Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F136/06—Butadiene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/42—Introducing metal atoms or metal-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/26—Incorporating metal atoms into the molecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F136/08—Isoprene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/22—Emulsion polymerisation
  • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
  • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F236/06—Butadiene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains

Definitions

• the present invention relates to a polymer composition containing a modified polymer having a boron-containing functional group and a production method.
• a method for synthesizing a polymer having various functional groups at the terminal, for example, a boron-containing functional group, by anionic polymerization is being studied.
• a method of introducing a boronic acid group, which is an example of a boron-containing functional group, into the terminal of a polymer has been studied, and a boronic acid group, which is a boron-containing functional group, or a polymer having a boronic acid group at the terminal is ethylene-.
• a resin modifier such as a compatibilizer for a thermoplastic resin having a hydroxyl group on the side chain of a vinyl alcohol copolymer or the like (see Patent Document 1).
• borinic acid group-modified polymer composed of at least one polymer of a styrene monomer and a diene monomer has been studied for tire applications for the purpose of improving the dispersibility of silica (see Patent Document 2).
• Patent Document 1 specifically, it is considered to obtain a conjugated diene-based polymer having boronic acid at the terminal by reacting the terminal of the active terminal polymer of anionic polymerization with trimethyl borate.
• the reactivity of the boric acid ester is not sufficient in the production method. It has been found that a large amount of unmodified polymer having no boronic acid group can be contained.
• Patent Document 2 describes that a conjugated diene-based polymer having a borinic acid group at the end of the polymer has an effect of improving silica dispersibility.
• a polymerizable composition containing only a borinic acid group-modified polymer can be obtained in a high yield.
• Borinic acid has high Lewis acidity and is excellent in reactivity with Lewis basic compounds, but it easily generates protons in the presence of water, which causes a decrease in storage stability in a conjugated diene polymer.
• an oligomer of a small molecule boronic acid is contained at the terminal, the reaction competes with the polymer, which may cause a problem such as a decrease in graft efficiency.
• the present invention has been made in view of the above circumstances, and a polymer having a boron-containing functional group suitable for modification of various materials such as modification of polar materials and dispersion of inorganic materials can be obtained in high yield. It is an object of the present invention to provide a polymer composition containing a modified polymer having a boron-containing functional group, which achieves both high reactivity to various polar functional groups and excellent storage stability (for example, heat resistance). And.
• a predetermined anionic polymerization active terminal polymer and a boric acid compound satisfying a predetermined parameter are used in the step of producing a polymer having a boron-containing functional group. It has been found that the desired polymer can be obtained in high yield. Furthermore, a specific polymer composition containing a modified polymer containing a predetermined boronic acid ester group and a modified polymer containing a predetermined borinic acid group is excellent in reactivity to polar functional groups and storage stability. We have found and completed the present invention.
• An active terminal polymer (Z) is obtained by anionic polymerization of at least one monomer selected from the group consisting of conjugated diene and aromatic vinyl compounds in the presence of an anionic polymerizable active metal or active metal compound.
• a method for producing a polymer composition containing. BOR (I) (In formula (I), B is a boron atom, O is an oxygen atom, and R is an organic group.) [2] The method for producing a polymer composition according to [1], wherein in the step (2), the polar compound is mixed with the boric acid compound and then added to the active terminal polymer (Z) for reaction. .. [3] A modified polymer containing a boronic acid group represented by the following formula (II), a modified polymer containing a boronic acid ester group represented by the following formula (III), and a boronic acid base represented by the following formula (IV).
• Polymer composition A modified polymer containing a borinic acid group represented by the following formula (V) or (VI), a modified polymer containing a borinic acid ester group represented by the following formula (VII) or (VIII), and the following formula (IX) or It contains 1 to 45% by mass of at least one borinic acid-based modified
• P 1 , P 2 and P 3 represent a polymer chain containing at least one monomer unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units.
• R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and at least one of R 1 and R 2 is an alkyl group having 1 to 12 carbon atoms. Yes, or R 1 and R 2 are bonded to form an alkylene chain having 2 to 24 carbon atoms.
• R 3 , R 4 and R 5 are each independently at least one monomer selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a conjugated diene unit and an aromatic vinyl compound unit.
• a polymer chain containing a unit, at least one of R 3 , R 4 and R 5 is selected from the group consisting of an alkyl group having 1 to 12 carbon atoms or a conjugated diene unit and an aromatic vinyl compound unit. It is a polymer chain containing one monomer unit, or R 3 and R 4 , R 3 and R 5 , or R 4 and R 5 are bonded to form an alkylene chain having 2 to 24 carbon atoms. R 3 , R 4 and R 5 may be bonded to form a trivalent saturated hydrocarbon chain having 3 to 36 carbon atoms, and M may be one alkali metal or alkaline earth. Shows 1/2 metal. )
• P 4 , P 5 , P 6 , P 7 , P 8 , P 9 , P 10 , P 11 and P 12 are at least one selected from the group consisting of conjugated diene units and aromatic vinyl compound units. Representing a polymer chain containing one monomeric unit, R 6 , R 7 , R 8 and R 9 each independently represent an alkyl group having 1 to 12 carbon atoms. R 10 and R 11 are independently hydrogen atoms or alkyl groups having 1 to 12 carbon atoms, and at least one of R 10 and R 11 is an alkyl group having 1 to 12 carbon atoms. Yes, or R 10 and R 11 are bonded to form an alkylene chain having 2 to 24 carbon atoms.
• R 12 represents an alkyl group having 1 to 12 carbon atoms.
• R 13 and R 14 are independently hydrogen atoms or alkyl groups having 1 to 12 carbon atoms, and at least one of R 13 and R 14 is an alkyl group having 1 to 12 carbon atoms. Yes, or R 13 and R 14 are bonded to form an alkylene chain having 2 to 24 carbon atoms.
• M represents one alkali metal or 1/2 alkaline earth metal.
• a weight containing a modified polymer containing a boronic acid ester group and a modified polymer containing a borinic acid group which achieve both high reactivity to a polar functional group and excellent storage stability (for example, heat resistance).
• a combined composition and a method for producing the polymer composition are provided.
• the polymer composition of the present invention comprises a modified polymer containing a boronic acid group represented by the following formula (II), a modified polymer containing a boronic acid ester group represented by the following formula (III), and the following formula (IV).
• a modified polymer containing a boronic acid group represented by the following formula (II) a modified polymer containing a boronic acid ester group represented by the following formula (III), and the following formula (IV).
• the modified polymer containing a boronic acid group is represented by the following formula (II).
• P 1 represents a polymer chain containing at least one monomer unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units.
• the modified polymer containing a boronic acid ester group is represented by the following formula (III).
• P 2 represents a polymer chain containing at least one monomer unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units, and R 1 and R 2 are independent of each other.
• at least one of Taft's steric parameter Es value is preferably ⁇ 0.30 or less, more preferably ⁇ 3.00 to ⁇ 0.30, and -1. It is more preferably .55 to ⁇ 0.39.
• R 1 and R 2 satisfy the above Es value.
• At least one of R 1 and R 2 is preferably an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an i-butyl group and a cyclohexyl group, preferably an isopropyl group and an n-butyl group.
• the group is more preferable, and the isopropyl group is even more preferable.
• R 1 and R 2 are preferably n-propyl group, isopropyl group, n-butyl group, sec-butyl group, i-butyl group or cyclohexyl group, preferably isopropyl group or n-. It is more preferably a butyl group and even more preferably an isopropyl group.
• the three-dimensional parameter Es value of Taft will be described below in the step (2) of the suitable production method of the polymer composition.
• the modified polymer containing a boronic acid base is represented by the following formula (IV).
• P 3 represents a polymer chain containing at least one monomeric unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units, and R 3 , R 4 and R 5 respectively.
• R 3 , R 4 and R 5 are polymer chains containing at least one monomer unit selected from the group consisting of an alkyl group having 1 to 12 carbon atoms or a conjugated diene unit and an aromatic vinyl compound unit.
• R 3 and R 4 , R 3 and R 5 , or R 4 and R 5 may be bonded to form an alkylene chain having 2 to 24 carbon atoms, and R 3 , R 4 and R 5 may be bonded to form a trivalent saturated hydrocarbon chain having 3 to 36 carbon atoms.
• At least one of the above R 3 , R 4 and R 5 preferably has a Taft steric parameter Es value of ⁇ 0.30 or less, and more preferably ⁇ 3.00 to ⁇ 0.30. , -1.55 to -0.39, more preferably. Further, it is a preferable embodiment that all of R 3 , R 4 and R 5 satisfy the above Es values.
• At least one of the above R 3 , R 4 and R 5 is preferably an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an i-butyl group or a cyclohexyl group, preferably an isopropyl group.
• the n-butyl group is more preferable, and the isopropyl group is even more preferable.
• all of R 3 , R 4 and R 5 are preferably n-propyl group, isopropyl group, n-butyl group, sec-butyl group, i-butyl group or cyclohexyl group, preferably isopropyl group.
• M is 1 alkali metal or 1/2 alkaline earth metal, preferably lithium, sodium, or potassium, and more preferably lithium.
• one alkali metal cation is monovalent with respect to one monovalent anion group represented by parentheses in the formula (IX), it corresponds to the valence of the anion group. It means that there is only one alkali metal.
• 1/2 of the alkaline earth metal means that the cation valence of the alkaline earth metal is divalent with respect to one monovalent anionic group represented by parentheses in the formula (IX).
• the valence of the anion group it means that the number of alkaline earth metals is 1/2.
• the modified polymer containing a borinic acid group is represented by the following formula (V) or formula (VI).
• P 4 and P 5 represent a polymer chain containing at least one monomer unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units.
• P 6 represents a polymer chain containing at least one monomer unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units, and R 6 is an alkyl group having 1 to 12 carbon atoms. Is shown.
• the above R 6 is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an i-butyl group and a cyclohexyl group, and the isopropyl group and the n-butyl group are preferable. More preferably, it is further preferably an isopropyl group.
• the modified polymer containing a borinic acid ester group is represented by the following formula (VII) or formula (VIII).
• P 7 and P 8 represent a polymer chain containing at least one monomer unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units, and R 7 has 1 to 12 carbon atoms.
• the alkyl group of is shown.
• the steric parameter Es value of Taft is preferably ⁇ 0.30 or less, more preferably ⁇ 3.00 to ⁇ 0.30, and more preferably ⁇ 1.55 to ⁇ 0.39. Is even more preferable.
• R 7 is preferably an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an i-butyl group, or a cyclohexyl group, more preferably an isopropyl group or an n-butyl group, and an isopropyl group. It is more preferable to have.
• P 9 represents a polymer chain containing at least one monomer unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units
• R 8 is an alkyl having 1 to 12 carbon atoms. It is a group
• R 9 is an alkyl group having 1 to 12 carbon atoms.
• the steric parameter Es value of Taft is preferably ⁇ 0.30 or less, more preferably ⁇ 3.00 to ⁇ 0.30, and more preferably ⁇ 1.55 to ⁇ 0.39. Is even more preferable.
• R 9 is preferably an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an i-butyl group, or a cyclohexyl group, more preferably an isopropyl group or an n-butyl group, and an isopropyl group. It is more preferable to have.
• R 8 is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an i-butyl group and a cyclohexyl group, and the isopropyl group and the n-butyl group are used. More preferably, it is further preferably an isopropyl group.
• the modified polymer containing a boric acid base is represented by the following formula (IX) or formula (X).
• P 10 and P 11 represent a polymer chain containing at least one monomer unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units, and R 10 and R 11 are R 10 and R 11 , respectively. Independently, it is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and at least one of R 10 and R 11 is an alkyl group having 1 to 12 carbon atoms, or R 10 and R 11 Is bonded to form an alkylene chain having 2 to 24 carbon atoms, and M represents one alkali metal or 1/2 alkaline earth metal.
• At least one of Taft's steric parameter Es value is preferably ⁇ 0.30 or less, more preferably ⁇ 3.00 to ⁇ 0.30, and -1. It is more preferably .55 to ⁇ 0.39. Further, it is a preferable embodiment that all of R 10 and R 11 satisfy the above Es value. At least one of R 10 and R 11 is preferably an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an i-butyl group and a cyclohexyl group, preferably an isopropyl group and an n-butyl group.
• R 10 and R 11 are preferably n-propyl group, isopropyl group, n-butyl group, sec-butyl group, i-butyl group or cyclohexyl group, preferably isopropyl group or n-. It is more preferably a butyl group and even more preferably an isopropyl group.
• M is 1 alkali metal or 1/2 alkaline earth metal, preferably lithium, sodium, or potassium, and more preferably lithium.
• P 12 represents a polymer chain containing at least one monomer unit selected from the group consisting of a conjugated diene unit and an aromatic vinyl compound unit, and R 12 is an alkyl group having 1 to 12 carbon atoms.
• R 13 and R 14 are independently hydrogen atoms or alkyl groups having 1 to 12 carbon atoms, and at least one of R 13 and R 14 is an alkyl group having 1 to 12 carbon atoms. Yes, or R 13 and R 14 are bonded to form an alkylene chain having 2 to 24 carbon atoms.
• M represents one alkali metal or 1/2 alkaline earth metal.
• At least one of Taft's steric parameter Es value is preferably ⁇ 0.30 or less, more preferably ⁇ 3.00 to ⁇ 0.30, and -1. It is more preferably .55 to ⁇ 0.39. Further, it is a preferable embodiment that all of R 13 and R 14 satisfy the above Es values. At least one of R 13 and R 14 is preferably an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an i-butyl group and a cyclohexyl group, preferably an isopropyl group and an n-butyl group.
• R 13 and R 14 are preferably n-propyl group, isopropyl group, n-butyl group, sec-butyl group, i-butyl group or cyclohexyl group, preferably isopropyl group or n-. It is more preferably a butyl group and even more preferably an isopropyl group.
• the R 12 is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an i-butyl group or a cyclohexyl group, and the isopropyl group and the n-butyl group are used. More preferably, it is further preferably an isopropyl group.
• the M is preferably lithium, sodium or potassium, and more preferably lithium.
• the above formulas (II) to (X) contain at least one monomer unit selected from the group consisting of conjugated diene units represented by P 1 to P 12 and aromatic vinyl compound units. Includes coalesced chains.
• conjugated diene which is a conjugated diene unit that can be contained in P 1 to P 12
• examples of the conjugated diene include butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, and 2-methyl-1, 3-pentadiene, 1,3-hexadiene, 1,3-octadien, 1,3-cyclohexadiene, 2-methyl-1,3-octadene, 1,3,7-octatriene, milsen, farnesene, chloroprene, etc.
• conjugated diene butadiene and isoprene are preferable, and butadiene is more preferable.
• the conjugated diene as the conjugated diene unit may be used alone or in combination of two or more.
• aromatic vinyl compound which is an aromatic vinyl compound unit that can be contained in P 1 to P 12
• examples of the aromatic vinyl compound include styrene, ⁇ -methyl styrene, 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, and 4-.
• 30% by mass or more of all the monomer units constituting the polymer chain of P 1 to P 12 is at least one monomer unit selected from the group consisting of butadiene and isoprene. be.
• the total content of the butadiene unit and the isoprene unit is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, based on the total monomer unit of the polymer chain to be P 1 .
• the content of the monomer units other than the butadiene unit and the isoprene unit is preferably 50% by mass or less, and 40. More preferably, it is by mass or less.
• the polymer chains to be P 1 to P 12 are homopolymer chains or copolymer chains of at least one monomer selected from the monomers selected from the group consisting of the above-mentioned conjugated diene and aromatic vinyl compounds. Random copolymer chains, block copolymer chains) or copolymer chains containing monomer units of monomers other than the above-mentioned monomers (random copolymer chains, block copolymer chains) can be mentioned. ..
• the weight average molecular weight (Mw) of the polymer chains of P 1 to P 12 is preferably 1,000 or more and 1,000,000 or less, and more preferably 2,000 or more and 500,000 or less. More preferably, it is 3,000 or more and 100,000 or less. Further, it is preferable that the weight average molecular weight (Mw) of the polymer composition of the present invention is also in the above range. When the Mw of the polymer chain is within the above range, the process passability during production tends to be excellent and the economic efficiency tends to be good. In the present invention, unless otherwise specified, Mw is a standard polystyrene-equivalent weight average molecular weight obtained from gel permeation chromatography (GPC) measurements.
• GPC gel permeation chromatography
• the molecular weight distribution (Mw / Mn) of the polymer chains having P 1 to P 12 is preferably 1.0 to 20.0, more preferably 1.0 to 10.0, still more preferably 1.0 to 5.0. , 1.0 to 2.0 are even more preferred, 1.0 to 1.5 are particularly preferred, and 1.0 to 1.2 are even more preferred.
• Mw / Mn is within the above range, the variation in the viscosity of the obtained modified polymer is small, which is more preferable.
• the molecular weight distribution (Mw / Mn) of the polymer composition of the present invention is preferably in the above range from the viewpoint that the variation in viscosity is small.
• Mn means a number average molecular weight
• Mn is a standard polystyrene-equivalent number average molecular weight obtained from GPC measurement.
• the molecular weight distribution (Mw / Mn) means the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene obtained by GPC measurement.
• the vinyl content of the polymer chains of P 1 to P 12 is not particularly limited, but is preferably 90 mol% or less, more preferably 0.01 to 90 mol%, and 0.1. -80 mol% is even more preferred, and 1-70 mol% is even more preferred. Further, it is preferable that the vinyl content of the polymer composition of the present invention is also in the above range.
• the "vinyl content” refers to 1,2-bonds, 3,4-bonds (other than farnesene), and 1,2-bonds, and 3,4-bonds (in the case of other than farnesene) in a total of 100 mol% of conjugated diene units contained in the polymer chain or polymer.
• the vinyl content is derived from conjugated diene units that are bonded in 1,2-bond, 3,4-bond (for non-farnesene), and 3,13-bond (for farnesene) using 1 H-NMR. It is calculated from the area ratio of the peak derived from the conjugated diene unit bonded to the peak of 1,4-bond (in the case of other than farnesene) and 1,13-bond (in the case of farnesene).
• the vinyl content of the polymer of the polymer chain having P 1 to P 12 can be designed according to the purpose. For example, when the vinyl content is less than 70 mol%, the glass transition temperature (Tg) of the polymer is used. ) Is low, and the fluidity and low temperature characteristics of the obtained polymer composition tend to be excellent.
• Tg glass transition temperature
• the vinyl content is determined by, for example, the type of solvent used in the step (1) and the polar compound used as necessary when the polymer composition of the present invention is produced by the method described later. , The desired value can be obtained by controlling the polymerization temperature and the like.
• the glass transition temperature (Tg) of the polymer chain having P 1 to P 12 is butadiene unit, isoprene unit and butadiene unit, vinyl content of conjugated diene unit other than isoprene unit, type of conjugated diene unit, single other than conjugated diene. Although it may vary depending on the content of the unit derived from the polymer, it is preferably ⁇ 150 to 50 ° C, more preferably ⁇ 130 to 50 ° C, and even more preferably ⁇ 130 to 30 ° C. When Tg is in the above range, for example, it is possible to suppress an increase in viscosity and facilitate handling.
• the glass transition temperature (Tg) of the polymer composition of the present invention is preferably in the above range from the viewpoint of ease of handling.
• Tg is the peak top value of DDSC obtained by differential scanning calorimetry (DSC) measurement.
• the polymer composition of the present invention is a modified polymer containing a boronic acid group represented by the above formula (II) and a boron represented by the above formula (III) with respect to the mass of all the polymers contained in the composition. 55 to 99% by mass of at least one boronic acid-based modified polymer (A) selected from the group consisting of a modified polymer containing an acid ester group and a modified polymer containing a boronic acid base represented by the following formula (IV).
• the polymer composition of the present invention contains the boronic acid-based modified polymer (A) and the borinic acid-based modified polymer (B) in the above proportions, so that the polymer composition has high reactivity with polar functional groups and is excellent.
• the polymer composition of the present invention typically means a mixture of a polymer modified with a boron-containing functional group and an unmodified polymer that is not modified by this functional group modification. Therefore, it is preferable that the polymer composition of the present invention comprises only a mixture of a polymer modified with a boron-containing functional group and an unmodified polymer that is not modified by the functional group modification.
• the content of the boronic acid-based modified polymer (A) and the borinic acid-based modified polymer (B) in the polymer composition is determined from the boron concentration in the polymer composition and the 11 B-NMR spectrum.
• a method for determining the boron concentration it can be determined by ICP emission analysis, and the contents of (A) and (B) are calculated from the area ratio of the signal in the 11 B-NMR spectrum.
• the areas of (A) and (B) are also contained in the area ratio of the GPC chart. The amount is calculated. When the degree of separation of peaks is low, the peaks are separated as Gaussian distribution peaks and the area ratio is calculated.
• the content ratios of the boronic acid-based modified polymer (A) and the boronic acid-based modified polymer (B) in the polymer composition of the present invention are boronic acid-based.
• the modified polymer (A) is preferably 65 to 99% by mass and the boronic acid-based modified polymer (B) is preferably 1 to 35% by mass, and the boronic acid-based modified polymer (A) is 68 to 99% by mass and the boronic acid-based modified polymer (B).
• the modified polymer (B) is more preferably 1 to 32% by mass, and the boronic acid-based modified polymer (A) is 79 to 99% by mass and the boronic acid-based modified polymer (B) is 1 to 31% by mass. Is more preferable, and 80 to 99% by mass of the boronic acid-based modified polymer (A) and 1 to 20% by mass of the boronic acid-based modified polymer (B) are particularly preferable.
• the content ratio of the boronic acid-based modified polymer (A) and the borinic acid-based modified polymer (B) in the polymer composition of the present invention is, for example, the three-dimensional parameter Es of Taft in the method for producing a modified polymer described later. It can be controlled by the value, reaction temperature, amount of polar compound and the like.
• the Mw of the boronic acid-based modified polymer (A) is preferably 2,000 or more and 200,000 or less, and more preferably 4,000 or more and 100,000 or less.
• the Mw of the borinic acid-based modified polymer (B) is preferably 4,000 or more and 400,000 or less, and more preferably 8,000 or more and 200,000 or less.
• the boron crosslinked trimer (C) represented by the following formula (XI) and the unmodified product having no boron-containing functional group are not modified as long as the reactivity of the polymer composition is not impaired.
• At least one of the polymers (D) may be further contained, and the content of the polymers (C) and (D) in the polymer composition is preferably 20% by mass or less, respectively.
• P 13 , P 14 and P 15 represent a polymer chain containing at least one monomer unit selected from the group consisting of conjugated diene units and aromatic vinyl compound units.
• the content of the modified polymer having a boron-containing functional group (typically, the modified polymer having a boron-containing functional group at the end) in the polymer composition is the mass of all the polymers contained in the composition. On the other hand, it is preferably 60% by mass or more, and more preferably 65% by mass or more.
• the boron content in the polymer composition can be determined by quantifying the boron content per weight of the polymer composition by ICP emission spectrometry.
• the boron content in the polymer composition is more preferably 0.001 to 5% by mass, preferably 0.003 to 2% by mass. It is more preferable to have.
• a production method including the following steps (1) and (2) is preferable.
• Step (1) An active terminal polymer (1) by anionic polymerization of at least one monomer selected from the group consisting of conjugated diene and aromatic vinyl compound in the presence of anionic polymerizable active metal or active metal compound.
• an active terminal polymer (Z) it is also referred to as an active terminal polymer (Z).
• the monomer as a structural unit derived from the monomer constituting the active terminal polymer (Z), description of preferred embodiments, etc., and derived from the monomer contained in the active terminal polymer (Z).
• Specific examples of structural units and description of preferred embodiments describe at least one monomer selected from the group consisting of conjugated diene units represented by P 1 to P 13 and aromatic vinyl compound units in the above-mentioned polymer compositions. It is the same as the description about the polymer chain containing a unit.
• the active end polymer (Z) having an anionic polymerization active end can be produced by using a known polymerization method. For example, by anionic polymerization of a monomer in the presence of a polar compound, using an anionic polymerizable active metal or an active metal compound as an initiator in a solvent inert to the polymerization terminal, the active terminal weight is used. A coalescence (Z) can be obtained.
• an organic alkali metal compound is preferable, and an organic lithium compound is more preferable.
• the active metal examples include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; and lanthanoid-based rare earth metals such as lanthanum and neodym. Among these, alkali metals and alkaline earth metals are preferable, and alkali metals are more preferable.
• an organic alkali metal compound is preferable.
• the organic alkali metal compound include organic monolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, hexyllithium, phenyllithium and stillbenlithium; Polyfunctional organic lithium compounds such as dilythionaphthalene, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene and the like can be mentioned.
• organolithium compounds are preferable.
• organolithium compound examples include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and pentyllithium.
• the solvent examples include aliphatic hydrocarbons such as n-butane, n-pentane, isopentan, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene. , Aromatic hydrocarbons such as toluene and xylene, and the like.
• aliphatic hydrocarbons such as n-butane, n-pentane, isopentan, n-hexane, n-heptane and isooctane
• alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane
• benzene Aromatic hydrocarbons such as toluene and xylene, and the like.
• a polar compound may be added during the above anionic polymerization.
• Polar compounds are usually used in anionic polymerization to adjust the microstructure (vinyl content) of the conjugated diene moiety without inactivating the reaction.
• the polar compound include ether compounds such as dibutyl ether, tetrahydrofuran and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides and phosphine compounds.
• the polar compound is usually used in an amount of 0.01 to 1000 mol per 1 mol of the organic alkali metal compound.
• the temperature of the anionic polymerization is usually in the range of ⁇ 80 to 150 ° C., preferably in the range of 0 to 100 ° C., and more preferably in the range of 10 to 90 ° C.
• the polymerization mode may be either a batch type or a continuous type.
• Step (2) Having at least two or more of the active terminal polymer (Z) and a partial structure represented by the following formula (I) (hereinafter, the structure is also referred to as a partial structure (I)), and The step BOR (I) of reacting a boric acid compound, wherein the stereo parameter Es value of at least one Taft of R bonded to the oxygen atom contained in the partial structure (I) is ⁇ 0.30 or less.
• B is a boron atom
• O is an oxygen atom
• R is an organic group
• the three-dimensional parameter Es value of Taft is a relative rate based on the effect of the substituent of the methyl group on the acid esterification reaction rate of the substituted carboxylic acid, and is a general steric bulkiness of the substituent. It is an index.
• Tetrahedron, 1978, Vol. Includes Es (Taft) values listed in Table 1 on pages 34,3553 to 3562, as well as values measured by methods according to the methods described above.
• This value has a methyl group value of 0.0, for example, a hydrogen atom value of 1.24, an ethyl group value of -0.08, an n-propyl group value of -0.36, and an isopropyl group.
• the value is -0.47, the value of n-butyl group is -0.39, the value of sec-butyl group is -1.13, the value of i-butyl group is -0.93, and the value of t-butyl group is -0.93. -1.54, the value of the cyclohexyl group is -0.79.
• the steric parameter Es value of Taft is preferably ⁇ 3.00 to ⁇ 0.30, and more preferably ⁇ 1.55 to ⁇ 0.39.
• a bulky boric acid compound having a steric parameter Es value of at least one Taft of R contained in the partial structure (I) of ⁇ 0.30 or less is difficult to form a cluster structure composed of the boric acid compound due to steric hindrance. Therefore, it is possible to obtain a polymer composition having high electrophilicity, improved reaction rate with the active terminal, and a high content ratio of the boric acid-based modified polymer (A). Further, from the viewpoint of further improving the reaction rate, it is a preferable embodiment that all of R bonded to the oxygen atom contained in the partial structure (I) satisfy the above Es value.
• an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an i-butyl group and a cyclohexyl group are preferable, an isopropyl group and an n-butyl group are more preferable, and an isopropyl group is used. Is even more preferable.
• the boric acid compound is a boric acid compound that has reactivity with the active terminal of the active terminal polymer (Z) obtained by anionic polymerization.
• the boric acid ester represented by the following formula (XII) is preferable.
• R 16 , R 17 and R 18 represent hydrocarbon groups having 1 to 12 carbon atoms. At least one of the above R 16 , R 17 and R 18 preferably has a Taft steric parameter Es value of ⁇ 0.30 or less, and more preferably ⁇ 3.00 to ⁇ 0.30. , -1.55 to -0.39, more preferably. Further, it is a preferable embodiment that all of the above R 16 , R 17 and R 18 satisfy the above Es value.
• At least one of the above R 16 , R 17 and R 18 is preferably an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an i-butyl group and a cyclohexyl group, preferably an isopropyl group and an n. -A butyl group is more preferable, and an isopropyl group is even more preferable. Further, all of R 16 , R 17 and R 18 are preferably n-propyl group, isopropyl group, n-butyl group, sec-butyl group, i-butyl group or cyclohexyl group, preferably isopropyl group. Alternatively, it is more preferably an n-butyl group, and even more preferably an isopropyl group.
• boric acid ester represented by the above formula (XII) examples include boric acid tri-n-propyl ester, boric acid tri n-butyl ester, boric acid triisopropyl ester, boric acid tri sec-butyl ester, and boric acid tri. Examples thereof include i-butyl ester and boric acid tricyclohexyl ester. Among these, boric acid tri-n-propyl ester, boric acid tri-n-butyl ester, and boric acid triisopropyl ester are preferable.
• the boric acid compound is used in an amount of preferably 0.5 to 10 mol, more preferably 1 to 5 mol, based on 1 mol of the active terminal polymer (Z).
• step (2) it is preferable to mix the polar compound with the boric acid compound and then react this mixture with the active terminal polymer (Z).
• the polar compound examples include ether compounds such as dibutyl ether, tetrahydrofuran and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides and phosphine compounds.
• the polar compound is usually used in an amount of 0.01 to 1000 mol with respect to the boric acid compound used in the step (2). By adding the polar compound, the molecular association of the boric acid compound can be dissociated and the reactivity can be enhanced.
• the reaction temperature of the active terminal polymer (Z) and the boric acid compound in the above step (2) is usually in the range of ⁇ 80 to 150 ° C., preferably in the range of 0 to 100 ° C., more preferably in the range of 10 to 90 ° C. be.
• a polymerization inhibitor for the active terminal polymer (Z) may be further added.
• the polymerization inhibitor include alcohols such as methanol, ethanol, n-propanol and isopropanol.
• the reaction mode of step (2) may be either a batch type or a continuous type.
• the polymer composition obtained by the production method of the present invention is recovered from the reaction product obtained in the above step (2).
• the method for recovering the polymer composition is not particularly limited, but when the reaction product is obtained as a solution containing the polymer composition in step (2), for example, the obtained solution is used as a poor solvent such as methanol.
• the polymer composition can be recovered by isolating the polymer composition by precipitating the polymer composition or washing the polymer solution with water, separating the polymer composition, and then drying the mixture.
• polymer composition ( ⁇ ) The polymer composition obtained in the present invention (hereinafter, also referred to as polymer composition ( ⁇ )) is further added with other components such as a polymer ( ⁇ ) other than the polymer composition ( ⁇ ). It may be used as a resin composition.
• the other polymer ( ⁇ ) may be a thermoplastic polymer ( ⁇ 1) or a curable polymer ( ⁇ 2).
• thermoplastic polymer ( ⁇ 1) examples include acrylic resins such as polymethyl methacrylate and (meth) acrylic acid ester polymers or copolymers; polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polybutene-. 1.
• Olefin-based resins such as poly-4-methylpentene-1, polynorbornene; ethylene-based ionomers; polystyrene, styrene-maleic anhydride copolymer, high-impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, Styrene resins such as ACS resin and MBS resin; styrene-methyl methacrylate copolymer; styrene-methyl methacrylate-maleic anhydride copolymer; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polylactic acid; nylon 6, Polyamides such as nylon 66 and polyamide elastomers; polycarbonate; polyvinyl chloride; polyvinylidene chloride; polyvinylacetate; polyvinyl alcohol partially saponified; polyvinyl alcohol; ethylene-vinyl alcohol copolymer; polyacetal; vinylidene fluoride; poly
• Examples of the curable polymer ( ⁇ 2) include epoxy resin, unsaturated polyester resin, epoxy (meth) acrylate resin, ester (meth) acrylate resin, phenol resin, urea resin, melamine resin, thermosetting urethane resin, and silicon.
• Examples thereof include resins, imide resins, furan resins, alkido resins, allyl resins, and diallyl phthalate resins.
• epoxy resins and unsaturated polyesters can be obtained from the viewpoints of availability and basic physical properties of the cured product, as well as the ability to remove air bubbles and the toughness of the obtained cured product to obtain a more excellent polymer composition.
• Resins and epoxy (meth) acrylate resins are preferable, among them, epoxy resins and unsaturated polyester resins are more preferable, and epoxy resins are even more preferable.
• the curable polymer ( ⁇ 2) may be used alone or in combination of two or more.
• ⁇ ) is preferably 50/50 to 99/1.
• additives may be added to the resin composition to the extent that the effects of the present invention are not impaired.
• the other polymer ( ⁇ ) is a thermoplastic polymer ( ⁇ 1)
• such additives include, for example, a reinforcing agent or filler such as calcium carbonate, silica, carbon black, glass fiber, clay, and a process oil.
• a reinforcing agent or filler such as calcium carbonate, silica, carbon black, glass fiber, clay, and a process oil.
• Polyethylene glycol, glycerin, phthalates and other plasticizers can be used as additives.
• examples of other additives include heat stabilizers, antioxidants, ultraviolet absorbers, colorants, pigments, lubricants, and surfactants.
• a foaming agent can be mentioned as the additive, and a foam can be produced from a polymer composition containing the foaming agent and the thermoplastic polymer ( ⁇ 1).
• the additive may be a curing agent, a curing accelerator, a known rubber, a thermoplastic elastomer, a core-shell particle, or the like.
• examples thereof include agents, fillers (inorganic particles such as silica, talc, calcium carbonate, aluminum hydroxide, etc.), flame retardants, defoaming agents, pigments, dyes, antioxidants, weather resistant agents, lubricants, and mold release agents.
• the method for mixing the other polymer ( ⁇ ) with the polymer composition ( ⁇ ) of the present invention can be prepared by a usual method for mixing a polymer substance according to the composition ratio of each component and the like.
• a resin composition can be prepared by, for example, a mixing device such as an extruder, a mixing roll, a Banbury mixer, or a kneader.
• a method of melt-kneading using these mixing devices is a preferred embodiment.
• the resin composition is prepared by a method of sufficiently mixing, for example, with a mixer, melt-kneading with a mixing roll, an extruder, or the like, and then cooling and pulverizing. can.
• Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn) By gel permeation chromatography (GPC), the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the conjugated diene-based graft copolymer and the polymer at each stage of its production. was calculated in terms of standard polystyrene.
• the boron-containing functional group introduction rate is determined by decomposing the polymer composition from which unreacted boric acid compounds have been removed by washing with water using a microwave cracker, and then using ICP emission analysis to determine the boron atom content and gel permeation chromatography (GPC). It was calculated from the component ratio of the polymer component by measurement.
• the boron-containing functional group introduction rate is determined from the sum of the boronic acid-based modified polymer (A) and the borinic acid-based modified polymer (B) obtained by removing the mass of the unmodified product from the total mass of the polymer composition.
• the reactivity of the modified polymer was evaluated by 1 H-NMR from the following index from the change in the signal when catechol was added to the deuterated solution of the polymer in the same amount as the starting end of the polymer.
• the amount of the starting terminal of the polymer was calculated by 1 H-NMR from the integral ratio of the alkyl group derived from alkyllithium and the integral ratio of the signal of the double bond derived from the structural unit derived from the conjugated diene.
• Heat resistance The heat resistance of the modified polymer was evaluated by visually changing the appearance during heating. The heat resistance was evaluated by the following index from the appearance after applying the modified polymer to the slide glass and heating it at 100 ° C. for 12 hours in the atmosphere. A: No change in appearance B: Gelling or yellowing
• Example 1 (Step (1)) A sufficiently dried 5 L autoclave was replaced with nitrogen, 1200 g of cyclohexane and 54.0 g of sec-butyllithium (10.5 mass% cyclohexane solution) were charged, the temperature was raised to 50 ° C., and then the polymerization temperature was changed to 50 ° C. under stirring conditions. 1300 g of butadiene was sequentially added at 10 ml / min while controlling so as to be. After the addition of butadiene, the mixture was heated for 1 hour to complete the polymerization.
• Step (2) To the polymerization solution obtained in step (1), 16.6 g of triisopropyl borate was added to introduce boronic acid into the polymerization terminal. Ion-exchanged water was added to the obtained polymer solution and stirred to wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase are separated, the polymer solution phase is recovered and dried under reduced pressure at 90 ° C. for 12 hours to obtain a boronic acid-based modified polymer (A1) and borin. A polymer composition (1) containing an acid-based modified polymer (B1) was obtained. The physical characteristics of the obtained polymer composition (1) are shown in Table 2.
• Example 2 (Step (1)) A sufficiently dried 5 L autoclave was replaced with nitrogen, 1200 g of cyclohexane, 54.0 g of sec-butyllithium (10.5 mass% cyclohexane solution), and 2.06 g of tetramethylethylenediamine (TMEDA) were charged, and the temperature was raised to 50 ° C. Under stirring conditions, 1300 g of butadiene was sequentially added at 10 ml / min while controlling the polymerization temperature to 50 ° C. After the addition of butadiene, the mixture was heated for 1 hour to complete the polymerization.
• TMEDA tetramethylethylenediamine
• Step (2) To the polymerization solution obtained in step (1), 16.6 g of triisopropyl borate was added to introduce boronic acid into the polymerization terminal. Ion-exchanged water was added to the obtained polymer solution and stirred to wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase are separated, the polymer solution phase is recovered and dried under reduced pressure at 90 ° C. for 12 hours to obtain a boronic acid-based modified polymer (A2) and borin. A polymer composition (2) containing an acid-based modified polymer (B2) was obtained. The physical characteristics of the obtained polymer composition (2) are shown in Table 2.
• Step (1) A sufficiently dried 5 L autoclave was replaced with nitrogen, 1200 g of cyclohexane and 54.0 g of sec-butyllithium (10.5 mass% cyclohexane solution) were charged, the temperature was raised to 50 ° C., and then the polymerization temperature was changed to 50 ° C. under stirring conditions. 1300 g of butadiene was sequentially added at 10 ml / min while controlling so as to be. After the addition of butadiene, the mixture was heated for 1 hour to complete the polymerization.
• Step (2) After 2.06 g of TMEDA was added to the polymerization solution obtained in the step (1), 16.6 g of triisopropyl borate was added to introduce boronic acid into the polymerization terminal. Ion-exchanged water was added to the obtained polymer solution and stirred to wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase are separated, the polymer solution phase is recovered and dried under reduced pressure at 90 ° C. for 12 hours to obtain a boronic acid-based modified polymer (A3) and borin. A polymer composition (3) containing an acid-based modified polymer (B3) was obtained. The physical characteristics of the obtained polymer composition (3) are shown in Table 2.
• Examples 4 and 6 The same procedure as in Example 3 was carried out except that the types and amounts of the compounds added in each step were changed as shown in Table 1, and the boronic acid-based modified polymer and the borinic acid-based modified polymer polymer compositions (4), (6). ) was obtained. The physical characteristics of the obtained polymer compositions (4) and (6) are shown in Table 2.
• Examples 5 and 7 The same procedure as in Example 1 was carried out except that the type and amount of the compound added in each step were changed as shown in Table 1, and the boronic acid-based modified polymer and borinic acid-based modified polymer polymer compositions (5), (7). ) was obtained. The physical characteristics of the obtained polymer compositions (5) and (7) are shown in Table 2.
• Example 8 (Step (1)) A sufficiently dried 5 L autoclave was replaced with nitrogen, 1200 g of cyclohexane and 54.0 g of sec-butyllithium (10.5 mass% cyclohexane solution) were charged, the temperature was raised to 50 ° C., and then the polymerization temperature was changed to 50 ° C. under stirring conditions. 1640 g of isoprene was sequentially added at 10 ml / min while controlling so as to be. After the addition of isoprene, the mixture was heated for 1 hour to complete the polymerization.
• Step (2) A mixture of 2.06 g of TMEDA and 16.6 g of triisopropyl borate was added to the polymerization solution obtained in the step (1), and boronic acid was introduced into the polymerization terminal. Ion-exchanged water was added to the obtained polymer solution and stirred to wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase are separated, the polymer solution phase is recovered and dried under reduced pressure at 90 ° C. for 12 hours to obtain a boronic acid-based modified polymer (A8) and borin. A polymer composition (8) containing an acid-based modified polymer (B8) was obtained. The physical characteristics of the obtained polymer composition (8) are shown in Table 2.
• Step (1) A sufficiently dried 5 L autoclave was substituted with nitrogen, charged with 1300 g of cyclohexane, 54.0 g of sec-butyllithium (10.5 mass% cyclohexane solution), and 8.0 g of tetrahydrofuran, heated to 50 ° C., and then stirred under stirring conditions. A monomer mixed solution of 1000 g of butadiene and 377 g of isoprene was sequentially added while controlling the polymerization temperature to be 50 ° C., and polymerization was carried out for 1 hour.
• Step (2) A mixture of 2.06 g of TMEDA and 16.6 g of triisopropyl borate was added to the polymerization solution obtained in the step (1), and boronic acid was introduced into the polymerization terminal. Ion-exchanged water was added to the obtained polymer solution and stirred to wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase are separated, the polymer solution phase is recovered and dried under reduced pressure at 90 ° C. for 12 hours to obtain a boronic acid-based modified polymer (A9) and borin. A polymer composition (9) containing an acid-based modified polymer (B9) was obtained. The physical characteristics of the obtained polymer composition (9) are shown in Table 2.
• Step (1) A sufficiently dried 5 L autoclave was replaced with nitrogen, 1300 g of cyclohexane and 54.0 g of sec-butyllithium (10.5 mass% cyclohexane solution) were charged, the temperature was raised to 50 ° C., and then the polymerization temperature was changed to 50 ° C. under stirring conditions. 580 g of styrene was added and polymerized while controlling so as to be. Next, 8.0 g of tetrahydrofuran was added, and 1000 g of butadiene was sequentially added at 10 ml / min. After the addition of butadiene, the mixture was heated for 1 hour to complete the polymerization.
• Step (2) A mixture of 2.06 g of TMEDA and 16.6 g of triisopropyl borate was added to the polymerization solution obtained in the step (1), and boronic acid was introduced into the polymerization terminal. Ion-exchanged water was added to the obtained polymer solution and stirred to wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase are separated, the polymer solution phase is recovered and dried under reduced pressure at 90 ° C. for 12 hours to obtain a borinic acid-based modified polymer (A10) and borin.
• A10 borinic acid-based modified polymer
• a polymer composition (10) containing an acid-based modified polymer (B10) (borinic acid-based modified conjugated diene-based block copolymer (A10) and borinic acid-based modified conjugated diene-based block copolymer (B10)) was obtained.
• the physical characteristics of the obtained polymer composition (10) are shown in Table 2.
• Example 1 The same procedure as in Example 1 was carried out except that the type and amount of the compound added in each step were changed as shown in Table 1, and the polymer composition containing the boronic acid-based modified polymer and the borinic acid-based modified polymer (11). , (12) was obtained. The physical characteristics of the obtained polymer compositions (11) and (12) are shown in Table 2.
• Step (1) A sufficiently dried 5 L autoclave was replaced with nitrogen, 1200 g of cyclohexane and 54.0 g of sec-butyllithium (10.5 mass% cyclohexane solution) were charged, the temperature was raised to 50 ° C., and then 1300 g of butadiene was sequentially added at 10 ml / min. did. After the addition of butadiene, the mixture was heated for 1 hour to complete the polymerization.
• Step (2) 14.2 g of methanol was added to the polymerization solution obtained in step (1) to terminate the polymerization. Ion-exchanged water was added to the obtained polymer solution and stirred to wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase are separated, the polymer solution phase is recovered and dried under reduced pressure at 90 ° C. for 12 hours to obtain a weight containing the conjugated diene-based polymer (13). The combined composition (13) was obtained. The physical characteristics of the obtained polymer composition (13) are shown in Table 2.
• Step (1) A fully dried 5 L autoclave was replaced with nitrogen, and 1200 g of cyclohexane, 54.0 g of sec-butyllithium (10.5 mass% cyclohexane solution) and 3.1 g of 2,2-ditetrahydrofurylpropane were charged, and the temperature was raised to 50 ° C. Then, under stirring conditions, 1300 g of butadiene was sequentially added at 10 ml / min while controlling the polymerization temperature to 50 ° C. After the addition of butadiene, the mixture was heated for 1 hour to complete the polymerization.
• Step (2) 27.6 g of phenylboronic acid anhydride was added to the polymerization solution obtained in the step (1), and borinic acid was introduced into the polymerization terminal. Ion-exchanged water was added to the obtained polymer solution and stirred to wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase are separated, the polymer solution phase is recovered and dried under reduced pressure at 90 ° C. for 12 hours to contain a borinic acid-based modified polymer (B14). The polymer composition (14) was obtained. The physical characteristics of the obtained polymer composition (14) are shown in Table 2.
• Table 2 shows the physical characteristics of the polymer compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 4.
• a boronic acid-based modified polymer (A) suitable for modifying polar materials and dispersing inorganic materials can be obtained in high yield.
• the polymer composition containing the boronic acid-based modified polymer and the borinic acid-based modified polymer obtained in the present invention in a specific ratio has both high reactivity with polar functional groups and excellent storage stability.
• the polymer composition and the resin composition containing the polymer include interior and exterior parts for automobiles, electric / electronic parts, packaging materials, sporting goods, daily miscellaneous goods, laminating materials, elastic materials, various rubber products, medical supplies. , Various adhesives, various coating primers, etc. Can be effectively used in a wide range of fields.

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