KR20220029889A - Method for preparing hydrogenated conjugated diene polymer and hydrogenated conjugated diene polymer prepared by the method - Google Patents

Abstract

The present invention relates to a preparation method of a hydrogenated conjugated diene-based polymer, and more specifically, to a preparation method of a hydrogenated conjugated diene-based polymer which comprises: a step (S10) of preparing a conjugated diene-based polymer comprising a coupling agent linking group comprising a conjugated diene-based monomer unit and silyl hydride; and a step (S20) of hydrogenation of the conjugated diene-based polymer using hydrogen gas, wherein the hydrogenation is carried out under the presence of a catalyst comprising a compound represented by chemical formula 1 (see the description of the present invention) and a hydrogenated conjugated diene-based polymer prepared therefrom.

Description

Method for producing a hydrogenated conjugated diene-based polymer and a hydrogenated conjugated diene-based polymer prepared therefrom

The present invention relates to a method for producing a hydrogenated conjugated diene-based polymer by hydrogenation of a conjugated diene-based polymer and a hydrogenated conjugated diene-based polymer prepared therefrom.

The conjugated diene-based polymer is polymerized from a conjugated diene monomer such as butadiene and isoprene to include an unsaturated double bond in the polymer. These unsaturated double bonds may be advantageously applied when additionally functionalizing or crosslinking the conjugated diene-based polymer. However, these unsaturated double bonds have a problem in that they are easily oxidized or deteriorated by light or heat. Accordingly, a method of hydrogenating unsaturated double bonds has been proposed in order to improve heat resistance, oxidation resistance, weather resistance, ozone resistance, and the like of a conjugated diene-based polymer.

As a method of hydrogenating the unsaturated double bond of a conjugated diene-based polymer, Korean Patent Application Laid-Open No. 10-2005-0019107 discloses an alkoxysilane coupling agent, particularly a block copolymer using a tetraalkoxysilane coupling agent, a nickel or cobalt-based catalyst It is disclosed that hydrogenation reaction is carried out using a catalyst composition containing an aluminum-based cocatalyst. In addition, in Korea Patent Application Laid-Open No. 10-2006-0012653, a catalyst composition comprising an aluminum-based cocatalyst in a nickel or cobalt-based catalyst with respect to a block copolymer using an alkoxysilane coupling agent, particularly an alkyl trialkoxysilane coupling agent. It is disclosed to carry out a hydrogenation reaction using However, according to Korean Patent Application Laid-Open No. 10-2005-0019107 and Korean Patent Application Laid-Open No. 10-2006-0012653, an aluminum-based promoter must be included in addition to a nickel- or cobalt-based catalyst during the hydrogenation reaction of a block copolymer. And, the necessity of such a co-catalyst eventually increases the process cost and causes a decrease in productivity.

In addition, as a method of hydrogenating the unsaturated double bond of a conjugated diene-based polymer, a hydrogenation reaction using an organometallic compound called a Tebbe reagent as a catalyst is also known. In particular, Korean Patent Application Laid-Open No. 10-2017-0026365 discloses a hydrogenation reaction using a Tebbe reagent and a silane compound having a silyl hydride bond, and Korean Patent Publication No. 2018-0061068 discloses a titanium compound, lithium, A hydrogenation reaction using an organometallic compound containing magnesium or aluminum and an oligomer containing a polyglycol segment is disclosed. However, even according to Korea Patent Application Laid-Open No. 10-2017-0026365 and Korean Patent Publication No. 10-2018-0061068, in addition to Tebbe reagent or titanium compound catalyst during hydrogenation of a conjugated diene-based polymer, a silyl hydride bond a silane compound having; An organometallic compound containing lithium, magnesium, or aluminum, and an oligomer containing a polyglycol segment must be included as a cocatalyst, and the necessity of such a cocatalyst ultimately increases process cost and lowers productivity.

KR10-2005-0019107A KR10-2006-0012653A KR10-2017-0026365A KR10-2018-0061068A

The present invention has been devised to solve the problems of the prior art, and an object of the present invention is to prepare a hydrogenated conjugated diene-based polymer having a high hydrogenation rate without a cocatalyst during the hydrogenation reaction of the conjugated diene-based polymer.

In order to solve the above problems, the present invention comprises the steps of preparing a conjugated diene-based polymer comprising a coupling agent linking group comprising a conjugated diene-based monomer unit and a silyl hydride (S10); and hydrogenating the conjugated diene-based polymer using hydrogen gas (S20), wherein the hydrogenation reaction is carried out in the presence of a catalyst including a compound represented by the following formula (1). A method for preparing a polymer is provided.

[Formula 1]

In Formula 1, Cp is each independently a substituted or unsubstituted cyclopentadienyl group

In addition, the present invention is a hydrogenated conjugated diene prepared by the method for producing a hydrogenated conjugated diene-based polymer, including a coupling agent linking group including a conjugated diene-based monomer unit and a silyl hydride, and having a hydrogenation rate of 99% or more with respect to a double bond to provide a polymer.

According to the present invention, the coupling agent coupling group of the conjugated diene-based polymer includes a coupling agent coupling group including silyl hydride, and when hydrogenation of the conjugated diene-based polymer including the coupling group is carried out, hydrogenation at a high hydrogenation rate without a cocatalyst There is an effect that the production of a conjugated diene-based polymer is possible.

Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.

The terms or words used in the description and claims of the present invention should not be construed as being limited to their ordinary or dictionary meanings, and the inventor must properly understand the concept of the term in order to best describe his invention. Based on the principle that can be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

In the present invention, the term 'alkyl group' may refer to a monovalent aliphatic saturated hydrocarbon, and linear alkyl groups such as methyl, ethyl, propyl and butyl and isopropyl, sec-butyl, ter It may mean including all branched alkyl groups such as tert-butyl and neopentyl.

In the present invention, the term 'alkenyl group' may mean a monovalent aliphatic unsaturated hydrocarbon including one or two or more double bonds.

In the present invention, the term 'alkynyl group' may mean a monovalent aliphatic unsaturated hydrocarbon including one or two or more triple bonds.

In the present invention, the term 'cycloalkyl group' may refer to a monovalent aliphatic saturated or unsaturated cyclic hydrocarbon. Here, the unsaturated cyclic hydrocarbon includes one or two or more unsaturated bonds in a ring structure formed from the hydrocarbon, but may mean a cyclic hydrocarbon other than an aromatic hydrocarbon.

In the present invention, the term 'aryl group' may mean a cyclic aromatic hydrocarbon, and also a monocyclic aromatic hydrocarbon in which one ring is formed, or a polycyclic aromatic hydrocarbon in which two or more rings are bonded. It may mean including all hydrocarbons.

In the present invention, the term 'heteroalkyl group' may mean including one or two or more heteroatoms, ie, atoms other than carbon and hydrogen, in a monovalent aliphatic saturated or unsaturated hydrocarbon. Here, the hetero atom may be an oxygen (O), nitrogen (N), or sulfur (S) atom. Also, the heteroalkyl group may mean including all of an alkoxy group, an amino group, and a sulfide group.

In the present invention, the term 'heterocyclic group' may mean including both a cycloalkyl group or an aryl group in which a carbon atom in a cycloalkyl group or an aryl group is substituted with one or more hetero atoms. Here, the hetero atom may be an oxygen (O), nitrogen (N), or sulfur (S) atom. In addition, the number of ring atoms of the heterocyclic group may mean the number of atoms forming a ring including carbon and hetero atoms.

In the present invention, the term 'monomer unit' may refer to a component, structure, or material itself derived from a monomer. it could mean

The term 'polymer' used in the present invention may refer to a homopolymer formed by polymerization from one type of monomer.

The term 'block' used in the present invention may refer to a group of repeating units composed only of repeating units derived from the same monomer as only the same monomers participate in the polymerization reaction in the copolymer. It may mean a block formed only with vinyl monomer units, and the conjugated diene-based polymer block may mean a block formed only with conjugated diene-based monomer units.

The term 'coupling agent coupling group' used in the present invention may refer to a remainder part of the coupling agent formed while the polymer block is coupled by the coupling agent as a part of the block copolymer.

The term 'anionic active polymer' used in the present invention is a polymer formed by an anionic polymerization reaction, and may refer to a polymer capable of additional polymerization or reaction by maintaining an anionic state at one end of the polymer. can mean

As used herein, the term 'composition' includes reaction products and decomposition products formed from materials of the composition, as well as mixtures of materials comprising the composition.

The present invention provides a method for producing a hydrogenated conjugated diene-based polymer.

According to an embodiment of the present invention, the hydrogenated conjugated diene-based polymer manufacturing method comprises the steps of preparing a conjugated diene-based polymer including a conjugated diene-based monomer unit and a coupling agent linking group including a silyl hydride (S10) ); and hydrogenating the conjugated diene-based polymer using hydrogen gas (S20), wherein the hydrogenation reaction may be carried out in the presence of a catalyst including a compound represented by the following formula (1).

[Formula 1]

In Formula 1, Cp may each independently be a substituted or unsubstituted cyclopentadienyl group.

According to an embodiment of the present invention, the step (S10) is a step for preparing a conjugated diene-based polymer to be subjected to a hydrogenation reaction, and the conjugated diene-based polymer prepared in this step is a coupling agent containing silyl hydride. It is characterized in that it contains a linking group. In this regard, in Patent Document 1 (Korean Patent Application Laid-Open No. 10-2005-0019107), when a coupling agent containing a silyl hydride as in the present invention is used as a coupling agent, a nickel or cobalt-based catalyst is added to an aluminum-based catalyst. It is disclosed that when a hydrogenation reaction is carried out using a catalyst composition including a cocatalyst, severe decomposition or extreme decomposition of the polymer occurred during the hydrogenation reaction, that is, the hydrogenation reaction. This is expected to occur in the same problem in Patent Document 2 (Korean Patent Application Laid-Open No. 10-2006-0012653) using the same catalyst system as in Patent Document 1. However, as in the present invention, when the conjugated diene-based polymer includes a coupling agent linking group including silyl hydride, during the hydrogenation reaction in the step (S20) to be described, a catalyst comprising the compound represented by Formula 1 When used as a catalyst for a hydrogenation reaction, hydrogenation is possible at a high hydrogenation rate without a separate cocatalyst, in addition to the catalyst containing the compound represented by Formula 1, and at the same time, it is possible to prevent decomposition of the conjugated diene-based polymer during the hydrogenation reaction. can have an effect.

According to an embodiment of the present invention, the step (S20) is a step of performing a hydrogenation reaction on the conjugated diene-based polymer prepared in the step (S10) using hydrogen gas, which is represented by Formula 1 It is characterized in that a catalyst comprising a compound is used. As in the present invention, when a catalyst including the compound represented by Formula 1 is used as a catalyst for the hydrogenation reaction, it prevents decomposition of the conjugated diene-based polymer during the hydrogenation reaction and includes the compound represented by Formula 1 In addition to the catalyst, there is an effect that hydrogenation is possible at a high hydrogenation rate without a separate cocatalyst.

That is, according to an embodiment of the present invention, the conjugated diene-based polymer including a coupling agent linking group including the silyl hydride prepared in the step (S10), and the formula 1 used as a catalyst in the step (S20) The catalyst containing the compound represented by is essential to be included simultaneously to prevent decomposition of the conjugated diene-based polymer during the hydrogenation reaction and to enable hydrogenation at a high hydrogenation rate without a separate cocatalyst.

According to an embodiment of the present invention, the substituted cyclopentadienyl group may mean a cyclopentadienyl group substituted with a substituent other than hydrogen, and the unsubstituted cyclopentadienyl group is not substituted with a substituent other than hydrogen. It may mean a cyclopentadienyl group that is not.

According to an embodiment of the present invention, the compound represented by Formula 1 may be a compound represented by Formula 2 below.

[Formula 2]

In Formula 2, R ¹ to R ¹⁰ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, and 6 to carbon atoms. An aryl group having 30, a heteroalkyl group having 1 to 30 carbon atoms, or a heterocyclic group having 5 to 30 ring atoms, or two adjacent ones of R ¹ to R ¹⁰ may be connected to each other to form a ring.

As a specific example, R ¹ to R ¹⁰ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, 6 to 20 carbon atoms of an aryl group, a heteroalkyl group having 1 to 20 carbon atoms, or a heterocyclic group having 5 to 20 ring atoms, or two adjacent ones of R ¹ to R ¹⁰ are connected to each other to form a ring.

In a more specific example, R ¹ to R ¹⁰ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a cycloalkyl group having 6 to carbon atoms It may be an aryl group of 10, a heteroalkyl group of 1 to 10 carbon atoms, or a heterocyclic group of 5 to 10 ring atoms, or two adjacent ones of R ¹ to R ¹⁰ are connected to each other to form a ring.

According to an embodiment of the present invention, the compound represented by Formula 1 may be an unsubstituted cyclopentadienyl group, and more specifically, the compound represented by Formula 1 may be a Tebbe reagent.

According to an embodiment of the present invention, the conjugated diene-based polymer prepared in step (S10) is a conjugated diene-based polymer including an aromatic vinyl-based monomer unit, a conjugated diene-based monomer unit, and a coupling agent linkage group including a silyl hydride. may be, and as a specific example, it may be a block copolymer including an aromatic vinyl-based polymer block, a conjugated diene-based polymer block, and a coupling agent connecting group including a silyl hydride. In this case, the target of the hydrogenation reaction in step (S20) may be a carbon-carbon double bond included in the conjugated diene-based monomer unit or the conjugated diene-based monomer unit of the conjugated diene-based polymer block.

According to an embodiment of the present invention, the step (S10) comprises the steps of preparing an anionic active aromatic vinyl-based polymer by polymerizing an aromatic vinyl-based monomer in the presence of an organolithium compound (S1); In the presence of the anionic active aromatic vinyl-based polymer prepared in step (S1), adding a conjugated diene-based monomer and polymerizing to prepare an anionic active diblock copolymer (S2); And in the presence of the anionic active diblock copolymer prepared in step (S2), by adding and reacting a coupling agent containing silyl hydride to prepare a block copolymer including a coupling agent linkage (S3) can be implemented including.

According to an embodiment of the present invention, step (S1) may be a step for preparing an aromatic vinyl-based polymer forming an aromatic vinyl-based polymer block. As a specific example, step (S1) may be carried out by anionic polymerization by introducing an aromatic vinylic monomer in the presence of an organolithium compound in a hydrocarbon-based solvent.

According to an embodiment of the present invention, the hydrocarbon-based solvent does not react with the organolithium compound, and can be used as long as it is generally used for an anionic polymerization reaction, and specifically, butane, n-pentane, n-hexane, n-heptane, or linear or branched aliphatic hydrocarbon compounds such as iso-octane; cyclic aliphatic hydrocarbon compounds unsubstituted or substituted with an alkyl group such as cyclopentane, cyclohexane, cycloheptane, methyl cyclohexane or methyl cycloheptane; and an aromatic hydrocarbon compound unsubstituted or substituted with an alkyl group such as benzene, toluene, xylene or naphthalene, and any one of them, or a mixture of two or more thereof may be used.

In addition, according to an embodiment of the present invention, the organolithium compound is a polymerization initiator for initiating an anionic polymerization reaction, and is n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, ethyllithium, isopropyl It may be at least one selected from the group consisting of lithium, cyclohexyl lithium, allyl lithium, vinyl lithium, phenyl lithium, and benzyl lithium.

According to an embodiment of the present invention, since step (S1) is carried out by an anionic polymerization reaction, the aromatic vinyl-based polymer prepared in step (S1) may be an anionic active aromatic vinyl-based polymer, and specifically, It can be obtained as a solution phase containing an active aromatic vinyl-based polymer.

According to an embodiment of the present invention, the aromatic vinyl-based monomer for forming the aromatic vinyl-based polymer block is styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, and 1-vinylnaphthalene. , 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene may be at least one selected from the group consisting of, and a specific example may be styrene.

According to an embodiment of the present invention, the input content of the aromatic vinyl-based monomer is 5% to 50% by weight, 10% to 40% by weight, or 20% by weight based on the total content of the aromatic vinyl-based monomer and the conjugated diene-based monomer. It may be from weight % to 40 weight %, and within this range, there is an excellent effect in mechanical properties of the block copolymer and the hydrogenated conjugated diene-based polymer hydrogenated therefrom.

According to an embodiment of the present invention, the step (S2) may be a step for preparing a diblock copolymer in which a conjugated diene-based polymer block is formed in addition to the aromatic vinyl-based polymer block. As a specific example, in step (S2), in the solution containing the anionically active aromatic vinyl polymer obtained in step (S1), in the presence of the anionically active aromatic vinyl polymer, a conjugated diene monomer is added and anionic polymerization is performed. can be carried out. Here, the anionic polymerization reaction with respect to the conjugated diene-based monomer may be initiated from an anionic active aromatic vinyl-based polymer.

According to an embodiment of the present invention, since the step (S2) is carried out by an anionic polymerization reaction, the diblock copolymer prepared in the step (S2) may be an anionic active diblock copolymer, and specifically, an anion It can be obtained as a solution phase comprising the active diblock copolymer.

According to an embodiment of the present invention, the conjugated diene-based monomer for forming the conjugated diene-based polymer block is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1 , 3-octadiene, isoprene, 2-phenyl-1,3-butadiene, and 2-halo-1,3-butadiene (halo means halogen atom) may be at least one selected from the group consisting of, specific examples, 1,3-butadiene.

According to an embodiment of the present invention, the input content of the conjugated diene-based monomer is 50% to 95% by weight, 60% to 90% by weight, or 60% by weight based on the total content of the aromatic vinyl-based monomer and the conjugated diene-based monomer. It may be from weight % to 80 weight %, and there is an excellent effect in mechanical properties of the block copolymer and the hydrogenated conjugated diene-based polymer hydrogenated therefrom within this range.

According to an embodiment of the present invention, in the step (S3), in the solution phase containing the anion active diblock copolymer obtained in the step (S2), in the presence of the anion active diblock copolymer, silyl hydride It can be carried out by a coupling reaction in which a coupling agent is added and reacted. Here, the coupling reaction with respect to the coupling agent may be carried out from an anionic active site of the anionic active diblock copolymer.

According to an embodiment of the present invention, since the step (S3) is carried out by a coupling reaction, the block copolymer prepared in the step (S3) is a die containing an aromatic vinyl-based polymer block and a conjugated diene-based polymer block. The block copolymer may be a triblock copolymer linked by a coupling agent containing silyl hydride, and specifically, the triblock copolymer is a solution containing the anionic active diblock copolymer obtained in step (S2). Since it is carried out by the coupling reaction by the introduction of the coupling agent in the phase, it can be obtained as a solution phase containing the triblock copolymer.

According to an embodiment of the present invention, the coupling agent coupling group including the silyl hydride may be a coupling group formed by a coupling reaction between the diblock copolymer and the coupling agent, and the coupling agent for forming the coupling agent coupling group It may be a coupling agent comprising silyl hydride.

According to an embodiment of the present invention, the silyl hydride may be a compound represented by the following formula (3).

[Formula 3]

In Formula 3, R ¹ to R ⁴ are each independently hydrogen, a halogen group, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms, wherein at least one of R ¹ to R ⁴ is hydrogen, and at least one of R ¹ to R ⁴ is a halogen group or an alkoxy group having 1 to 30 carbon atoms. it can be a gimmick

As a specific example, in Formula 3, R ¹ to R ⁴ are each independently hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 1 to 20 carbon atoms. of the alkoxy group, at least one of R ¹ to R ⁴ may be hydrogen, and at least two or more of R ¹ to R ⁴ may be a halogen group or an alkoxy group having 1 to 20 carbon atoms.

As a more specific example, in Formula 3, R ¹ to R ⁴ are each independently hydrogen, a halogen group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, but R ¹ At least one or more of R ⁴ may be hydrogen, and at least two or more of R ¹ to R ⁴ may be a halogen group or an alkoxy group having 1 to 10 carbon atoms.

According to an embodiment of the present invention, the compound represented by Chemical Formula 3 is trimethoxysilane (HSi(OMe) ₃ ), triethoxysilane (HSi(OEt) ₃ ), trichlorosilane (HSiCl ₃ ), t Libromosilane (HSiBr ₃ ), dimethoxysilane (H ₂ Si(OMe) ₂ ), diethoxysilane (H ₂ Si(OEt) ₂ ), dichlorosilane (H ₂ SiCl ₂ ), dibromosilane (H ₂ SiBr ₂ ) ) and dichlorophenylsilane (HSiPhCl ₂ ) may be at least one selected from the group consisting of, and in this case, the mechanical properties of the conjugated diene-based polymer including a coupling group linking group are excellent and the hydrogenation rate is very excellent.

According to an embodiment of the present invention, the conjugated diene-based polymer comprising a coupling agent linking group including the conjugated diene-based monomer unit and silyl hydride prepared in step (S10) has a number average molecular weight (Mn) of 100,000 g/ It may be mol to 150,000 g/mol, 105,000 g/mol to 140,000 g/mol, or 110,000 g/mol to 132,000 g/mol.

According to one embodiment of the present invention, the conjugated diene-based polymer comprising a coupling agent linking group including the conjugated diene-based monomer unit and silyl hydride prepared in step (S10) is, in step (S3), anionic active di In the presence of the block copolymer, when a coupling agent containing silyl hydride is added and reacted, a diblock copolymer that is not subjected to a coupling reaction by the coupling agent may be included in the form of a composition. That is, in the conjugated diene-based polymer prepared in step (S10), in step (S3), a diblock copolymer including an aromatic vinyl-based polymer block and a conjugated diene-based polymer block is connected by a coupling agent containing silyl hydride. It may be a conjugated diene-based polymer composition comprising a triblock copolymer and a diblock copolymer not connected by a coupling agent. At this time, the content of the diblock copolymer may be 10 wt% to 50 wt%, 20 wt% to 45 wt%, or 30 wt% to 43 wt%, and the content of the diblock copolymer is, (S3) During the coupling reaction of the step, it may be adjusted according to the reaction environment and coupling efficiency.

According to an embodiment of the present invention, the hydrogenation reaction of step (S20) is a reaction in which hydrogen is added to an unsaturated double bond included in the conjugated diene-based monomer unit of the conjugated diene-based polymer, so that the unsaturated double bond becomes a saturated single bond can As a specific example, in the hydrogenation reaction, a catalyst in an active state is formed by electron distribution in the catalyst system, a pi-complex between the catalyst and the polymer is formed, and hydrogen is added to the double bond. is carried out

According to an embodiment of the present invention, the hydrogenation reaction of the step (S20) includes the steps of pumping the conjugated diene-based polymer using hydrogen gas to the reactor substituted with hydrogen gas (S21); adding the catalyst to the reactor to which the conjugated diene-based polymer is pressurized (S22); and increasing the pressure of hydrogen gas inside the reactor to which the catalyst is added (S23).

According to an embodiment of the present invention, the catalyst introduced in step (S22) may be dissolved in an organic solvent and then added. The organic solvent may be a hydrocarbon-based solvent, and a specific example may be cyclohexane.

According to an embodiment of the present invention, during the hydrogenation reaction, the pressure of hydrogen gas may be 5 bar to 20 bar, 8 bar to 15 bar, or 9 bar to 12 bar, and safety during the hydrogenation reaction within this range There is an effect that it is possible to carry out the hydrogenation reaction at a high hydrogenation rate while securing it.

According to an embodiment of the present invention, the catalyst has a Ti atom content of 1 ppm to 10 ppm, 2 ppm to 8 ppm, or 4 ppm to 6 ppm of the compound represented by Formula 1 compared to the content of the conjugated diene-based polymer It may be added so as to be, and within this range, there is an effect of securing a high hydrogenation rate during the hydrogenation reaction of the conjugated diene-based polymer.

According to an embodiment of the present invention, the step (S20) may be carried out in the absence of a co-catalyst. As a specific example, the catalyst in step (S20) may not include a co-catalyst. As a more specific example, the catalyst in step (S20) may not include a silyl hydride-based cocatalyst. That is, according to the method for producing a hydrogenated conjugated diene-based polymer according to the present invention, there is an effect of producing a hydrogenated conjugated diene-based polymer at a high hydrogenation rate without a cocatalyst during the hydrogenation reaction in step (S20).

In addition, the present invention provides a hydrogenated conjugated diene-based polymer prepared by the method for producing the hydrogenated conjugated diene-based polymer.

According to an embodiment of the present invention, the hydrogenated conjugated diene-based polymer may include a coupling agent linking group including a conjugated diene-based monomer unit and a silyl hydride, and a hydrogenation rate for a double bond of 99% or more. Here, the hydrogenation rate may refer to a ratio in which hydrogen is added to an unsaturated double bond included in the conjugated diene-based monomer unit of the conjugated diene-based polymer so that the unsaturated double bond becomes a saturated single bond, and specifically, 1 of butadiene before and after hydrogenation It may be calculated from the ratio of the peak integral of the ,2-bound amount (4.8 ppm to 5.1 ppm) and the 1,4-bound amount (5.2 ppm to 5.5 ppm). However, when the conjugated diene-based monomer is not butadiene but other types of conjugated diene-based monomers such as isoprene, the amount of double bonds according to the type of each monomer instead of the amount of 1,2-bonds and 1,4-bonds can be calculated.

According to an embodiment of the present invention, the conjugated diene-based polymer prepared in step (S10) is a conjugated diene-based polymer including an aromatic vinyl-based monomer unit, a conjugated diene-based monomer unit, and a coupling agent linkage group including a silyl hydride. may be, and thus, the hydrogenated conjugated diene-based polymer prepared in step (S20) may include an aromatic vinyl-based monomer unit, an ethylene monomer unit, an olefin-based monomer unit, and a coupling agent linking group including a silyl hydride. . That is, the hydrogenated conjugated diene-based polymer may be a conjugated diene-based polymer in which a conjugated diene-based monomer unit is converted into an ethylene monomer unit and an olefin-based monomer unit by a hydrogenation reaction.

According to an embodiment of the present invention, the conjugated diene-based polymer prepared in step (S10) is a block copolymer comprising an aromatic vinyl-based polymer block, a conjugated diene-based polymer block, and a coupling agent linker including a silyl hydride. Accordingly, the hydrogenated conjugated diene-based polymer prepared in step (S20) may include an aromatic vinyl-based polymer block; an olefin-based polymer block comprising an ethylene monomer unit and an olefin-based monomer unit; and a coupling agent linking group including silyl hydride. That is, the hydrogenated conjugated diene-based polymer may be a conjugated diene-based polymer comprising an olefin-based polymer block in which the conjugated diene-based monomer unit of the conjugated diene-based polymer block is converted into an ethylene monomer unit and an olefin-based monomer unit by a hydrogenation reaction. .

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

Example

Example 1

After replacing the inside of the 10 L autoclave reactor with nitrogen gas, 4,500 g of cyclohexane, 65 g of styrene, and 0.6 g of tetramethylethylenediamine were added, and the temperature inside the reactor was raised to 50°C. Then, 0.79 g of n-butyllithium was added and polymerization was performed for 30 minutes. Then, 435 g of 1,3-butadiene was added and polymerization was performed for 30 minutes. Then, 0.2 g of trimethoxysilane (HSi(OMe) ₃ ) was added and reacted for 10 minutes to prepare a styrene-butadiene-styrene block copolymer (SBS). At this time, the number average molecular weight of the prepared block copolymer was 132,000 g/mol, and the content of the diblock copolymer was 30% by weight.

Subsequently, after replacing the inside of the 2 L autoclave reactor with hydrogen gas, 1,000 g of the prepared styrene-butadiene-styrene block copolymer was pressurized using 1 bar of hydrogen gas. After the pressure transfer is completed, the internal temperature of the reactor is stabilized at 70° C., and Tebbe reagent (CAS No. 67719-69-1) is dissolved in 2 g of cyclohexane so that the Ti atom content is 5 ppm compared to the copolymer. , was introduced into the reactor. After that, the pressure of hydrogen gas inside the reactor was increased to 10 bar, and the reaction was carried out for 2 hours. After completion of the reaction, methanol was added to precipitate and recover a styrene-ethylene-butylene-styrene (SEBS) block copolymer (SEBS), which is a hydrogenated styrene-butadiene-styrene block copolymer.

Example 2

In Example 1, it was carried out in the same manner as in Example 1, except that 0.12 g of dichlorosilane (H ₂ SiCl ₂ ) was added instead of 0.2 g of trimethoxysilane (HSi(OMe) ₃ ). At this time, the number average molecular weight of the prepared block copolymer was 119,000 g/mol, and the content of the diblock copolymer was 41 wt%.

Example 3

In Example 1, it was carried out in the same manner as in Example 1, except that 0.21 g of dichlorophenylsilane (HSiPhCl ₂ ) was added instead of 0.2 g of trimethoxysilane (HSi(OMe) ₃ ). At this time, the number average molecular weight of the prepared block copolymer was 126,000 g/mol, and the content of the diblock copolymer was 36 wt%.

Example 4

In Example 1, trimethoxysilane (HSi(OMe) ₃ ) Instead of 0.2 g, diethoxysilane (H ₂ Si(OEt) ₂ ) 0.14 g was added in the same manner as in Example 1, except that 0.14 g did At this time, the number average molecular weight of the prepared block copolymer was 110,000 g/mol, and the content of the diblock copolymer was 43 wt%.

Comparative Example 1

After replacing the inside of the 10 L autoclave reactor with nitrogen gas, 4,500 g of cyclohexane, 65 g of styrene, and 0.6 g of tetramethylethylenediamine were added, and the temperature inside the reactor was raised to 50°C. Then, 0.79 g of n-butyllithium was added and polymerization was performed for 30 minutes. Then, 435 g of 1,3-butadiene was added and polymerization was performed for 30 minutes. Then, 0.14 g of dimethyldichlorosilane (Me ₂ SiCl ₂ ) was added and reacted for 10 minutes to prepare a styrene-butadiene-styrene block copolymer (SBS). At this time, the number average molecular weight of the prepared block copolymer was 125,000 g/mol, and the content of the diblock copolymer was 36 wt%.

Subsequently, after replacing the inside of the 2 L autoclave reactor with hydrogen gas, 1,000 g of the prepared styrene-butadiene-styrene block copolymer was pressurized using 1 bar of hydrogen gas. After the pressure transfer is completed, the internal temperature of the reactor is stabilized at 70° C., and Tebbe reagent (CAS No. 67719-69-1) is dissolved in 2 g of cyclohexane so that the Ti atom content is 5 ppm compared to the copolymer. , was introduced into the reactor. After that, the pressure of hydrogen gas inside the reactor was increased to 10 bar, and the reaction was carried out for 2 hours. After completion of the reaction, methanol was added to precipitate and recover a styrene-ethylene-butylene-styrene (SEBS) block copolymer (SEBS), which is a hydrogenated styrene-butadiene-styrene block copolymer.

Comparative Example 2

In Comparative Example 1, in addition to dissolving Tebbe reagent (CAS No. 67719-69-1) in 2 g of cyclohexane to have a Ti atom content of 5 ppm compared to the copolymer, polymethylhydrosiloxane as a cocatalyst , number average molecular weight of 1,700 g/mol to 3,200 g/mol) was dissolved so that 200 equivalents of Si atoms compared to Ti atoms were dissolved, and then it was carried out in the same manner as in Comparative Example 1, except that it was introduced into the reactor.

Comparative Example 3

After replacing the inside of the 10 L autoclave reactor with nitrogen gas, 4,500 g of cyclohexane, 65 g of styrene, and 0.6 g of tetramethylethylenediamine were added, and the temperature inside the reactor was raised to 50°C. Then, 0.79 g of n-butyllithium was added and polymerization was performed for 30 minutes. Then, 435 g of 1,3-butadiene was added and polymerization was performed for 30 minutes. Thereafter, 0.22 g of methyltrimethoxysilane (MeSi(OMe) ₃ ) was added and reacted for 10 minutes to prepare a styrene-butadiene-styrene block copolymer (SBS). At this time, the number average molecular weight of the prepared block copolymer was 131,000 g/mol, and the content of the diblock copolymer was 30% by weight.

Subsequently, after replacing the inside of the 2 L autoclave reactor with hydrogen gas, 1,000 g of the prepared styrene-butadiene-styrene block copolymer was pressurized using 1 bar of hydrogen gas. After the pressure transfer is completed, the internal temperature of the reactor is stabilized at 70° C., and Tebbe reagent (CAS No. 67719-69-1) is dissolved in 2 g of cyclohexane so that the Ti atom content is 5 ppm compared to the copolymer. , was introduced into the reactor. After that, the pressure of hydrogen gas inside the reactor was increased to 10 bar, and the reaction was carried out for 2 hours. After completion of the reaction, methanol was added to precipitate and recover a styrene-ethylene-butylene-styrene (SEBS) block copolymer (SEBS), which is a hydrogenated styrene-butadiene-styrene block copolymer.

Comparative Example 4

In Comparative Example 3, in addition to dissolving Tebbe reagent (CAS No. 67719-69-1) in 2 g of cyclohexane to have a Ti atom content of 5 ppm compared to the copolymer, polymethylhydrosiloxane as a cocatalyst , a number average molecular weight of 1,700 g/mol to 3,200 g/mol) was dissolved so that 200 equivalents of Si atoms compared to Ti atoms were dissolved, and then it was carried out in the same manner as in Comparative Example 3, except that it was introduced into the reactor.

Experimental example

10 mg of a sample was collected from each of the hydrogenated polymers prepared in Examples 1 to 4 and Comparative Examples 1 to 4, dissolved in C ₂ D ₂ Cl ₄ , a solvent for NMR measurement, and 500 MHz NMR from Varian was used. ¹ H NMR was measured to confirm the hydrogenation rate, and the types of coupling agents, catalysts and cocatalysts used in each Example and Comparative Example are shown in Table 1.

The hydrogenation rate was calculated from the ratio of the peak integrals of the amount of 1,2-bonds (4.8 ppm to 5.1 ppm) and 1,4-bonds (5.2 ppm to 5.5 ppm) of butadiene before and after hydrogenation.

division Example comparative example One 2 3 4 One 2 3 4 coupling agent HSi(OMe) ₃ H ₂ SiCl ₂ HSiPhCl ₂ H2Si(OEt) ₂ Me ₂ SiCl ₂ Me ₂ SiCl ₂ MeSi(OMe) ₃ MeSi(OMe) ₃ catalyst Tebbe Tebbe Tebbe Tebbe Tebbe Tebbe Tebbe Tebbe cocatalyst - - - - - PMHS - PMHS Hydrogenation rate (%) 99 99 99 99 51 99 54 99

As shown in Table 1 above, when hydrogenation reaction is performed with a catalyst containing Tebbe reagent for the conjugated diene-based polymer coupled with a coupling agent containing silyl hydride according to the present invention, the hydrogenated conjugated diene-based polymer Since peaks hardly appeared at the 1,2-bond and 1,4-bond positions of the butadiene, it was confirmed that the hydrogenated conjugated diene-based polymer could be prepared at a high hydrogenation rate without a cocatalyst.

On the other hand, in the case of Comparative Examples 1 and 3 using a silane-based coupling agent that does not contain silyl hydride as the coupling agent, it was confirmed that the hydrogenation rate was very low because the hydrogenation reaction was carried out without a cocatalyst, and it was confirmed in Comparative Examples 2 and 4 As can be seen, it was confirmed that a co-catalyst was essential to exhibit a hydrogenation rate of 99%.

From these results, it was confirmed that, when the hydrogenation reaction of the conjugated diene-based polymer is carried out according to the present invention, it is possible to produce a hydrogenated conjugated diene-based polymer having a high hydrogenation rate without a cocatalyst.

Claims (10)

Preparing a conjugated diene-based polymer comprising a coupling agent linking group comprising a conjugated diene-based monomer unit and silyl hydride (S10); and
By using hydrogen gas, a hydrogenation reaction of the conjugated diene-based polymer comprises a step (S20),
The hydrogenation reaction is a method for producing a hydrogenated conjugated diene-based polymer that is carried out in the presence of a catalyst comprising a compound represented by the following formula (1):
[Formula 1]

In Formula 1,
Cp is each independently a substituted or unsubstituted cyclopentadienyl group. According to claim 1,
The compound represented by the formula (1) is a hydrogenated conjugated diene-based polymer production method which is a compound represented by the following formula (2):
[Formula 2]

In Formula 2,
R ¹ to R ¹⁰ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, A heteroalkyl group having 1 to 30 carbon atoms or a heterocyclic group having 5 to 30 ring atoms, or two adjacent ones of R ¹ to R ¹⁰ may be connected to each other to form a ring. According to claim 1,
The step (S10) is,
Preparing an anionic active aromatic vinyl-based polymer by polymerizing an aromatic vinyl-based monomer in the presence of an organolithium compound (S1);
In the presence of the anionic active aromatic vinyl-based polymer prepared in step (S1), adding a conjugated diene-based monomer and polymerizing to prepare an anionic active diblock copolymer (S2); and
In the presence of the anionic active diblock copolymer prepared in step (S2), a coupling agent containing silyl hydride is added and reacted to prepare a block copolymer including a coupling agent linking group (S3) A method for producing a hydrogenated conjugated diene-based polymer that is carried out by According to claim 1,
The silyl hydride is a method for preparing a hydrogenated conjugated diene-based polymer, which is a compound represented by the following Chemical Formula 3:
[Formula 3]

In Formula 3,
R ¹ to R ⁴ are each independently hydrogen, a halogen group, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, a cycloalkyl group having 6 to 30 carbon atoms An aryl group, or an alkoxy group having 1 to 30 carbon atoms,
At least one of R ¹ to R ⁴ is hydrogen,
At least one of R ¹ to R ⁴ is a halogen group or an alkoxy group having 1 to 30 carbon atoms. According to claim 1,
The silyl hydride is at least one selected from the group consisting of trimethoxysilane, triethoxysilane, trichlorosilane, tribromosilane, dimethoxysilane, diethoxysilane, dichlorosilane, dibromosilane and dichlorophenylsilane A method for producing a phosphorus hydrogenated conjugated diene-based polymer. According to claim 1,
In the hydrogenation reaction, the hydrogen gas pressure is 5 bar to 20 bar hydrogenated conjugated diene-based polymer production method. According to claim 1,
The method for producing a hydrogenated conjugated diene-based polymer wherein the catalyst is added so that the Ti atom content of the compound represented by Formula 1 is 1 ppm to 10 ppm relative to the content of the conjugated diene-based polymer. Containing a coupling agent linking group comprising a conjugated diene-based monomer unit and silyl hydride,
A hydrogenated conjugated diene-based polymer having a hydrogenation ratio to double bonds of 99% or more. 9. The method of claim 8,
The hydrogenated conjugated diene-based polymer is a hydrogenated conjugated diene-based polymer comprising an aromatic vinyl-based monomer unit, an ethylene monomer unit, an olefin-based monomer unit, and a coupling agent linking group including a silyl hydride. 9. The method of claim 8,
The hydrogenated conjugated diene-based polymer is an aromatic vinyl-based polymer block; an olefin-based polymer block comprising an ethylene monomer unit and an olefin-based monomer unit; And a hydrogenated conjugated diene-based polymer comprising a coupling agent linking group comprising a silyl hydride.