting group: P, Pbis (trimethylsilyl) phosphinopropylmethyldimethoxy-silane, P, Pbis (trimethylsilyl) phosphinopropyltrimethoxy-silane, P, Pbis (trimethylsilyl) phosphinopropyltriethoxy-silane, P, Pbis (trimethylsilyl) phosphinopropylmethyldietoxy-silane, P, Pbis (trimethylsilyl) phosphinoethyl-ethyl, Phosphoethyl-ethyl, Phosphoethyl-ethyl, PPetition 870190089753, of 10/09/2019, p. 30/97
26/86 bis (trimethylsilyl) silane fosfinoetilmetildimetóxi, P, PBIS (trimethylsilyl) silane fosfinoetilmetildietóxi, 3dimetilfosfinopropiltrimetóxi silane, silane 3dietilfosfinopropiltrimetóxi, 3dimetilfosfinopropiltrietóxi silane, 3dietilfosfinopropiltrietóxi silane, silane 3etilmetilfosfinopropiltrimetóxi, 3etilmetilfosfinopropiltrietóxi silane, silane 3dimetilfosfinopropilmetildimetóxi, 3dietilfosfinopropilmetildimetóxi silane, 3dimetilfosfinopropiletildimetóxi silane, silane 3dietilfosfinopropiletildimetóxi, 3dimetilfosfinopropildimetilmetóxi silane, silane 3dimetilfosfinopropildietilmetóxi, 3dietilfosfinopropildimetilmetóxi silane, silane 3dietilfosfinopropildietilmetóxi, 3etilmetilfosfinopropilmetildimetóxi silane, silane 3etilmetilfosfinopropiletildimetóxi, 3dimetilfosfinopropilmetildietóxi silane, silane 3dietilfosfinopropilmetildietóxi, 3dimetilfosfinopropiletildietóxi silane, silane 3dietilfosfinopropiletildietóxi , 3dimethylphosphinopropyldimethylethyloxy-silane, 3di metilfosfinopropildietiletóxi silane, silane 3dietilfosfinopropildimetiletóxi, 3dietilfosfinopropildietiletóxi silane, silane 3etilmetilfosfinopropilmetildietóxi, 3etilmetilfosfinopropiletildietóxi silane, silane 3difenilfosfinopropiltrimetóxi, 3difenilfosfinopropiltrietóxi silane, silane 3difenilfosfinopropilmetildimetóxi, 3difenilfosfinopropilmetildietóxi silane, silane Strimetilsililmercaptopropilmetildimetóxi S
Petition 870190089753, of 10/09/2019, p. 31/97
27/86 trimethylsililmercaptopropyltrimethoxy silane, Strimethylsilmercaptopropyltriethoxy silane, Strimethylsililmercaptopropylmethyldiethoxy silane, Strimethylsililmercaptoethyltrimethoxyethylethylmethylethylmethylethylmethylethylmethylethylmethylethylmethyl. Preferred are the following: 3diphenylphosphinopropyltrimethoxy-silane, 3diphenylphosphinopropyltriethoxy-silane, Strimethylsililmercaptopropylmethyldimethoxy-silane, Strimethylsilyl-methoxy-silane, Strimethylsilyl-methoxy-propane.
The reaction of the first alkoxy silane compound and the conjugated diene polymer that has an active alkali metal or alkaline earth metal terminal results in the connection between the active terminal portion of alkali metal or alkaline earth metal and a portion (i.e., a alkoxy group) of at least two alkoxy groups, thus producing a modified conjugated diene polymer that has the onion convertible group and the remaining alkoxy-silyl group or groups. All of the first alkoxy silane compounds mentioned above have the same functionality in terms of their reactivity with the conjugated diene polymer that has an active alkali metal or alkaline earth metal terminal, its reaction or interaction with carbon black and / or silica used as a reinforcing agent, when the rubber composition is formulated, and its ability to provide excellent low hysteresis loss behavior, once the cross-linked rubber composition has been produced, and
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28/86 those species not explored in the examples below can also be used in the present invention.
The modification reaction - in which the first alkoxy silane compound is introduced into the active alkali metal or alkaline earth metal terminal of the conjugated diene polymer - can be carried out, for example, as a solution reaction. In a solution reaction, the solution may contain unreacted monomer that has been used for polymerization. The modification reaction regime is not particularly limited, and the modification reaction can be carried out using a batch reactor or it can be carried out in a continuous regime using equipment, such as, for example, a reactor multi-stage continuous or in-line mixer. This modification reaction is preferably carried out before carrying out, for example, solvent removal, water treatment, heat treatment and operations required for the polymer isolation, and the like, and after the completion of the polymerization reaction.
Regarding the amount of use of the first alkoxysilane compound in this modification reaction, the first alkoxysilane compound is added in an amount that is preferably at least 0.1 molar equivalents and, more preferably, at least 0.3 molequivalent with reference to the active site of the conjugated diene polymer obtained by anionic polymerization. When the amount is less than 0.1 mol-equivalent, the modification reaction will not proceed properly and the dispersibility of the reinforcing agent will not experience satisfactory improvement, resulting in a deterioration of the crosslinked rubber composition in terms of resistance to traction, wear resistance,
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29/86 wet slip resistance and low hysteresis loss performance.
There are no particular limitations on the method for adding the first alkoxy silane compound used as a modifying agent, and it can be added all at once, it can be added in parts or it can be added continuously. Among these methods, the method of adding everything at once is preferred. In addition, the first alkoxy silane compound can be added in the form of a solution in which, for example, the following is used as the solvent: the conjugated diene monomer, as described in paragraph 11 of this specification, the compound of aromatic vinyl described in paragraph 12, the hydrocarbon solvent described in paragraph 19 or the randomization element described in paragraph 20.
The polymerization temperature for the conjugated diene polymer can be used without change as the temperature of the modification reaction. In specific terms, the range of 0 to 120 ° C is preferred and 20 to 100 ° C is more preferred. The viscosity of the polymer tends to increase when a lower temperature is used, although the active polymerization terminals are likely to be deactivated when a higher temperature is used. Consequently, a temperature outside the numerical range indicated above is therefore disadvantaged. The reaction time in the primary modification reaction is preferably from 1 minute to 5 hours and, more preferably, is from 2 minutes to 1 hour.
A coupling agent can also be added and used in combination with the first alkoxysilane compound in the production of the conjugated diene polymer. Specific examples of this
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30/86 coupling has already been provided above. The coupling agent is added at the stage where the conjugated diene polymer is modified by the first alkoxy silane compound mentioned above.
In this way, the coupling agent that is used in combination with the first alkoxy silane compound and that reacts with the active polymerization terminal can be exemplified by at least one compound selected from the group consisting of (a) compounds of isocyanate and / or isothiocyanate compounds, (b) amide compounds and / or imide compounds, (c) substituted pyridyl ketone compounds and / or substituted pyridyl vinyl compounds, (d) silicon compounds, (e) ester, (f) ketone compounds, (g) tin compounds, (h) epoxy compounds, (i) phosphate ester compounds, (j) compounds containing an acid anhydride group, (k) aryl compounds containing vinyl and (l) compounds that contain a halogenated carbon group.
Among these compounds, favorable examples of component (a) isocyanate compounds and isothiocyanate compounds are 2,4-tolylenedi-isocyanate, 2,6tolylenedi-isocyanate, diphenylmethanedi-isocyanate, diphenylmethanedi-isocyanate of the polymeric type (C-MDI), isophoronadisocyanate, hexamethylenediisocyanate, 1,3,5benzenotriisocyanate and phenyl-1,4-diisothiocyanate.
Favorable examples of component (b) amide compounds and imide compounds are amide compounds, such as succinamide, phthalamide, N, N, N ', N'tetramethylphthalamide, oxamide and N, N, N', N ' -tetramethyloxamide and imide compounds, such as succinimide, Nmethylsuccinimide, maleimide, N-methylmaleimide, phthalimide and N-methylphthalimide.
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31/86
Favorable examples of component (c) substituted pyridyl ketone compounds and substituted pyridyl vinyl compounds are dibenzoylpyridine, diacetylpyridine and divinylpyridine.
compounds
Favorable examples of component (d) of are dibutyldichlorosilane methyltrichlorosilane, methyldichlorosilane, tetrachlorosilane, triethoxy-methylsilane, triphenoxy-methylsilane, trimetoxysilane methyltriethoxy-silane
4,5-epoxyheptylmethyldimethoxy silane bis (triethoxysilylpropyl) tetrasulfide.
Favorable examples of component (e) ester compounds are diethyl adipate, diethyl malonate, diethyl phthalate, diethyl glutarate and diethyl maleate.
Specific favorable examples of component (f) ketone compounds are N, N, N ', N'-tetramethyl-4,4'diaminobenzophenone, N, N, N', N'-tetraethyl-4,4'diaminobenzophenone, N , N-dimethyl-1-aminobenzoquinone,
N, N, N ', N'-tetramethyl-1,3-diaminobenzoquinone, N, N-dimethyl-1aminoanthraquinone and N, N, N', N'-tetramethyl-1,4diaminoanthraquinone.
Favorable examples of component (g) tin compounds are tetrachloro-tin, tetrabromo-tin, trichlorobutyl-tin, trichloromethyl-tin, trichlorooctyl-tin, dibromodimethyl-tin, dichlorodimethyl-tin, dichlorodibutyl-tin, dichlorodioctyl-1,2-dichlorodioctyl bis (trichlorostanil) ethane,
1,2-bis (methyldichlorostanil) ethane, 1,4bis (trichlorostanil) butane, 1,4bis (methyldichlorostanyl) butane, ethyl tin tristearate, butyl tin trisoctanoate, tristearate
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32/86 butyl tin, butyl tin trislaurate, dibutyl tin bisoctanoate, dibutyl tin bis stearate and dibutyl tin bislaurate.
Favorable examples of component (h) epoxy compounds are the polyglycidyl ethers of polyhydric alcohols, for example, ethylene glycol diglycidyl ether and glycerol triglycidyl ether; polyglycidyl ethers of aromatic compounds having at least two phenyl groups, for example, diglycidylated bisphenol A; polyepoxy compounds, such as 1,4-diglycidylbenzene, 1,3,5-triglycidylbenzene and polypoxylated liquid polybutadiene; tertiary amines containing epoxy group, such as 4,4'-diglycidyl diphenylmethylamine and 4,4'diglycidyldibenzylmethylamine; glycidylamino compounds, such as diglycidylaniline, diglycidyl orthotoluidine, tetraglycidyl metaxylenediamine, tetraglycidylaminodiphenylmethane, tetraglycidyl-pphenylenediamine, diglycidylaminomethylcyclohexane and tetraglycidyl-1,3-bis-cyclohexane; and compounds containing the epoxy group and another functional group, for example, 3-glycidoxypropyltrimethoxy-silane, 3-glycidoxypropyltriethoxy-silane, 3-glycidoxypropyltributoxy-silane, epoxy-modified silicones, epoxidized soy oil and epoxidized flax oil.
Favorable examples of component (i) phosphate ester compounds are polyhalogenated phosphorus compounds, such as trichlorophosphine and tribromophosphine; phosphite ester compounds, such as trisnonylphenyl phosphite, trimethyl phosphite and triethyl phosphite; as well as trimethyl phosphate and triethyl phosphate.
Favorable examples of component (j) compounds of the acid anhydride group are anhydride
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33/86 pyromelitic and copolymers of styrene maleic anhydride.
Favorable examples of component (k) vinyl-containing aryl compounds are divinylbenzene, diisopropenylbenzene and divinylbenzene oligomers.
Favorable examples of component (l) compounds that contain a halogenated carbon group are trichloropropane, tribromopropane and tetrachlorobutane.
A single of these compounds for co-use with the first alkoxy silane compound and reactive with the active polymerization terminal can be used on its own or two or more can be used in combination.
The coupling agent is used in an amount of no more than 1 mol and, preferably, from 0.1 to 0.5 mol, depending on the amount of coupling substituent on the coupling agent per 1 gram-atom equivalent of alkali metal or alkaline earth metal in the polymerization initiator. When the amount is greater than 1 mol, the conversion of the first alkoxy silane compound declines and, for example, excellent low hysteresis loss behavior is not obtained for the crosslinked rubber composition.
[Step (b)]
Step (b) is a step of mixing the modified conjugated diene polymer obtained in step (a) with the onium generator and a second alkoxy-silane compound that has at least one alkoxy-silyl group and at least one molecule in one molecule. a group convertible to onio by the onio generator.
Any of the following three modalities can be used for step (b).
The first modality]
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This includes a step (b-1) of mixing the modified conjugated diene polymer obtained in step (a) with the second alkoxy-silane compound that has at least one alkoxy-silyl group and at least one
group convertible to onium for one generator in onium and an stage (b-2) to mix the mixture obtained at step (b -1) common onium generator. [The second modality]This includes a stage (b-3) in mix O
modified conjugated diene polymer obtained in step (a) with an onium generator and a step (b-4) of mixing the mixture obtained in step (b-3) with the second alkoxysilane compound that has in one molecule at least one alkoxy-silyl group and at least one group convertible to onium by an onium generator.
[The third modality]
This includes a step (b-5) in which the modified conjugated diene copolymer obtained in step (a), the onium generator, and the second alkoxy-silane compound that has at least one alkoxy-silyl group in one molecule and at least one group convertible to onion by an onium generator, are all intermixed at the same time.
Each of the components used in step (b) will now be described.
The alkoxy-silyl group in the second alkoxy-silane compound can be exemplified by the same alkoxy-silyl groups as in the first alkoxy-silane compound.
The second alkoxy-silane compound contains at least one alkoxy-silyl group, but, seen from the reaction efficiency perspective, it preferably has two or three and, more preferably, it has three.
The onion convertible group in the second alkoxy silane compound can be exemplified by amino groups
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35/86 primary, secondary amino groups, tertiary amino groups, imino groups, pyridyl groups, primary phosphine groups, secondary phosphine groups, tertiary phosphine groups and thiol groups. A single second alkoxy silane compound can be used on its own or two or more can be used in combination.
The compound that has an alkoxy-silyl group and that has a primary amino group, secondary amino group, tertiary amino group, imino group, pyridyl group, primary phosphine group, secondary phosphine group, tertiary phosphine group or thiol group can be exemplified by the former alkoxy silane compounds provided above as examples, in connection with step (a), but can also be exemplified by 3-aminopropyltrimethoxy silane, 3 aminopropyltriethoxysilane, 3-mercaptomethyltrimethoxysilane, 3-mercaptomethyltriethoxy silane, 3mercaptopropyltrimethoxy silane -mercaptopropyltriethoxysilane, aminophenyltrimethoxy-silane, aminophenyltriethoxysilane, 3- (N-methylamino) propyltrimethoxy-silane, 3- (Nmethylamino) propyltriethoxy-silane, N- (2-aminoethyl) -3aminopropyl-amino-6-amino-propyltrimethoxy silane, the mercaptosilane compounds provided as examples in Japanese Patent Application open to public inspection no. 2006-249069, 3-glycidoxypropyltrimethoxy-silane, 3-glycidoxypropyltriethoxy-silane, 3-glycidoxypropyltributoxy-silane, epoxy-modified silicones, 2- (3,4-epoxy-cyclohexyl) ethyltrimethoxy-silane, 3-glyoxyethyl-ethylene-propyl-trisoxy silane, 3isocyanatopropyltrimethoxy-silane and 3isocyanatopropylmethyldietoxy-silane.
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The second alkoxy silane compound and the other components (for example, the modified conjugated diene polymer obtained in step (a)) can be mixed, for example, in the form of a solution. There are no particular limitations on the mixing regime, and mixing can be carried out using a batch mixer or it can be performed continuously using a device, such as, for example, a continuous multi-stage mixer or an in-line mixer. This mixing reaction is preferably carried out prior to carrying out solvent removal, water treatment, heat treatment, operations required for polymer isolation, and the like, and after the completion of the polymerization reaction.
The amount of use of the second alkoxy silane compound in this mixing step is preferably at least 0.2 mol-equivalent and more preferably at least 0.3 mol-equivalent with reference to the active site of the diene polymer conjugate produced by anionic polymerization. When the amount is less than 0.2 molequivalent, the incorporation of the second alkoxysilane compound with the accompanying onium generation will be inadequate and the reinforcing agent dispersibility will not experience a satisfactory improvement, resulting in a deterioration for the crosslinked rubber composition in the tensile strength, wear resistance, wet slip resistance and low hysteresis loss performance. The second alkoxysilane compound can also be used in conjunction with the first alkoxysilane compound. In this case, the first alkoxy silane compound should be used in an amount that is at least 1.2 mol-equivalents with reference to the location
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37/86 active of the conjugated diene polymer produced by anionic polymerization.
There are no particular limitations on the method for adding the second alkoxy silane compound used as a modifying agent and it can be added all at once, it can be added in parts or it can be added continuously, where the adding everything at once is preferred. In addition, the second alkoxy silane compound can be added in the form of a solution in which, for example, the hydrocarbon solvent described in paragraph 19 of this specification or the randomization element described in paragraph 20 of this specification is the solvent .
The polymerization temperature for the conjugated diene polymer can be used without changing the temperature during mixing the second alkoxy silane compound and the other components (for example, the modified conjugated diene polymer obtained in step (a)). In specific terms, the range of 0 to 120 ° C is preferred and 20 to 100 ° C is more preferred. The viscosity of the polymer tends to increase when a lower temperature is used, although the active polymerization terminals are likely to deactivate when the temperature is higher, and a temperature outside the above-indicated numerical range is therefore disadvantaged. The mixing time is preferably from 1 minute to 5 hours and more
preference is from 2 minutes onion generator can to 1 hour.be exemplified perO halides in metal, such as halide compounds in silicon, halide compounds tin compounds in
aluminum halide, titanium halide compounds, zirconium halide compounds, germanium halide compounds, gallium halide compounds, compounds of
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38/86 zinc halide, and so on; inorganic acid esters, such as sulfate esters, phosphate esters, carbonate esters, nitrate esters, and so on; inorganic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, carbonic acid, phosphoric acid, and so on; inorganic acid salts, such as potassium fluoride, tetramethylammonium fluoride, tetra-n-butylammonium fluoride, and so on; and organic acids, such as carbonic acid, sulfonic acid, and so on. The following are the most preferred from the point of view of ease of acquisition and ease of handling: silicon halide compounds, tin halide compounds, aluminum halide compounds, titanium halide compounds, zirconium halide compounds , germanium halide compounds, gallium halide compounds, zinc halide compounds, sulfate esters, phosphate esters, carbonic acid and sulfonic acid.
The onium-generating compound can be exemplified by silicon tetrachloride, tin tetrachloride, trimethylsilyl chloride, dimethyldichlorosilane, methyltrichlorosilane, methyl dichlorosilane, diethylaluminium chloride, ethyl aluminum sesquichloride, ethylene chloride, zinc chloride, zinc chloride, chloride , zirconium tetrachloride, zirconocene dichloride, germanium tetrachloride, gallium trichloride, diethyl sulfate, dimethyl sulfate, magnesium lauryl ether sulfate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, 2-ethyl hexate phosphate , triphenyl phosphate, tricresyl phosphate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate,
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39/86 nitrocellulose, nitroglycerin, nitroglycol, formic acid, acetic acid, oxalic acid, maleic acid, citric acid, malic acid, fumaric acid, malonic acid, acrylic acid, crotonic acid, succinic acid, glutaric acid, itaconic acid, tartaric acid , sebacic acid, terephthalic acid, isophthalic acid, βmercaptopropionic acid, benzenesulfonic acid, ptoluenesulfonic acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid, iodhydric acid, sulfuric acid, nitric acid, carbonic acid, phosphoric acid, potassium fluoride, potassium fluoride and tetra-n-butylammonium fluoride.
All of these onio generators have the same functionality in terms of being able to generate onio from the convertible to onio group, and those species not explored in the examples below can also be used in the present invention.
The onium generator can be mixed with the other components (for example, the mixture of the modified conjugated diene polymer obtained in step (a) with the second alkoxy silane compound), for example, in the form of a solution. The mixing regime is not particularly limited and mixing can be carried out using a batch mixer or it can be carried out in a continuous regime using equipment, such as, for example, a continuous multistage mixer or a lined mixer.
The onium generator is used in an amount that is preferably at least 0.5 mol-equivalent and more preferably at least 1.0 mol-equivalent with reference to the active site of the conjugated diene polymer obtained by the polymerization anionic. When the amount is less than 0.5 mol-equivalent, the generation of onium is not
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40/86 proceeds properly and the rubber shape retention behavior may deteriorate.
There are no particular limitations on the method for adding the onium generator, and it can be added all at once, it can be added in parts or it can be added continuously. Among these methods, the all-in-one addition method is preferred. In addition, the onium generator can be added in the form of a solution in which, for example, the hydrocarbon solvent described in paragraph 19 of this specification or the element of randomization described in paragraph 20 of this specification is the solvent.
The polymerization temperature for the conjugated diene polymer can be used without changing the temperature when mixing the onium generator and the other components (for example, mixing the modified conjugated diene polymer obtained in step (a) with the second alkoxy silane compound). In specific terms, the range of 0 to 120 ° C is preferred and 20 to 100 ° C is more preferred. The viscosity of the polymer tends to increase when a lower temperature is used, although the active polymerization terminals are likely to undergo deactivation when the temperature is higher, and a temperature outside the numerical range indicated above is therefore disadvantaged. The mixing time is preferably from 1 minute to 5 hours and more preferably from 2 minutes to 1 hour.
In the method of the present invention for the production of a modified conjugated diene rubber, the addition of the onium generator can be followed by the recovery of the modified conjugated diene polymer by removing solvent (for example, steam distillation) and
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41/86 known drying operation for the production of conjugated diene polymers.
There are no particular limitations on the method of forming an onium structure through contact between water and the onium generator and, for example, the following methods are preferred: (i) a method in which water is directly added to the solution of onium polymer after step (b) and mixing is performed; (ii) a method in which a solution is prepared by dissolving water in an organic solvent that is soluble in both an organic solvent and in water, for example, an alcohol, and this solution is added to the polymer solution after step ( b) and mixing is performed; and (iii) a method in which, after step (b), the water is mixed with the polymer solution and / or the polymer at the same time as the removal of solvent by means of a steam distillation step. Among these methods, method (iii) - where after step (b) the water is mixed with the polymer solution and / or the polymer at the same time as the removal of solvent by means of a steam distillation step - it is particularly preferred, from the point of view of forming an effective onium structure.
The reaction temperature is preferably 30 to 150 ° C and more preferably 80 to 120 ° C.
The modified conjugated diene polymer used in this step takes the form of the polymer solution generated by producing the modified conjugated diene polymer and used as such without removing solvent.
Alternatively, this polymer solution can be subjected to solvent removal by means of, for example, steam distillation, and the conjugated diene polymer obtained by further drying can then be redissolved in a
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42/86 solvent, for example, cyclohexane, and this can be used.
[2] The modified conjugated diene rubber
The modified conjugated diene rubber of this embodiment consists of the modified conjugated diene rubber obtained by the method of producing modified conjugated diene rubber described above. This modified conjugated diene rubber has a high Mooney viscosity, excellent shape stability and excellent processability. The Mooney viscosity (ML1 + 4, 100 ° C) of the modified conjugated diene rubber of this modality is preferably 30 to 150 and more preferably 40 to 120. Format stability tends to decline when Mooney viscosity ( ML1 + 4, 100 ° C) is less than 30. When, on the other hand, the Mooney viscosity (ML1 + 4, 100 ° C) exceeds 150, the processability is unsatisfactory and mixing / kneading with ingredients of the composition becomes very problematic. When the Mooney viscosity is too high, it can be placed in the indicated range by means of oil extension with a common extender oil. An aromatic oil, naphthenic oil, paraffinic oil or aromatic substitute oil that has a PCA of not more than 3% by weight, by the IP346 method, are preferably used for the extender oil. The amount of use of the extender oil can be freely selected, but it is typically 10 to 50 parts by weight (i.e., parts by weight) per 100 parts by weight of the modified conjugated diene rubber. When an extender oil is used, it is often used in an amount of incorporation generally 20 to 37.5 parts by mass. In addition, using classification based on the oil production process, T-DAE oil (treated distilled aromatic extract),
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43/86 T-RAE oil (residual aromatic extract treated), MES oil (moderate extract solvate) and RAE oil (residual aromatic extract) are suitably used.
[3] The composition of rubber
In one embodiment of the rubber composition of the present invention, the modified conjugated diene polymer described above is incorporated as a rubber component. The details of this are described below.
[3-1] The rubber component
The modified conjugated diene rubber incorporated in the rubber composition of this embodiment contains the modified conjugated diene polymer described above. The percentage content of the modified conjugated diene polymer in the modified conjugated diene rubber is preferably at least 20% by weight, more preferably at least 30% by weight, and particularly preferably at least 40%, in large scale. A percentage content of at least 20% by weight can provide even better mechanical properties for the crosslinked rubber composition, for example, tensile strength and tensile elongation, and even better crack growth resistance and wear resistance. .
The modified conjugated diene rubber may contain a single species of modified conjugated diene polymer or may contain two or more species of modified conjugated diene polymers. In addition, a rubber component in addition to the modified conjugated diene polymer can also be present in the modified conjugated diene rubber. This other rubber component can be exemplified by natural rubber, synthetic isoprene rubber, butadiene rubber,
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44/86 modified butadiene, styrene-butadiene rubber, modified styrene-butadiene rubber, ethylene-a-olefin copolymer rubber, ethylene-a-olefin-diene copolymer rubber, acrylonitrile-butadiene copolymer rubber, rubber chloroprene, halogenated butyl rubber, styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, random styrene-butadiene-isoprene copolymer rubber, styrene-acrylonitrile-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, acrylonitrile-butadiene copolymer polystyrene-polybutadiene-polystyrene block, and mixtures of those mentioned above. A crosslinked rubber that has excellent low hysteresis loss behavior can be produced when another rubber component known to be usable for rubber compositions for tire applications is also incorporated.
[3-2] Other components (carbon black, silica)
The rubber composition of this embodiment preferably also contains carbon black and / or silica. Carbon black can be specifically exemplified by varying degrees of carbon black, such as furnace carbon blacks, as represented by SRF, GPF, FEF, HAF, ISAF, SAF, ISAF-HS, ISAF-LS, IISAF-HS , HAF-HS, and HAF-LS; acetylene carbon blacks; thermal carbon blacks; channel carbon blacks; graphite; graphite fiber; fullerenes, and so on. A carbon black that has an iodine (IA) absorption of at least 60 mg / g and an absorption of dibutyl phthalate (DBP) of at least 80 ml / 100 g is preferred. The use of carbon black provides a great improvement in the adhesion performance and failure resistance of the crosslinked rubber composition. HAF, ISAF and SAF, which provide excellent resistance to
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45/86 wear, are particularly preferred. A single carbon black can be used or two or more carbon blacks can be used in combination.
Silica can be specifically exemplified by wet method silica (hydrated silicic acid), dry method silica (anhydrous silicic acid), colloidal silica, precipitated silica, calcium silicate and aluminum silicate. Among these, wet method silicas are preferred due to the fact that they provide the most significant improvement in failure resistance and the best balance between wet grip behavior and low rolling resistance performance. In addition, the use of a highly dispersible silica is also preferred from the point of view of providing good dispersibility in the rubber and from the point of view of properties and processability. A single silica can be used or two or more silicas can be used in combination.
The rubber composition of this modality preferably contains from 20 to 130 parts by mass of carbon black and / or silica per 100 parts by weight of the rubber component (the sum of the modified conjugated diene rubber and the other component or rubber components), where 25 to 110 parts by mass is even more preferred when viewed from the perspective of improvement in reinforcement performance and improvement in the various properties thus generated. In a low percentage of carbon black and / or silica, the improvement, for example, in the resistance to failure, will tend to be inadequate. In a large percentage of content for carbon black and / or silica, the processability of the rubber composition will tend to be reduced. For these reasons, the percentage of content is
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situates preferably in banner numeric previously indicated. The incorporation of an charge of phase double of carbon-silica in rubber in copolymer gives gift invention makes it possible get the same benefits favorable that the co-use of black of smoke with silica. THE
carbon-silica double-phase charge is a so-called silica-coated carbon black, in which the silica is chemically bonded on the surface of the carbon black and is commercially available under the product names CRX2000, CRX2002 and CRX2006 from Cabot Corporation . The amount of incorporation of double-phase carbon-silica filler is preferably from 1 to 100 parts by weight and more preferably from 5 to 95 parts by weight, in each case per 100 parts by weight for the total rubber component.
When silica is incorporated as a reinforcing agent in the rubber composition of this embodiment, a silane coupling agent is also preferably incorporated in order to produce further improvements in the reinforcing effect. This silane coupling agent can be exemplified by bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysylethyl) tetrasulfide, bis (3-trimetoxyethylsilpropyl), bis (2-trimethoxyisylethyl) tetrasulfide, 3-mercaptopropyltrimethoxy-silane, 3-mercaptopropyltriethoxy-silane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxy-silane, 3-trimethoxyethylpropyl-niethyl-trimethyl-trimethyl-trimethyl-trimethyl-trimethyl, dimethyl
2-triethoxy-silylethyl-N, N-dimethylthiocarbamoylmethylsulfide,
3-trimethoxy-silylpropyl-benzothiazolyl-tetrasulfide, 3-
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47/86 sililpropilbenzoliltetrassulfeto triethoxysilane, 3-triethoxysilylpropyl methacrylate monossulfeto, monossulfeto 3-trimethoxysilylpropyl methacrylate, bis (3-dietóximetilsililpropil) tetrassulfeto, 3-mercaptopropildimetóximetilsilano, metilsililpropil-dimethoxy-N, Ndimetiltiocarbamoiltetrassulfeto, dimetóximetilsililpropilbenzotiazoliltetrassulfeto and mercaptosilane compounds given as examples in the Order of Japanese Patent open to public inspection n. 2006-249069.
The commercially available products can be exemplified by the products “NXT Silano”, “NXT Z
Silano ”,“ NXT-Low-V Silano ”and“ NXT Ultra Low-V Silano ”together with Momentive Performance Materials Inc .; the product “VP Si363” with Degussa; and the product “11MERCAPTOUNDECILTRIMETÓXI-SILANO” with Gelest, Inc.
Preferred among the above are the following, from the point of view of enhancement in reinforcement performance: bis (3-triethoxysilylpropyl) polysulfide, 3-trimethoxysilylpropylbenzothiaziltetrasulfide, and the mercaptosilane compounds provided as examples in the open Japanese Patent Application public inspection no. 2006-249069.
A single of these silane coupling agents can be used or two or more can be used in combination. The amount of silane coupling agent incorporation varies depending on a function, for example, of the type of silane coupling agent, but is preferably 1 to 20 parts by weight and more preferably 3 to 15 parts by weight. mass, in each case per 100 parts by mass of silica. When the amount is less than 1 part by mass, it tends to be difficult for the effects as a coupling agent to be properly manifested. When, on the other hand, when the quantity is greater than 20 parts in
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48/86 mass, the rubber component then tends to be prone to gelation.
There are no particular limitations on the composition ingredients for the rubber composition of the present invention. A compatibilizer can also be added during mixing / kneading to improve processability during mixing / kneading or to produce additional improvements in balance between wet slip resistance, low hysteresis loss behavior and wear resistance. Preferred compatibilizers are organic compounds selected from compounds containing epoxy group, carboxylic acid compounds, carboxylate ester compounds, ketone compounds, ether compounds, aldehyde compounds, compounds containing hydroxyl group and compounds containing amino group, or are silicone compounds selected from alkoxy silane compounds, siloxane compounds and aminosilane compounds. The following compounds are specific examples of organic compound compatibilizers.
Compounds containing epoxy group: butyl glycidyl ether, diglycidyl ether, propylene oxide, neopentyl glycol diglycidyl ether, epoxy resins, epoxidized soybean oil and epoxidized aliphatic acid esters.
Carboxylic acid compounds: adipic acid, octylic acid and methacrylic acid.
Carboxylate ester compounds: acrylate esters, diethyl acrylate, ethyl methacrylate, orthoacetate esters, ethyl acetoacetate, butyl acetate, isopropyl acetate, dimethyl carbonate, p-hydroxyphenyl acetate, polyester type plasticizers and plasticizers of the stearic acid type.
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Ketone compounds: methylcyclohexanone and acetylacetone.
Ether compounds: isopropyl ether and dibutyl ether.
Aldehyde compounds: undecylene aldehyde, decyl aldehyde, vanillin, 3,4-dimethoxy-benzaldehyde and cuminaldehyde.
Amino group-containing compounds: isopropylamine, diisopropylamine, triethylamine, 3-ethoxy-propylamine, 2-ethylhexylamine, isopropanolamine, N-ethylethylenediamine, ethyleneimine, hexamethylenediamine, 3-lauryloxypropylamine, aminophenol, aniline, anilinine, aniline, 3-amine, aniline, aniline, aniline, aniline, aniline, aniline, aniline, aniline, aniline, aniline, aniline, aniline, amine, aniline, aniline, amine. , N-methyldiethanolamine, Nmethylethanolamine, 3-amino-1-propanol, ethylamine hydrochloride and n-butylamine hydrochloride.
Hydroxyl-containing compounds: isopropyl alcohol, butanol, octanol, octanediol, ethylene glycol, methylcyclohexanol, 2-mercaptoethanol, 3-methyl-3-methoxy-1-butanol, 3-methyl-1,5-pentanediol, 1-octadecanol, diethylene glycol, butylene glycol, dibutylene glycol and triethylene glycol.
Compounds containing epoxy group, compounds containing amino group and compounds containing hydroxyl group are preferred over the above.
The following compounds are specific examples of silicone compound compatibilizers.
Alkoxy silane compounds: trimethylmethoxysilane, trimethylethoxy silane, dimethyldimethoxy silane, methyltriethoxy silane, methyltriphenoxy silane, tetraethoxysilane, methylldiethoxy silane and vinyltrimethoxy silane.
Siloxane compounds: dimethylsiloxane oligomer, silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, silicone-modified oil
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50/86 polyether, alkyl modified silicone oil, superior aliphatic ester modified silicone oil, superior alkoxy modified silicone oil and silicone oil containing superior aliphatic acid.
Aminosilane compounds: hexamethyldisilazane, nonamethyltrisilazane, anilinotrimethylsilane, bis (dimethylamino) dimethylsilane, bis (diethylamino) dimethylsilane and triethylaminosilane. The compounds of silazane and bis (dimethylamino) dimethylsilane are preferred among the above.
Various chemicals and additives commonly used in the rubber industry can be added on an optional basis to the rubber composition of this modality within a range that does not detract from the objectives of the present invention. The chemicals and additives that can be added to the rubber composition of this modality can be exemplified by crosslinking agents (for example, vulcanizing agents), vulcanizing aids, processing aids, vulcanization accelerators, process oils, aging inhibitors (ie, antioxidants), burn inhibitors, zinc white, stearic acid, and so on.
The vulcanizing agent can be exemplified by sulfur, sulfur halides, organoperoxides, quinonadioximes, polyvalent organic amine compounds and alkylphenol resins containing methylol group.
Sulfur is generally used among these vulcanizing agents. It is preferably used from 0.1 to 5 parts by weight and more preferably from 0.5 to 3 parts by weight per 100 parts by weight of the modified conjugated diene rubber (starting rubber;
rubber components). Stearic acid is generally
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51/86 used as a vulcanization aid and processing aid. The amount of use of the vulcanization aid and the processing aid is generally from 0.5 to 5 parts by weight per 100 parts by weight of the modified conjugated diene rubber.
There are no particular limitations on the vulcanization accelerator, and the vulcanization accelerator can be exemplified by sulfenamide type compounds, guanidine type compounds, thiuram type compounds, thiourea type compounds, thiazole type compounds, dithiocarbamate type compounds and compounds xanthic acid type. Preferred examples of the vulcanization accelerator are 2-mercaptobenzothiazole, dibenzothiazildisulfide, N-cyclohexyl-2benzothiazilsulfenamide, Nt-butyl-2benzothiazolsulfenamide, N-oxyethylene-2benzothiazolsulfenamide, N-oxy-ethyl-2-benzyl-2-benzyl , diphenylguanidine, diortotolylguanidine and orthotolylbisguanidine. The vulcanization accelerator is generally used from 0.1 to 5 parts by weight, and preferably from 0.4 to 4 parts by weight per 100 parts by weight of the modified conjugated diene rubber.
The rubber composition of the present invention can be produced by mixing (ie kneading) using a mixer (ie kneading), for example, an open mixer (or open kneading), most prominently a cylinder, or a closed mixer (or closed kneader), most prominently a Banbury mixer. In addition, the rubber composition of the present invention can be used for various rubber products by inducing
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52/86 cross-linking (vulcanization) after a molding process. The crosslinked rubber composition (the crosslinked rubber composition) of this modality is well suited for use in tire applications such as, for example, a tire tread, undercoat, carcass, side band, bead, and so on. onwards, and is well suited for application as a vibration-damping rubber, marine bumper material, belt, hose and other industrial products. The crosslinked rubber composition of this modality is particularly well suited for use as a tire tread rubber.
The properties of the modified conjugated diene polymer (produced by step (a)), the modified conjugated diene rubber (produced by step (b)), the rubber composition and the crosslinked rubber composition in the present invention are as set out below .
Seen from the perspective of maintaining a balance between the shape stability of the modified conjugated diene rubber and the processability during the production of the rubber composition, the conjugated diene polymer, before modification, has an average weighted molecular weight according to polystyrene and determined by gel permeation chromatography (GPC), preferably
10,000 to 1,500,000, more preferably 50,000 The 1,000,000 and particularly preferably, 1000.00 The 800,000. Seen from the perspective of keep one balance between loss-of-behavior hysteresis
the resulting crosslinked rubber composition and its resistance to wet slip, the glass transition temperature of the conjugated diene rubber
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The modified 53/86 is preferably less than or equal to 0 ° C, more preferably less than or equal to -5 ° C and particularly preferably less than or equal to -10 ° C.
Seen from the perspective of maintaining a balance between the shape stability of the modified conjugated diene rubber and the processability during the production of the rubber composition, the Mooney viscosity (ML1 + 4, 100 ° C) of the modified conjugated diene rubber is preferably from 30 to 150 and more preferably from 40 to 120.
Seen from the perspective of the shape stability of the modified conjugated diene rubber, the cold flow value (mg / minute) of the modified conjugated diene rubber is preferably not greater than 1.5, more preferably, not greater than 1.0 and, particularly preferably, not greater than 0.5.
Viewed from a processability perspective during tire manufacturing, the Mooney viscosity (ML1 + 4, 100 ° C) of the rubber composition is preferably from 20 to 150, more preferably from 30 to 130 and, particularly preferably, from 40 to 110.
The tensile strength index (JIS K 6301, module 300%) for the crosslinked rubber is preferably at least 100 and more preferably at least 103.
The index for tan δ at 0 ° C of the crosslinked rubber is preferably at least 125 and more preferably at least 130.
The index for tan δ at 70 ° C of the crosslinked rubber is preferably at least 130 and more preferably at least 135.
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The wear resistance index (JIS K 6264,
No. of loading, 25 ° C) for the crosslinked rubber is preferably at least 105, more preferably at least 107 and particularly preferably at least 109.
EXAMPLES
The present invention is specifically described below on the basis of examples, but the present invention is not limited to these examples. In the examples and comparative examples, parts and% are on a mass basis (ie, weight basis), except where specifically stated otherwise. The following methods were used to measure the different property values.
[bound styrene content (%)]: determined by 1H-NMR at 500 MHz [vinyl content (%)]: determined by 1H-NMR at 500 MHz [glass transition temperature (° C)]: measured accordingly with ASTM D 3418 [re-modification molecular weight]: This was determined as polystyrene from the retention time that corresponds to the top of the maximum peak in the GPC curve obtained by gel permeation chromatography (GPC) (HLC-8120GPC ( product name (available from Tosoh Corporation))).
(GPC conditions) column: 2 x GMHHXL (product name, available from Tosoh Corporation) column temperature: 40 ° C mobile phase: tetrahydrofuran flow rate: 1.0 mL / minute sample concentration: 10 mg / 20 mL
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55/86 [Mooney viscosity (ML1 + 4, 100 ° C)]: This was determined based on JIS K 6300, using an L rotor and the following conditions: preheating for 1 minute, run time of rotor = 4 minutes, temperature =
100 ° C.
[cold flow value]: The copolymer was maintained at a temperature of 50 ° C and was extruded from a 6.35 mm orifice under a pressure condition of 24.1 kPa. In 10 minutes from the start of the extrusion (after the extrusion rate had become constant), the amount (mg) of copolymer extrusion was measured every 30 minutes for 90 minutes. The average value was taken as the cold flow value (mg / minute). A higher numerical value indicates a less satisfactory shape stability due to the rubber and more difficult handling.
Example 1[Synthesis and evaluation gives diene rubber modified conjugate THE] 2,750 g in cyclohexane, 50.0 g of tetra- hydrofuran, 125 g in styrene and 365 g of 1,3-butadiene
were loaded into a 5 L autoclave reactor that had been replaced by nitrogen. The temperature of the reactor contents was adjusted to 10 ° C, followed by the addition of a solution of cyclohexane containing n-butyllithium (5.80 mmol) to initiate the polymerization. The polymerization was carried out adiabatically and a maximum temperature of 85 ° C was reached.
When the polymerization conversion had reached 99%, an additional addition of 10 g of butadiene was made and the polymerization was carried out for an additional 5 minutes, after which 10 g of the polymer solution was
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56/86 sampled in order to perform the measurement of the pre-modification of molecular weight. A solution of cyclohexane containing N, N-bis (triethylsilyl) aminopropylmethyldimethoxy silane (4.96 mmol) was added and a reaction was carried out for 15 minutes. After this reaction, a cyclohexane solution containing 3-aminopropyltriethoxy silane (4.96 mmol) was added to the polymer solution; the mixing was carried out for 5 minutes; a solution of cyclohexane containing silicon tetrachloride (3.93 mmol) was then added; and the mixing was subsequently carried out for 5 minutes. 2.0 g of 2,6-di-tert-butyl-p-cresol were then added to the resulting polymer solution. This was followed by the removal of solvent by steam distillation using hot water adjusted to pH = 9 with sodium hydroxide. The rubber was dried in a thermostat-regulated hot cylinder at 110 ° C to produce the modified conjugated diene rubber A.
The polymerization formula for the modified conjugated diene rubber A is given in table 1, while the properties of the modified conjugated diene rubber obtained A are given in table 2. Using the modified conjugated diene rubber A, a composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
Example 2 [Synthesis and evaluation of modified conjugated diene rubber B]
A modified conjugated diene rubber B was obtained using the same method as Example 1, but, in this case, using N, N ', N'-tris (trimethylsilyl) -N- (2aminoethyl) -3-aminopropyltriethoxy -silano in place of N, NPetição 870190089753, of 10/09/2019, p. 61/97
57/86 bis (triethylsilyl) aminopropylmethyldimethoxy silane used in
Example 1 and changing the amount of 3.93 mmol of silicon tetrachloride used in Example 1 to 5.17 mmol.
The polymerization formula for the modified conjugated diene rubber B is given in table 1, while the properties of the modified conjugated diene rubber obtained are given in table 2. Using the modified conjugated diene rubber B, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
Example 3
[Synthesis and evaluation of diene rubber modified conjugate C] 2,750 g in cyclohexane, 10.3 g of tetra- hydrofuran, 50 g in styrene and 440 g of 1,3-butadiene
were loaded into a 5 L autoclave reactor that had been replaced by nitrogen. The temperature of the reactor contents was adjusted to 10 ° C, followed by the addition of a solution of cyclohexane containing n-butyllithium (5.80 mmol) to initiate the polymerization. The polymerization was carried out adiabatically and the maximum temperature of 90 ° C was reached.
When the polymerization conversion had reached 99%, an additional addition of 10 g of butadiene was made and the polymerization was carried out for an additional 5 minutes, after which 10 g of the polymer solution was sampled in order to perform the pre-measurement. molecular weight modification. The cyclohexane solution containing 1- (3-triethoxy-silylpropyl) -2,2,5,5-tetramethyl-1-aza-2,5disilacyclopentane (2.48 mmol) was added and the reaction
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58/86 was performed for 15 minutes. After this reaction, a cyclohexane solution containing 3-aminopropyltriethoxysilane (2.48 mmol) was added to the polymer solution; the mixing was carried out for 5 minutes; a solution of cyclohexane containing silicon tetrachloride (2.69 mmol) was then added; and the mixing was subsequently carried out for 5 minutes. 2.0 g of 2,6-di-tert-butyl-pcresol were then added to the resulting polymer solution. This was followed by the removal of solvent by steam distillation using hot water adjusted to pH = 5 with sulfuric acid. The rubber was dried in a hot cylinder regulated by thermostat at 110 ° C to produce the modified conjugated diene rubber C.
The polymerization formula for the modified conjugated diene rubber C is given in table 1, while the properties of the modified conjugated diene rubber obtained are given in table 2. With the use of the modified conjugated diene rubber C, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
Example 4 [Synthesis and evaluation of modified conjugated diene rubber D]
A modified conjugated diene rubber D was obtained using the same method as in Example 2, but in this case, using N- [3- (trimethoxy-silyl) propyl] -N, N'dietyl-N'- trimethylsilylethane-1,2-diamine in place of
N, N ', N'-tris (trimethylsilyl) -N- (2-aminoethyl) -3aminopropyltriethoxy silane used in Example 2.
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The polymerization formula for the modified conjugated diene rubber D is given in table 1, while the properties of the modified conjugated diene rubber obtained are given in table 2. With the use of the modified conjugated diene rubber D, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
Example 5 [Synthesis and evaluation of the modified conjugated diene rubber E]
A modified conjugated diene rubber E was obtained using the same method as in Example 2, but in this case, using 3- (4-trimethylsilyl-1piperazine) propyltriethoxy silane in place of N, N ', N' tris (trimethylsilyl) -N- (2-aminoethyl) -3-aminopropyltriethoxysilane used in Example 2.
The polymerization formula for the modified conjugated diene rubber E is given in table 1, while the properties of the modified conjugated diene rubber obtained E are given in table 2. With the use of the modified conjugated diene rubber E, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
Example 6 [Synthesis and evaluation of the modified conjugated diene rubber F]
A modified F-conjugated diene rubber was obtained using the same method as Example 1, but, in this case, using bis [3- (triethoxy
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60/86 silyl) propyl) trimethylsilylamine (2.48 mmol) in place of the N, N-bis (triethylsilyl) aminopropylmethyldimethoxy silane (4.96 mmol) used in Example 1 and changing the amount of 3.93 mmol of the addition of silicon tetrachloride used in Example 1 to 3.31 mmol.
The polymerization formula for the modified conjugated diene rubber F is given in table 1, while the properties of the modified conjugated diene rubber obtained are given in table 2. With the use of the modified conjugated diene rubber F, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
Example 7 [Synthesis and evaluation of the modified conjugated diene rubber G]
A modified G-conjugated diene rubber was obtained using the same method as in Example 1, but in this case, using 3-diethylaminopropyltriethoxy silane in place of the N, N-bis (triethylsilyl) aminopropylmethyldimethoxysilane used in Example 1.
The polymerization formula for the modified conjugated diene rubber G is given in table 1, while the properties of the modified conjugated diene rubber obtained are given in table 2. With the use of the modified conjugated diene rubber G, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
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Example 8 [Synthesis and evaluation of the modified conjugated diene rubber H]
A modified H-conjugated diene rubber was obtained using the same method as Example 1, but in this case, using S-trimethylsilylmercaptopropyltriethoxysilane in place of N, Nbis (triethylsilyl) aminopropylmethyldimethoxy silane used in Example 1.
The polymerization formula for the modified conjugated diene rubber H is given in table 1, while the properties of the modified conjugated diene rubber obtained are given in table 2. With the use of the modified conjugated diene rubber H, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
Example 9 [Synthesis and evaluation of modified conjugated diene rubber I]
A modified conjugated diene rubber I was obtained using the same method as in Example 1, but in this case, using 3-diphenylphosphinopropyltrimethoxy silane in place of the N, N-bis (triethylsilyl) aminopropylmethyldimethoxysilane used in Example 1.
The polymerization formula for the modified conjugated diene rubber I is given in table 1, while the properties of the modified conjugated diene rubber I are given in table 2. With the use of the modified conjugated diene rubber I, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and the
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Example 10 [Synthesis and evaluation of the modified conjugated diene rubber J]
A modified conjugated diene rubber J was obtained using the same method as Example 1, but in this case, using mercaptopropyltriethoxy silane in place of the 3-aminopropyltriethoxy silane used in Example 1.
The polymerization formula for the modified conjugated diene rubber J is given in table 1, while the properties of the modified conjugated diene rubber obtained are given in table 2. With the use of the modified conjugated diene rubber J, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
Example 11 [Synthesis and evaluation of modified conjugated diene rubber K]
A cyclohexane solution containing 2,750 g of cyclohexane, 3.25 g of 2,2-di (tetrahydrofuryl) propane, 125 g of styrene, 365 g of 1,3-butadiene, and piperidine (4 , 70 mmol) was loaded into a 5 L autoclave reactor that had been replaced with nitrogen. The temperature of the reactor contents was adjusted to 10 ° C, followed by the addition of a solution of cyclohexane containing n-butyl lithium (5.80 mmol) to initiate the polymerization. The polymerization was carried out adiabatically and the maximum temperature of 85 ° C was reached.
When the polymerization conversion had reached 99%, an additional 10 g of butadiene
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63/86 was carried out and the polymerization was carried out for an additional 5 minutes, after which 10 g of the polymer solution was sampled in order to perform the pre-modification measurement of molecular weight. A solution of cyclohexane containing N, N-bis (triethylsilyl) aminopropylmethyldimethoxy silane (4.96 mmol) was added and the reaction was carried out for 15 minutes. After this reaction, the cyclohexane solution containing N-2- (aminoethyl) -3-aminopropyltrimethoxy-silane (4.96 mmol) was added to the polymer solution; the mixing was carried out for 5 minutes; a solution of cyclohexane containing silicon tetrachloride (6.34 mmol) was then added; and the mixing was subsequently carried out for 5 minutes. 4.0 g of 2,6-di-tert-butyl-p-cresol was then added to the resulting polymer solution. This was followed by the removal of solvent by steam distillation using hot water adjusted to pH = 10 with sodium hydroxide. The rubber was dried in a thermostat-controlled hot cylinder at 110 ° C to produce the modified conjugated diene rubber K.
The polymerization formula for the modified conjugated diene rubber K is given in table 1, while the properties of the modified conjugated diene rubber obtained are given in table 2. With the use of the modified conjugated diene rubber K, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
Example 12 [Synthesis and evaluation of the modified conjugated diene rubber L]
A modified conjugated diene rubber L was obtained using the same method as Example 11, but in this case
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64/86 case, with the use of 3-aminopropyltriethoxy silane (9.92 mmol) in place of the N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (4.96 mmol) used in Example 11.
The polymerization formula for the modified conjugated diene rubber L is given in table 1, while the properties of the modified conjugated diene rubber obtained are given in table 2. With the use of the modified conjugated diene rubber L, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
Example 13 [Synthesis and evaluation of the modified conjugated diene rubber M]
A modified conjugated diene rubber M was obtained using the same method as Example 11, but in this case, using 3-aminopropyltriethoxy silane in place of the N-2- (aminoethyl) -3-aminopropyltrimethoxy silane used in Example 11 and using diethyl aluminum chloride (20.4 mmol) in place of the silicon tetrachloride (6.34 mmol) used in Example 11.
The polymerization formula for the modified conjugated diene rubber M is given in table 1, while the properties of the modified conjugated diene rubber obtained are given in table 2. Using the modified conjugated diene rubber M, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
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Example 14 [Synthesis and evaluation of the modified conjugated diene rubber N]
A modified N-conjugated diene rubber was obtained using the same method as Example 13, but in this case, using titanium tetrachloride (5.10 mmol) in place of the diethyl aluminum chloride (20.4 mmol) used in Example 13.
The polymerization formula for the modified conjugated diene rubber N is given in table 1, while the properties of the modified conjugated diene rubber obtained are given in table 2. With the use of the modified conjugated diene rubber N, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
Example 15 [Synthesis and evaluation of modified conjugated diene rubber O]
A modified conjugated diene rubber O was obtained using the same method as Example 13, but in this case, using isopropyl acid phosphate (13.61 mmol) in place of diethyl aluminum chloride (20.4 mmol) used in Example 13.
The polymerization formula for modified conjugated diene rubber O is given in table 1, while the properties of the modified conjugated diene rubber obtained O are given in table 2. With the use of modified conjugated diene rubber O, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and the
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66/86 property valuation was performed. The results are shown in table 4.
Example 16 [Synthesis and evaluation of modified conjugated diene rubber P]
2,750 g of cyclohexane, 100.0 g of tetrahydrofuran, 180 g of styrene and 310 g of 1,3-butadiene were loaded into a 5 L autoclave reactor that had been replaced by nitrogen. The temperature of the reactor contents was adjusted to 20 ° C, followed by the addition of a solution of cyclohexane containing n-butyllithium (4.60 mmol) to initiate the polymerization. The polymerization was carried out adiabatically and the maximum temperature of 85 ° C was reached.
When the polymerization conversion had reached 99%, an additional addition of 10 g of butadiene was made and the polymerization was carried out for an additional 5 minutes, after which 10 g of the polymer solution was sampled in order to perform the pre-measurement. molecular weight modification. A solution of cyclohexane containing N, N-bis (triethylsilyl) aminopropylmethyldimethoxy silane (3.93 mmol) was added and the reaction was carried out for 15 minutes. After this reaction, a solution of cyclohexane containing 3-aminopropyltriethoxy silane (3.93 mmol) was added to the polymer solution; the mixing was carried out for 5 minutes; a solution of cyclohexane containing silicon tetrachloride (3.12 mmol) was then added; and the mixing was subsequently carried out for 5 minutes. 2.0 g of 2,6-di-tert-butyl-p-cresol was then added to the resulting polymer solution; 187.5 g of naphthenic oil (trademark: SNH46, available from Sankyo Yuka Kogyo Kabushiki Kaisha) was then added; and mixing was carried out for 5 minutes. This
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67/86 was followed by the removal of solvent through steam distillation using hot water adjusted to pH = 9 with sodium hydroxide. The rubber was dried in a thermostatically regulated hot cylinder at 110 ° C to produce the modified conjugated diene rubber P.
The polymerization formula for the modified conjugated diene rubber P is given in table 1, while the properties of the modified conjugated diene rubber obtained P are given in table 2. Using the modified conjugated diene rubber P, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
Example 17 [Synthesis and evaluation of the modified conjugated diene rubber Q]
A modified conjugated diene rubber Q was obtained using the same method as in Example 3, but in this case, with the addition of the silicon tetrachloride used in Example 3 first and 3-aminopropyltriethoxy-silane in second place.
The polymerization formula for the modified conjugated diene rubber Q is given in table 1, while the properties of the modified conjugated diene rubber obtained are given in table 2. With the use of the modified conjugated diene rubber Q, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
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Example 18 [Synthesis and evaluation of the modified conjugated diene rubber R]
A modified conjugated diene rubber R was obtained using the same method as in Example 3, but in this case, with the addition of 3-aminopropyltriethoxy-silane and the silicon tetrachloride used in Example 3 at the same time.
The polymerization formula for the modified conjugated diene rubber R is given in table 1, while the properties of the modified conjugated diene rubber obtained R are given in table 2. With the use of the modified conjugated diene rubber R, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
Comparative example 1 [Synthesis and evaluation of modified conjugated diene rubber S]
A modified conjugated diene rubber S was obtained using the same method as in Example 1, but in this case, without the addition of the 3-aminopropyltriethoxy-silane used in Example 1.
The polymerization formula for the modified conjugated diene rubber S is given in table 1, while the properties of the modified conjugated diene rubber obtained are given in table 2. With the use of the modified conjugated diene rubber S, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
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Comparative example 2 [Synthesis and evaluation of the modified conjugated diene rubber T]
A modified conjugated diene rubber T was obtained using the same method as in Comparative Example 1, but in this case, by changing the amount of 3.93 mmol silicon tetrachloride used in Comparative Example 1 to 2.69 mmol.
The polymerization formula for the modified conjugated diene rubber T is given in table 1, while the properties of the modified conjugated diene rubber obtained are given in table 2. Using the modified conjugated diene rubber T, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
Comparative example 3 [Synthesis and evaluation of the modified conjugated diene rubber U]
A U-modified conjugated diene rubber was obtained using the same method as in Example 1, but in this case, without the addition of the silicon tetrachloride used in Example 1.
The polymerization formula for the modified conjugated diene rubber U is given in table 1, while the properties of the modified conjugated diene rubber obtained U are given in table 2. Using the modified conjugated diene rubber U, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
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Comparative example 4 [Synthesis and evaluation of modified conjugated diene rubber V]
A modified conjugated diene rubber V was obtained using the same method as in Example 16, but in this case, without the addition of the 3-aminopropyltriethoxy-silane used in Example 16.
The polymerization formula for modified conjugated diene rubber V is given in table 1, while the properties of the modified conjugated diene rubber obtained V are given in table 2. Using the modified conjugated diene rubber V, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
Comparative example 5 [Synthesis and evaluation of modified conjugated diene rubber W]
A modified conjugated diene rubber W was obtained using the same method as Example 1, but in this case, using tetraethoxy silane in place of the N, Nbis (triethylsilyl) aminopropylmethyldimethoxy silane used in Example 1 and changing the 3.93 mmol silicon tetrachloride addition amount used in Example 1 to 2.69 mmol.
The polymerization formula for the modified conjugated diene rubber W is given in table 1, while the properties of the modified conjugated diene rubber obtained are given in table 2. With the use of the modified conjugated diene rubber W, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and the
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71/86 property valuation was performed. The results are shown in table 4.
Comparative example 6 [Synthesis and evaluation of modified conjugated diene rubber X]
A modified conjugated diene rubber X was obtained using the same method as Comparative Example 5, but in this case, using stannous 2-ethylhexanoate in place of the silicon tetrachloride used in Comparative Example 5.
The polymerization formula for the modified conjugated diene rubber X is given in table 1, while the properties of the modified conjugated diene rubber obtained X are given in table 2. Using the modified conjugated diene rubber X, the composition of rubber was prepared according to the composition formula given in table 3 and was vulcanized and property evaluation was carried out. The results are shown in table 4.
Comparative example 7 [Synthesis and evaluation of Y conjugated diene rubber]
2,750 g of cyclohexane, 50.0 g of tetrahydrofuran, 125 g of styrene and 365 g of 1,3-butadiene were loaded into a 5 L autoclave reactor that had been replaced by nitrogen. The temperature of the reactor contents was adjusted to 10 ° C, followed by the addition of a solution of cyclohexane containing n-butyllithium (5.80 mmol) to initiate the polymerization. The polymerization was carried out adiabatically and the maximum temperature of 85 ° C was reached.
When the polymerization conversion had reached 99%, an additional 10 g of butadiene
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72/86 was carried out and the polymerization was carried out for an additional 5 minutes, after which a solution of cyclohexane containing silicon tetrachloride (1.04 mmol) was added and the reaction was carried out for 15 minutes. 2.0 g of 2,6-ditherc-butyl-p-cresol was then added to the resulting polymer solution. This was followed by the removal of solvent by steam distillation using hot water adjusted to pH = 9 with sodium hydroxide. The rubber was dried in a thermostat-regulated hot cylinder at 110 ° C to produce the Y-conjugated diene rubber.
The polymerization formula for Y conjugated diene rubber is given in table 1, while the properties of the Y conjugated diene rubber are given in table 2. With the use of Y conjugated diene rubber, the rubber composition was prepared according to the composition formula given in table 3 and was vulcanized and the property evaluation was carried out. The results are shown in table 4.
[The method for mixing (kneading) the rubber composition and property evaluation]
Using a Plastomill (250 cc capacity) equipped with a temperature control device, the following were mixed / kneaded in a first stage mix / knead at a fill rate of 72% and 60 rpm: the rubber of modified conjugate diene of the present invention, butadiene rubber, natural rubber, extender oil, carbon black, silica, silane coupling agent, stearic acid, aging inhibitor and zinc white (i.e., zinc oxide). Then, after the mixture obtained as described above was cooled to room temperature, the sulfur and vulcanization accelerator were
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73/86 mixed / kneaded in a second stage mix / knead. It was molded and vulcanized with a vulcanization press for a prescribed period of time at 160 ° C and the following property assessments, which are indicative of the tire's performance, were carried out.
(i) Mooney viscosity: The pre-vulcanized rubber composition was used for the measurement sample and the measurement was performed according to JIS K 6300 using an L rotor and the following conditions: preheating for 1 minute, run time of the rotor = 4 minutes and temperature = 100 ° C.
(ii) Tensile strength: The 300% modulus was measured according to JIS K 6301. This is reported as an index, in which the higher numerical values indicate greater tensile strength and are therefore better.
(iii) tan δ at 0 ° C: Vulcanized rubber was used as the measurement sample. The measurement was carried out at a dynamic tensile strain of 0.14%, an angular velocity of 100 radians per second and 0 ° C using a dynamic spectrometer (manufactured by
Rheometrics (U.S.)). This is reported as an index, where higher numerical values indicate greater wet slip resistance, and thus are better.
(iv) tan δ at 70 ° C: Vulcanized rubber was used as the measurement sample. The measurement was carried out at a dynamic tensile strain of 0.7%, an angular velocity of 100 radians per second and 70 ° C using a dynamic spectrometer (manufactured by
Rheometrics (U.S.)). This is reported as an index, in which the higher numerical values indicate a lower low hysteresis loss character and are therefore better.
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74/86 (v) Wear resistance: Vulcanized rubber was used as the measurement sample. The measurement was carried out at 25 ° C with a 10 N load according to JIS K 6264, using a DIN abrasion tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.). This is reported as an index, where higher numerical values indicate better wear resistance.
As is evident from Table 2, the modified conjugated diene rubber U of Comparative Example 3, which did not use an onium generator, has a very high cold flow value, thus demonstrating a problem in terms of retention shape by rubber.
As is also evident from Table 4, the compositions of the present invention, which use a conjugated diene rubber modified according to the present invention, are shown to have a substantially improved balance between wet slip resistance and wetting behavior. low hysteresis loss, without a loss in tensile strength or wear resistance.
The results of the property evaluations for the modified diene rubbers S to V of Comparative Examples 1 to 4 demonstrate that both steps (a) and (b) of the present invention are crucial for improving the balance between resistance to wet slip and low hysteresis loss behavior.
The results of the property assessments for the modified conjugated diene rubber W of Comparative Example 5 demonstrate that the modification in step (a) with an alkoxy silane compound that has an on-convertible group is crucial for the improvement of the
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75/86 balance between low hysteresis loss behavior and tensile strength, wear resistance and wet slip resistance.
The results of property assessments for the modified conjugated diene rubber X of Comparative Example 6 demonstrate that the use of an onium generator is crucial for improving the balance between the
behavior of loss in hysteresis low and the resistance tensile strength to wear and the resistance to Slipping wet, and that a general catalyst gives
condensation of alkoxy silane compound is irrelevant for the display of satisfactory performance.
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Example1 Example2 Example3 Example4 Example5 Example6 Example7 Example8 Example9 Example10 Example11 Example12 Example13 Example14 Example15 Example16 Example17 Example18 Modified conjugated diene rubber typeTHE B Ç D AND F G H I J K L M N O P Q R Polymerization formula Solvent : cyclohexane (g) 2750 2750 2750 2750 2750 2750 2750 2750 2750 2750 2750 2750 2750 2750 2750 2750 2750 2750 Vinyl content modifier : tetrahydrofuran (g) 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 - - - - - 100.0 10.3 10.3 : 2,2-di (tetra-hydrofuryl) propane (mmol) - - - - - - - - - - 3.25 3.25 3.25 3.25 3.25 - - - Polymerization monomer : styrene (g) 125 125 50 125 125 125 125 125 125 125 125 125 125 125 125 180 50 50 : butadiene (g) 365 365 440 365 365 365 365 365 365 365 365 365 365 365 365 210 440 440 : supplementary butadiene (g) 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Polymerization initiator : piperidine (mmol) - - - - - - - - - - 4.70 4.70 4.70 4.70 4.70 - - - : n-butyl lithium (mmol) 5.80 5.80 5.80 5.80 5.80 5.80 5.80 5.80 5.80 5.80 5.80 5.80 5.80 5.80 5.80 4.60 5.80 5.80 First alkoxy silane compound : N-Si-1 *1(mmol) 4.96 - - - - - - - - 4.96 4.96 4.96 4.96 4.96 4.96 3.93 - - : N-Si-2 *2(mmol) - 4.96 - - - - - - - - - - - - - - - - : N-Si-3 * 3(mmol) - - 2.48 - - - - - - - - - - - - - 2.48 2.48 : N-Si-4 * 4(mmol) - - - 4.96 - - - - - - - - - - - - - - : N-Si-5 * 5(mmol) - - - - 4.96 - - - - - - - - - - - - - : N-Si-6 * 6(mmol) - - - - - 2.48 - - - - - - - - - - - - : N-Si-7 * 7(mmol) - - - - - - 4.96 - - - - - - - - - - - : S-Si-1 * 8(mmol)- - - - - - 4.96 - - - - - - - - - -
76/86
Petition 870190089753, of 10/09/2019, p. 81/97
: P-Si-1 * 9(mmol) - - - - - - - - 4.96 - - - - - - - - - : Si-1 * 10(mmol) - - - - - - - - - - - - - - - - - - Second alkoxy silane compound : N-1 * 11 (mmol) 4.96 4.96 2.48 4.96 4.96 4.96 4.96 4.96 4.96 - - 9.92 4.96 4.96 4.96 3.93 2.48 2.48 : N-2 * 12 (mmol) - - - - - - - - - - 4.96 - - - - - - - : S-1 * 13 (mmol) - - - - - - - - - 4.96 - - - - - - - - Onion generator : Cl-1 * 14 (mmol) 3.93 5.17 2.69 5.17 5.17 3.31 3.93 3.93 3.93 3.93 6.34 6.34 - - - 3.12 2.69 2.69 : Cl-2 * 15 (mmol) - - - - - - - - - - - - 20.4 - - - - - : Cl-3 * 16 (mmol) - - - - - - - - - - - - - 5.10 - - - - : P-1 * 17 (mmol) - - - - - - - - - - - - - - 13.61 - - - Catalystcondensation : Sn-1 * 18 (mmol) - - - - - - - - - - - - - - - - - - Extender oil :oil * 19 (mmol) - - - - - - - - - - - - - - - 187.5 - -
77/86 * 1: N, N-bis (triethylsilyl) aminopropylmethyldimethoxy silane * 2: N, N ', N-tris (trimethylsilyl) -N- (2-aminoethyl) -3-aminopropyltriethoxy-silane * 3: 1- (3-triethoxy-silylpropyl) -2,2,5,5-tetramethyl-1-aza-2,5-disylacyclopentane * 4: N- [3- (trimethoxy-silyl) -propyl] -N, N'-diethyl -N'-trimethylsilyl-ethane-1,2-diamine 5 * 5: 3- (4-trimethylsilyl-1-piperazine) propyltriethoxysilane * 6: bis [3- (triethoxy-silyl) propyl] trimethylsilylamine * 7: 3-diethylaminopropyltriethoxy -silane * 8: S-trimethylsilylmercaptopropyltriethoxy-silane
Petition 870190089753, of 10/09/2019, p. 82/97 * 9: 3-diphenylphosphinopropyltrimethoxy-silane * 10: tetraethoxy-silane * 11: 3-aminopropyltriethoxy-silane * 12: N-2- (aminoethyl) -3-aminopropyltrimethoxy * 13: mercaptopropyltriethoxy-silane * 14: tetrachloride silicon * 15: diethyl aluminum chloride * 16: titanium tetrachloride * 17: isopropyl acid phosphate * 18: stannous 2-ethylhexanoate * 19: naphthenic oil (PCA content: less than
-silano
3%)
Petition 870190089753, of 10/09/2019, p. 83/97
78/86
Comparative example 1 Comparative example2 Comparative example3 Comparative example 4 Comparative example5 Comparative example6 Comparative example7 Modified conjugated diene rubber types T U V W X Y Polymerization formula Solvent : cyclohexane (g) 2750 2750 2750 2750 2750 2750 2750 Vinyl content modifier : tetrahydrofuran (g) 50.0 50.0 50.0 100.0 50.0 50.0 50.0 : 2,2-di (tetrahydrofuryl) propane (mmol) - - - - - - - Polymerization monomer : styrene (g) 125 125 125 180 125 125 125 : butadiene (g) 365 365 365 310 365 365 365 : supplementary butadiene (g) 10 10 10 10 10 10 10 Polymerization initiator : piperidine (mmol) - - - - - - - : n-butyl lithium (mmol) 5.80 5.80 5.80 4.60 5.80 5.80 5.80 First alkoxy silane compound : N-Si-1 * 1 (mmol) 4.96 4.96 4.96 3.93 - - - : N-Si-2 * 2 (mmol) - - - - - - - : N-Si-3 * 3 (mmol) - - - - - - - : N-Si-4 * 4 (mmol) - - - - - - - : N-Si-5 * 5 (mmol) - - - - - - - : N-Si-6 * 6 (mmol) - - - - - - - : N-Si-7 * 7 (mmol) - - - - - - - : S-Si-1 * 8 (mmol)- - - - - -
79/86
Petition 870190089753, of 10/09/2019, p. 84/97
: P-Si-1 * 9 (mmol) - - - - - - - : Si-1 * 10 (mmol) - - - - 4.96 4.96 - Second alkoxy silane compound : N-1 * 11 (mmol) - - 4.96 - 4.96 4.96 - : N-2 * 12 (mmol) - - - - - - - : S-1 * 13 (mmol) - - - - - - - Onion generator : Cl-1 * 14 (mmol) 3.93 2.69 - 3.12 2.691.04 : Cl-2 * 15 (mmol) - - - - - - - : Cl-3 * 16 (mmol) - - - - - - - : P-1 * 17 (mmol) - - - - - - - Condensation catalyst : Sn-1 * 18 (mmol) - - - - - 2.69 - Extender oil :oil * 19 (mmol) - - - 187.5 - - -
80/86 * 1: N, N-bis (triethylsilyl) aminopropylmethyldimethoxy silane * 2: N, N ', N-tris (trimethylsilyl) -N- (2-aminoethyl) -3-aminopropyltriethoxy-silane * 3: 1- (3-triethoxy-silylpropyl) -2,2,5,5-tetramethyl-1-aza-2,5-disylacyclopentane * 4: N- [3- (trimethoxy-silyl) -propyl] -N, N'-diethyl -N'-trimethylsilyl-ethane-1,2-diamine 5 * 5: 3- (4-trimethylsilyl-1-piperazine) propyltriethoxy-silane * 6: bis [3- (triethoxy-silyl) propyl] trimethylsilylamine * 7: 3 -diethylaminopropyltriethoxy-silane * 8: S-trimethylsilylmercaptopropyltriethoxy-silane
Petition 870190089753, of 10/09/2019, p. 85/97 * 9: 3-diphenylphosphinopropyltrimethoxy-silane * 10: tetraethoxy-silane * 11: 3-aminopropyltriethoxy-silane * 12: N-2- (aminoethyl) -3-aminopropyltrimethoxy * 13: mercaptopropyltriethoxy-silane * 14: tetrachloride silicon * 15: diethyl aluminum chloride * 16: titanium tetrachloride * 17: isopropyl acid phosphate * 18: stannous 2-ethylhexanoate * 19: naphthenic oil (PCA content: less than
-silano
3%)
Petition 870190089753, of 10/09/2019, p. 86/97
81/86
Example1 Example2 Example3 Example4 Example5 Example6 Example7 Example8 Example9 Example10 Example11 Example12 Example13 Example14 Example15 Example16 Example17 Example18 Modified conjugated diene rubber typeTHE B Ç D AND F G H I J K L M N O P Q R [modified conjugated diene rubber properties] Bonded styrene content (pasta%) 25 25 10 25 25 25 25 25 25 25 25 25 25 25 25 36 10 10 Vinyl content (%) 55 56 41 55 55 54 56 55 56 56 56 56 56 56 56 62 40 41 Glass transition temperature (° C) -30 -31 -60 -31 -30 -30 -30 -31 -30 -31 -32 -32 -33 -32 -32 -13 -60 -60 Weighted average molecular weight before modification (x10 ⁴ ) 20 20 18 19 20 19 20 20 20 20 19 19 20 19 20 27 18 18 ViscosityMooney (ML1 + 4,100 ° C) 65 73 68 65 64 63 58 50 46 58 68 74 61 63 68 52 71 66 Cold flow value (mg / minute) 0.2 0.1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.1 0.2 0.2 0.2 0.2 0.1 0.2
82/86
Petition 870190089753, of 10/09/2019, p. 87/97
Comparative example 1 Comparative example2 Comparative example3 Comparative example 4 Comparative example5 Comparative example6 Comparative example7 Modified conjugated diene rubber types T U V W X Y [modified conjugated diene rubber properties] Bonded styrene content (pasta%) 25 25 25 36 25 25 25 Vinyl content (%) 56 56 55 62 55 56 55 Glass transition temperature (° C) -31 -30 -30 -13 -31 -31 -37 Weighted average molecular weight before modification (x104) 20 20 20 27 20 20 20 Mooney Viscosity (ML1 + 4,100 ° C) 60 58 15 49 43 53 50 Cold flow value (mg / minute) 0.2 0.3 > 10 0.4 0.7 0.4 0.2
83/86
Petition 870190089753, of 10/09/2019, p. 88/97
Composition formula (phr - parts per 100 of rubber) I II Modified conjugated diene rubber 70 96.25 Butadiene rubber * 1)30 Natural rubber 30Extender oil * 2) 37.5 11.25 Carbon black * 3) 5.6 5.6 Silica * 4) 70 70 Silane coupling agent * 5) 5.6 5.6 Stearic acid 2.0 2.0 Aging inhibitor * 6) 1.0 1.0 Zinc oxide 3.0 3.0 Vulcanization accelerator CZ * 7) 1.8 1.8 Vulcanization accelerator D * 8) 1.5 1.5 sulfur 1.5 1.5
84/86 * 1) BR01 manufactured by JSR Corporation * 2) SNH46 manufactured by Sankyo Yuka Kogyo Kabushiki Kaisha * 3) DIABLACK N339 manufactured by Mitsubishi Chemical Corporation * 4) NipsilAQ manufactured by Tosoh Silica Corporation * 5) Si69 manufactured by Evonik Industries * 6) NOCRAC 810NA manufactured by Ouchi Shinko Chemical Industrial * 7) NOCCELER CK manufactured by Ouchi Shinko Chemical Industrial * 8) NOCCELER D manufactured by Ouchi Shinko Chemical Industrial
Petition 870190089753, of 10/09/2019, p. 89/97
Example1 Example2 Example3 Example4 Example5 Example6 Example7 Example8 Example9 Example10 Example11 Example12 Example13 Example14 Example15 Example16 Example17 Example18 Modified conjugated diene rubber typeTHE B Ç D AND F G H I J K L M N O P Q R [crosslinked rubber composition properties] Composition formulaI I I I I I I I I I I I I I I II I I ViscosityMooney (ML1 + 4,100 ° C) 78 83 69 74 76 67 69 89 77 79 85 87 76 83 82 86 70 68 Tensile strength (index) 110 109 105 106 106 104 103 114 106 108 114 111 108 104 108 114 106 104 0 ° C tan δ (index) 134 144 132 130 131 134 127 131 129 133 142 146 143 141 144 129 131 132 70 ° C tan δ (index) 138 141 143 134 137 137 130 134 133 135 142 153 149 147 148 131 141 140 Wear resistance (index) 115 113 109 107 106 105 106 112 106 119 117 126 114 115 119 112 110 108
Petition 870190089753, of 10/09/2019, p. 90/97
Comparative example 1 Comparative example2 Comparative example3 Comparative example 4 Comparative example5 Comparative example6 Comparative example7 Modified conjugated diene rubber types T U V W X Y [crosslinked rubber composition properties] Composition formulaI I I II I I I Mooney Viscosity (ML1 + 4,100 ° C) 70 68 55 84 59 63 52 Tensile strength (index) 110 108 108 112 101 103 100 0 ° C tan δ (index) 123 121 123 114 104 103 100 70 ° C tan δ (index) 125 125 127 118 105 103 100 Wear resistance (index) 105 106 101 108 101 101 100
86/86

权利要求:
Claims (10)
[1]
1. Method of production of a modified conjugated diene rubber characterized by comprising:
(a) a reaction step of a first alkoxy-silane compound that has at least one convertible to an onion group in one molecule by an onium generator and at least one alkoxy-silyl group that has at least two alkoxy groups, with a conjugated diene polymer which has an active alkali metal or alkaline earth metal terminal and obtained by polymerizing a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound, to thereby obtain a diene polymer modified conjugate that has the onion convertible group and the alkoxy-silyl group; and (b) a step of mixing the modified conjugated diene polymer obtained in step (a) with the onium generator and a second alkoxy-silane compound having at least one alkoxy-silyl group and at least one group in one molecule. convertible to onio by the onio generator.
[2]
2. Production method of a modified conjugated diene rubber, according to claim 1, characterized by the fact that the onion convertible group in the first alkoxy silane compound is at least one type selected from the group consisting of nitrogen groups obtained by replacing two hydrogen atoms in a primary amine with two protecting groups, nitrogen groups obtained by replacing a hydrogen atom in a secondary amine with a protecting group, tertiary amino groups, imino groups, groups pyridyl, phosphorus-containing groups obtained by replacing two hydrogen atoms of a primary phosphine with two protecting groups, phosphorus-containing groups obtained by
Petition 870190089753, of 10/09/2019, p. 92/97
2/3 replacement of a hydrogen atom of a secondary phosphine by a protecting group, tertiary phosphine groups and sulfur-containing groups obtained by replacing a hydrogen atom in a thiol with a protecting group.
[3]
3. Method of producing a modified conjugated diene rubber according to either of claims 1 or 2, characterized in that the onium generator is at least one type selected from the group consisting of halide compounds silicon, tin halide compounds, aluminum halide compounds, titanium halide compounds, zirconium halide compounds, germanium halide compounds, gallium halide compounds, zinc halide compounds, sulfate esters, phosphate, carboxylic acids and sulfonic acids.
[4]
4. Method of producing a modified conjugated diene rubber according to any one of claims 1 to 3, characterized by the fact that the onion convertible group in the second alkoxysilane compound is at least one type selected from the group that consists of primary amino groups, secondary amino groups, tertiary amino groups, imino groups, pyridyl groups, primary phosphine groups, secondary phosphine groups, tertiary phosphine groups and thiol groups.
[5]
Method for the production of a modified conjugated diene rubber according to any one of claims 1 to 4, characterized in that it further comprises:
(c) a step of making a mixture obtained in step (b) coming into contact with water.
[6]
6. Method of production of a modified conjugated diene rubber, according to any of the
Petition 870190089753, of 10/09/2019, p. 93/97
3/3 claims 1 to 5, characterized in that the modified conjugated diene rubber contains the modified conjugated diene polymer, the second alkoxy silane compound and a condensation and hydrolysis product from the modified conjugated diene polymer and of the second alkoxy-silane compound, and have onium structures formed by these three materials.
[7]
7. Modified conjugated diene rubber characterized by being obtained by the method of producing a modified conjugated diene rubber as defined in any one of claims 1 to 6.
[8]
Rubber composition characterized by comprising the modified conjugated diene rubber as defined in claim 7, a silica and / or carbon black, and a crosslinking agent.
[9]
9. Cross-linked rubber composition characterized by being obtained by cross-linking the rubber composition as defined in claim 8.
[10]
10. Tire characterized in that it comprises the cross-linked rubber composition as defined in claim 9.

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同族专利:

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-07-16| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-10-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2019-11-05| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/10/2010, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2009242041|2009-10-21|

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PCT/JP2010/068621|WO2011049180A1|2009-10-21|2010-10-21|Method for producing modified conjugated diene rubber, modified conjugated diene rubber, and rubber composition|

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