JP2023068748A - Polymer composition comprising terminal polyfunctional group-modified polymer - Google Patents

Abstract

To provide a polymer composition comprising a terminal polyfunctional group-modified polymer with a good balance between excellent reactivity (for example, excellent adhesion to dissimilar materials) and high storage stability (for example, heat resistance), and a production method that can give a polymer composition containing a high proportion of the terminal polyfunctional group-modified polymer.SOLUTION: A polymer composition comprises 3-80 mass% of a terminal polyfunctional group-modified polymer (A) represented by a specific chemical formula (I) with a number average molecular weight of 3,000 or more and less than 100,000.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a polymer composition containing a terminal polyfunctional group-modified polymer and a method for producing the same.

In order to improve the properties of a composition containing a polymer, a method of incorporating a terminal functional group-modified polymer having a terminal functional group such as a hydroxyl group or an epoxide group may be considered. Applications of such terminal functional group-modified polymers include resin additives, dispersants for inorganic fillers, and adhesives for dissimilar materials. In general, when the amount of functional group modification in a functional group-modified polymer increases, the functional group concentration per polymer increases and reactivity improves, so it is expected that adhesion and other properties will improve as the functional group concentration increases. It is expected that the characteristics of

As a method for producing a terminal functional group-modified polymer by anionic polymerization, an anionic active terminal of the polymer chain obtained by anionic polymerization is reacted with a blocking agent having an electrophilic polar functional group such as epoxide or ester. A method is known (Patent Document 1). It is also known that the functional group concentration per polymer can be increased by using a polyfunctional compound having a plurality of functional groups (polyfunctional epoxy compound) as the sealant (Patent Document 2).

Japanese Patent Laid-Open No. 7-292159 WO2001/023467

Patent Document 2 discusses obtaining a conjugated diene-based polymer having a polyfunctional epoxy group at its terminal by reacting an anionic active terminal of a polymer with a polyfunctional epoxy compound. However, according to the studies of the present inventors, although a conjugated diene polymer having a polyfunctional epoxy group at the polymer terminal can be obtained by the method of Patent Document 2, the molar concentration of the epoxy group introduced at the polymer terminal was low, and there were cases where the adhesiveness was not sufficient when used as an adhesive component.

The present invention has been made in view of the above circumstances, and a terminal polyfunctional group-modified terminal that achieves both excellent reactivity (e.g., excellent adhesion to different materials) and excellent storage stability (e.g., heat resistance) An object of the present invention is to provide a polymer composition containing a polymer, and a production method for obtaining a polymer composition containing a high content of the terminal polyfunctional group-modified polymer.

As a result of extensive studies by the present inventors, a polymer composition containing a terminal polyfunctional group-modified polymer that satisfies a desired molecular weight and a desired functional group concentration can solve the above problems, and the terminal polyfunctional group In the step of producing a polymer composition containing a modified polymer, a predetermined anionic polymerization-active terminal polymer and a predetermined compound are allowed to coexist, and the association of anions is controlled while controlling the reactivity to obtain the desired polymerization. The inventors have found that the polymer composition containing a high content of coalescence can be easily obtained, and have completed the present invention.

（上記式中、Ｐ¹は、共役ジエン由来の単量体単位および芳香族ビニル化合物由来の単量体単位からなる群より選ばれる少なくとも一つの単量体単位を含む重合体鎖を示し、
Ｒ¹は、炭素数１～２０の２価の炭化水素基であり、該炭化水素基に含まれる、－ＣＨ₂－は、－Ｏ－または－Ｓ－で置換されていてもよく、該炭化水素基に含まれる三級炭素を含むＣＨはＮに置換されていてもよく；
Ｒ²、Ｒ³、及びＲ⁴は、炭素数１～１０の２価の炭化水素基であり、該炭化水素基に含まれる、－ＣＨ₂－は、－Ｏ－または－Ｓ－で置換されていてもよく、該炭化水素基に含まれる三級炭素を含むＣＨはＮに置換されていてもよく；
Ｒ⁵は、炭素数３～１３の２価の炭化水素基であり、該炭化水素基に含まれる、－ＣＨ₂－は、－Ｏ－または－Ｓ－で置換されていてもよく、該炭化水素基に含まれる三級炭素を含むＣＨはＮに置換されていてもよく、該炭化水素基に含まれる水素は、水酸基に置換されていてもよく；
Ｒ⁶、Ｒ⁷、及びＲ⁸は、水素、または炭素数１～２０の1価の炭化水素基であり、該炭化水素基に含まれる、－ＣＨ₂－は、－Ｏ－または－Ｓ－で置換されていてもよく、該炭化水素基に含まれる三級炭素を含むＣＨはＮに置換されていてもよい。）
［２］さらに下記式（ＩＩ）で示される変性重合体（Ｂ１）および下記式（ＩＩＩ）で示される変性重合体（Ｂ２）からなる群より選ばれる少なくとも１種の変性重合体（Ｂ）を含む［１］に記載の重合体組成物。

（上記式中、Ｐ²、Ｐ³、Ｐ⁴及びＰ⁵は、共役ジエン由来の単量体単位および芳香族ビニル化合物由来の単量体単位からなる群より選ばれる少なくとも一つの単量体単位を含む重合体鎖を示し、
Ｒ⁹及びＲ¹⁶は、炭素数１～２０の２価の炭化水素基であり、該炭化水素基に含まれる、－ＣＨ₂－は、－Ｏ－または－Ｓ－で置換されていてもよく、該炭化水素基に含まれる三級炭素を含むＣＨはＮに置換されていてもよく；
Ｒ¹⁰、Ｒ¹¹、Ｒ¹⁷及びＲ¹⁸は、炭素数１～１０の２価の炭化水素基であり、該炭化水素基に含まれる、－ＣＨ₂－は、－Ｏ－または－Ｓ－で置換されていてもよく、該炭化水素基に含まれる三級炭素を含むＣＨはＮに置換されていてもよく；
Ｒ¹²、Ｒ¹³、Ｒ¹⁹及びＲ²⁰は、炭素数３～１３の２価の炭化水素基であり、該炭化水素基に含まれる、－ＣＨ₂－は、－Ｏ－または－Ｓ－で置換されていてもよく、該炭化水素基に含まれる三級炭素を含むＣＨはＮに置換されていてもよく、該炭化水素基に含まれる水素は、水酸基に置換されていてもよく；
Ｒ¹⁴、Ｒ¹⁵、Ｒ²¹及びＲ²²は、水素、または炭素数１～２０の1価の炭化水素基であり、該炭化水素基に含まれる、－ＣＨ₂－は、－Ｏ－または－Ｓ－で置換されていてもよく、該炭化水素基に含まれる三級炭素を含むＣＨはＮに置換されていてもよい。）
［３］炭化水素溶媒中、アニオン重合可能な活性金属又は活性金属化合物と、共役ジエン及び芳香族ビニル化合物から選ばれる少なくとも１つを含む単量体成分とを反応させ、活性末端重合体（α）を作製する工程、
活性末端重合体（α）と、ルイス酸化合物（ａ）およびルイス塩基化合物（ｂ）からなる群より選ばれる少なくとも１つとを混合する工程、および
前記混合を経た活性末端重合体（α）と、３個以上のエポキシ基を有する多官能化合物とを反応させる工程を含む、
末端多官能基変性重合体を含む重合体組成物の製造方法。
［４］前記混合する工程において、ルイス酸化合物（ａ）およびルイス塩基化合物（ｂ）を混合する、［３］に記載の重合体組成物の製造方法。
［５］前記ルイス酸化合物（ａ）が下記式（ＩＶ）で示される化合物、アルキル亜鉛化合物およびアルキルマグネシウム化合物からなる群より選ばれる少なくとも１つである、［３］または［４］に記載の重合体組成物の製造方法。
ＭＲ²³ ₃ （ＩＶ）
（上記式中、Ｍは第１３族元素であり、Ｒ²³は、炭素数１～２０の1価の炭化水素基を示す。）
［６］式（ＩＶ）で示される化合物がアルキルアルミニウム化合物である、［５］に記載の重合体組成物の製造方法。
［７］前記ルイス塩基化合物（ｂ）が、エーテル化合物およびアミン化合物からなる群より選ばれる少なくとも１つである、［３］～［６］のいずれかに記載の重合体組成物の製造方法。
［８］前記多官能化合物が分子中に４個のエポキシ基を有する、請求項［３］～［７］のいずれかに記載の重合体組成物の製造方法。 That is, the present invention provides the following [1] to [8].
[1] A polymer composition containing 3 to 80% by mass of a terminal polyfunctional group-modified polymer (A) represented by the following formula (I) having a number average molecular weight of 3,000 or more and less than 100,000 .

(In the above formula, P ¹ represents a polymer chain containing at least one monomer unit selected from the group consisting of a monomer unit derived from a conjugated diene and a monomer unit derived from an aromatic vinyl compound,
R ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be substituted with —O— or —S—; CH containing a tertiary carbon contained in a hydrogen group may be substituted with N;
R ² , R ³ and R ⁴ are a divalent hydrocarbon group having 1 to 10 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is substituted with —O— or —S— CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N;
R ⁵ is a divalent hydrocarbon group having 3 to 13 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be substituted with —O— or —S—; CH containing a tertiary carbon contained in the hydrogen group may be substituted with N, and the hydrogen contained in the hydrocarbon group may be substituted with a hydroxyl group;
R ⁶ , R ⁷ and R ⁸ are hydrogen or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O— or —S— and CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N. )
[2] Furthermore, at least one modified polymer (B) selected from the group consisting of a modified polymer (B1) represented by the following formula (II) and a modified polymer (B2) represented by the following formula (III) The polymer composition according to [1], comprising:

(In the above formula, P ² , P ³ , P ⁴ and P ⁵ are at least one monomer unit selected from the group consisting of monomer units derived from conjugated dienes and monomer units derived from aromatic vinyl compounds. shows a polymer chain containing
R ⁹ and R ¹⁶ are divalent hydrocarbon groups having 1 to 20 carbon atoms, and -CH ₂ - contained in the hydrocarbon groups may be substituted with -O- or -S- , CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N;
R ¹⁰ , R ¹¹ , R ¹⁷ and R ¹⁸ are divalent hydrocarbon groups having 1 to 10 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O— or —S— optionally substituted, CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N;
R ¹² , R ¹³ , R ¹⁹ and R ²⁰ are divalent hydrocarbon groups having 3 to 13 carbon atoms, and —CH ₂ — contained in the hydrocarbon groups is —O— or —S— optionally substituted, CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N, and hydrogen contained in the hydrocarbon group may be substituted with a hydroxyl group;
R ¹⁴ , R ¹⁵ , R ²¹ and R ²² are hydrogen or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O— or — may be substituted with S—, and CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N; )
[3] In a hydrocarbon solvent, an anionically polymerizable active metal or active metal compound is reacted with a monomer component containing at least one selected from conjugated dienes and aromatic vinyl compounds to form an active terminal polymer (α ),
a step of mixing an active terminal polymer (α) with at least one selected from the group consisting of a Lewis acid compound (a) and a Lewis base compound (b), and the active terminal polymer (α) subjected to the mixing; Including the step of reacting with a polyfunctional compound having 3 or more epoxy groups,
A method for producing a polymer composition containing a terminal polyfunctional group-modified polymer.
[4] The method for producing a polymer composition according to [3], wherein the Lewis acid compound (a) and the Lewis base compound (b) are mixed in the mixing step.
[5] According to [3] or [4], wherein the Lewis acid compound (a) is at least one selected from the group consisting of a compound represented by the following formula (IV), an alkylzinc compound, and an alkylmagnesium compound. A method for producing a polymer composition.
^MR233 ₍ IV)
(In the above formula, M is a Group 13 element, and R ²³ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms.)
[6] The method for producing a polymer composition according to [5], wherein the compound represented by formula (IV) is an alkylaluminum compound.
[7] The method for producing a polymer composition according to any one of [3] to [6], wherein the Lewis base compound (b) is at least one selected from the group consisting of ether compounds and amine compounds.
[8] The method for producing a polymer composition according to any one of [3] to [7], wherein the polyfunctional compound has four epoxy groups in the molecule.

According to the present invention, a polymer composition containing a terminal polyfunctional group-modified polymer that achieves both excellent reactivity (e.g., excellent adhesion to different materials) and excellent storage stability (e.g., heat resistance), and Provided is a production method for obtaining a polymer composition containing a high content of the terminal polyfunctional group-modified polymer.

The present invention will be described in detail below.
The polymer composition of the present invention contains a terminal polyfunctional group-modified polymer (A) represented by the following formula (I) having a number average molecular weight of 3,000 or more and less than 100,000 in an amount of 3 to 80% by mass. Including in

The terminal polyfunctional group-modified polymer (A) is a polymer represented by the following formula (I).

In formula (I), P ¹ represents a polymer chain containing at least one monomer unit selected from the group consisting of conjugated diene-derived monomer units and aromatic vinyl compound-derived monomer units.
R ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be substituted with —O— or —S—; CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N.
R ² , R ³ and R ⁴ above are divalent hydrocarbon groups having 1 to 10 carbon atoms, and —CH ₂ — contained in the hydrocarbon groups is substituted with —O— or —S— CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N.
R ⁵ is a divalent hydrocarbon group having 3 to 13 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be substituted with —O— or —S—; CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N, and hydrogen contained in the hydrocarbon group may be substituted with a hydroxyl group.
R ⁶ , R ⁷ and R ⁸ are hydrogen or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O— or —S may be substituted with -, and CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N;

Examples of conjugated dienes that can be included in P ¹ as conjugated diene units include butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, and 2-methyl-1,3-pentadiene. , 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, farnesene, and chloroprene. Among these conjugated dienes, butadiene and isoprene are preferred, and butadiene is more preferred. The conjugated diene to be the conjugated diene unit may be used alone or in combination of two or more.

Examples of the aromatic vinyl compound that can be included in P ¹ include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4 -(phenylbutyl)styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylanthracene, N,N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, divinylbenzene, etc. is mentioned. Among these aromatic vinyl compounds, styrene, α-methylstyrene, and 4-methylstyrene are preferred. The aromatic vinyl compound to be the aromatic vinyl compound unit may be used alone or in combination of two or more.

In one preferred embodiment, at least one monomer unit selected from the group consisting of butadiene and isoprene accounts for 30% by mass or more of the total monomer units constituting the polymer chain of P ¹ . The total content of butadiene units and isoprene units is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, based on the total monomer units of the polymer chain forming P ¹ .

The content of monomer units other than butadiene units and isoprene units in the total monomer units constituting the polymer chain of P ¹ is preferably 50% by mass or less, and 40% by mass or less. is more preferred.

The polymer chain forming P ¹ is a homopolymer chain or copolymer chain (random copolymer chain) of at least one monomer selected from the group consisting of the above conjugated dienes and aromatic vinyl compounds. copolymer chains, block copolymer chains) or copolymer chains containing monomer units of monomers other than the above monomers (random copolymer chains, block copolymer chains).

The number average molecular weight (Mn) of the polymer chain that becomes P ¹ is 3,000 or more and less than 100,000, preferably 10,000 or more and less than 95,000, and 20,000 or more and less than 91,000. is more preferable. When the Mn of the polymer chain is within the above range, there is a tendency that the process passability during production is excellent and the economy is favorable. In the present invention, unless otherwise specified, Mn is the number average molecular weight in terms of standard polystyrene obtained from measurement by gel permeation chromatography (GPC).

The vinyl content of the polymer chain that becomes P ¹ is not particularly limited, but in one embodiment, it is preferably 90 mol% or less, more preferably 0.01 to 90 mol%, and 0.1 to 80 mol. % is more preferred, and 1 to 70 mol % is even more preferred. In the present invention, the “vinyl content” means 1,2-bonds, 3,4-bonds (other than farnesene), and 3,13-bond (in the case of farnesene) conjugated diene unit (1,4-bond (other than farnesene) and 1,13-bond (in the case of farnesene) diene units). Vinyl content is derived from conjugated diene units linked by 1,2-linkages, 3,4-linkages (for non-farnesene), and 3,13-linkages (for farnesene) using ¹ H-NMR. is calculated from the area ratio of the peak derived from the 1,4-bond (other than farnesene) and 1,13-bond (for farnesene) conjugated diene units.

The vinyl content of the polymer of the polymer chain that becomes P ¹ can be designed according to the purpose. For example, when the vinyl content is 70 mol% or less, the glass transition temperature (Tg) of the polymer is low. As a result, the obtained polymer composition tends to be excellent in fluidity and low-temperature properties.

When the polymer composition of the present invention is produced by, for example, the method described later, the vinyl content is determined by the type of solvent used in step (1), the polar compound used as necessary, A desired value can be obtained by controlling the polymerization temperature and the like.

The divalent hydrocarbon group having 1 to 20 carbon atoms that can be R ¹ includes alkylene having 1 to 20 carbon atoms and a divalent hydrocarbon group having an alicyclic hydrocarbon group having 3 to 20 carbon atoms (e.g., cycloalkylene having 3 to 20 carbon atoms), a divalent hydrocarbon group having an aromatic hydrocarbon group having 6 to 20 carbon atoms (such as an arylene group having 6 to 20 carbon atoms), and the like.
Examples of the group obtained by substituting —CH ₂ — of the above hydrocarbon group which can be R ¹ with —O— include a divalent ether group having 2 to 19 carbon atoms. Examples of groups obtained by substituting —CH ₂ — of the above hydrocarbon group which can be R ¹ with —S— include divalent thioether groups having 2 to 19 carbon atoms.
The group obtained by substituting -N- for CH containing a tertiary carbon in the hydrocarbon group that can be R ¹ is a divalent group obtained by removing two hydrogen atoms from a tertiary amine compound having 2 to 19 carbon atoms. is mentioned.
As the group for R ¹ , alkylene having 1 to 10 carbon atoms or a group represented by the following formula is preferable.

Among the groups represented by the above formulas, the following groups containing a cyclohexyl ring or an aromatic ring are more preferred.

The divalent hydrocarbon group having 1 to 10 carbon atoms that can be R ² , R ³ and R ⁴ includes alkylene having 1 to 10 carbon atoms and divalent hydrocarbon groups having alicyclic hydrocarbon groups having 3 to 10 carbon atoms. Hydrocarbon groups (e.g., cycloalkylene having 3 to 10 carbon atoms), divalent hydrocarbon groups having aromatic hydrocarbon groups having 6 to 10 carbon atoms (arylene groups having 6 to 10 carbon atoms, etc.), and the like. .
Examples of groups obtained by substituting —CH ₂ — of the above hydrocarbon groups which can be R ² , R ³ and R ⁴ with —O— include divalent ether groups having 2 to 9 carbon atoms. Examples of groups obtained by substituting -S- for -CH ₂ - of the above hydrocarbon groups that can be R ² , R ³ and R ⁴ include divalent thioether groups having 2 to 9 carbon atoms.
As a group in which CH containing a tertiary carbon in the hydrocarbon group which can be R ² , R ³ and R ⁴ is substituted with -N-, two hydrogen atoms are added from a tertiary amine compound having 2 to 9 carbon atoms. divalent groups excepted.
As groups for R ² , R ³ and R ⁴ , alkylene having 1 to 10 carbon atoms is preferable.

Examples of the divalent hydrocarbon group having 3 to 13 carbon atoms that can be R ⁵ include alkylene having 3 to 13 carbon atoms and a divalent hydrocarbon group having an alicyclic hydrocarbon group having 3 to 13 carbon atoms (e.g., cycloalkylene having 3 to 13 carbon atoms), a divalent hydrocarbon group having an aromatic hydrocarbon group having 6 to 13 carbon atoms (such as an arylene group having 6 to 13 carbon atoms), and the like.
Examples of groups obtained by substituting —CH ₂ — of the above hydrocarbon group which can be R ⁵ with —O— include divalent ether groups having 2 to 12 carbon atoms. Examples of groups obtained by substituting -S- for -CH ₂ - of the above hydrocarbon groups that can be R ² , R ³ and R ⁴ include divalent thioether groups having 2 to 12 carbon atoms.
The group obtained by substituting -N- for CH containing a tertiary carbon in the hydrocarbon group that can be R ⁵ is a divalent group obtained by removing two hydrogen atoms from a tertiary amine compound having 2 to 12 carbon atoms. is mentioned.
The group to be R ⁵ is preferably a group in which the hydrogen contained in a divalent hydrocarbon group having 3 to 13 carbon atoms is substituted with a hydroxyl group, and more preferably any group represented by the following formula. .

In the above formula, n is 1 to 10, the end marked with * is the end that binds to P ¹ , and the opposite end is the end that binds to N.

Examples of divalent hydrocarbon groups having 1 to 20 carbon atoms that can be R ⁶ , R ⁷ and R ⁸ include divalent hydrocarbon groups having alkylene having 1 to 20 carbon atoms and alicyclic hydrocarbon groups having 3 to 20 carbon atoms. Hydrocarbon groups (e.g., cycloalkylene having 3 to 20 carbon atoms), bivalent hydrocarbon groups having aromatic hydrocarbon groups having 6 to 20 carbon atoms (arylene groups having 6 to 20 carbon atoms, etc.), and the like. .
Examples of groups obtained by substituting —CH ₂ — of the above hydrocarbon groups which can be R ⁶ , R ⁷ and R ⁸ with —O— include divalent ether groups having 2 to 19 carbon atoms. Examples of groups obtained by substituting -S- for -CH ₂ - of the above hydrocarbon groups that can be R ⁶ , R ⁷ and R ⁸ include divalent thioether groups having 2 to 19 carbon atoms.
As a group in which CH containing a tertiary carbon in the hydrocarbon group that can be R ⁶ , R ⁷ and R ⁸ is substituted with -N-, two hydrogen atoms are substituted from a tertiary amine compound having 2 to 19 carbon atoms. divalent groups excepted.
R ⁶ , R ⁷ and R ⁸ are preferably hydrogen, methyl group, ethyl group and isopropyl group.

Mn of the terminal polyfunctional group-modified polymer (A) is 3,000 or more and less than 100,000, preferably 10,000 or more and less than 95,000, and 20,000 or more and less than 91,000 is more preferred.

The content of the terminal polyfunctional group-modified polymer (A) in the polymer composition of the present invention is 3 to 80% by mass. By including the terminal polyfunctional group-modified polymer (A) in the above ratio in the polymer composition of the present invention, excellent reactivity (for example, excellent adhesion to different materials) and excellent storage stability ( For example, heat resistance) can be compatible. From the viewpoint of making it easier to achieve both excellent reactivity with respect to polar functional groups and excellent storage stability, the content of the terminal polyfunctional group-modified polymer (A) is preferably 4 to 80% by mass. It is more preferably 15 to 80% by mass, even more preferably 45 to 80% by mass.

The polymer composition of the present invention further contains at least one selected from the group consisting of a modified polymer (B1) represented by the following formula (II) and a modified polymer (B2) represented by the following formula (III) of the modified polymer (B) may be contained.

In formulas (II) and (III), P ² , P ³ , P ⁴ and P ⁵ are at least selected from the group consisting of monomer units derived from conjugated dienes and monomer units derived from aromatic vinyl compounds. represents a polymer chain containing one monomer unit, R ⁹ and R ¹⁶ are divalent hydrocarbon groups having 1 to 20 carbon atoms, and -CH ₂ - contained in the hydrocarbon group is may be substituted with -O- or -S-, and CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N; R ¹⁰ , R ¹¹ , R ¹⁷ and R ¹⁸ are divalent hydrocarbon groups having 1 to 10 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O— or —S— It may be substituted, and CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N. R ¹² , R ¹³ , R ¹⁹ and R ²⁰ are divalent hydrocarbon groups having 3 to 13 carbon atoms, and —CH ₂ — contained in the hydrocarbon groups is —O— or —S— may be substituted, CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N, and hydrogen contained in the hydrocarbon group may be substituted with a hydroxyl group. R ¹⁴ , R ¹⁵ , R ²¹ and R ²² are hydrogen or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O— or — may be substituted with S—, and CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N;

Specific examples and preferred examples of monomers (conjugated dienes, aromatic vinyl compounds) that can be contained in P ² to P ⁵ as monomer units are the same as for P ¹ in formula (I) above. It is the same.
Descriptions of the polymer chains forming P ² to P ⁵ (preferred content of each monomer unit constituting the polymer chain, the form of the polymer chain, Mn and vinyl content, etc.) are given in the formula (I) above. is the same as for P ¹ of .

Specific examples and preferred examples of groups for R ⁹ and R ¹⁶ are the same as those for R ¹ in formula (I) above.
Specific examples and preferred examples of groups for R ¹⁰ , R ¹¹ , R ¹⁷ and R ¹⁸ are the same as for R ² , R ³ and R ⁴ in formula (I) above.
Specific examples and preferred examples of groups for R ¹² , R ¹³ , R ¹⁹ and R ²⁰ are the same as those for R ⁵ in formula (I) above.
Specific examples and preferred examples of groups for R ¹⁴ , R ¹⁵ , R ²¹ and R ²² are the same as for R ⁶ , R ⁷ and R ⁸ in formula (I) above.

Mn of the modified polymers (B1) and (B2) is usually 6,000 or more and less than 200,000, preferably 20,000 or more and less than 190,000, and 40,000 or more and less than 82,000. It is more preferable to have

The polymer composition of the present invention includes a modified polymer (C) represented by the following formula (V) and a modified polymer having no epoxy group represented by the following formula (VI) ( D) and at least one polymer selected from the group consisting of the unmodified polymer (E).

In formula (V) and formula (VI), P ⁶ , P ⁷ , P ⁸ , P ⁹ , P ¹⁰ , P ¹¹ and P ¹² are monomer units derived from conjugated dienes and monomers derived from aromatic vinyl compounds. represents a polymer chain containing at least one monomer unit selected from the group consisting of monomeric units, R ²³ and R ²⁹ are a divalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group The -CH ₂ - contained may be substituted with -O- or -S-, and the CH containing the tertiary carbon contained in the hydrocarbon group may be substituted with N. R ²⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be substituted with —O— or —S—; CH containing a tertiary carbon contained in a hydrogen group may be substituted with N. R ²⁵ , R ²⁶ , R ²⁷ , R ³⁰ , R ³¹ , R ³² and R ³³ are divalent hydrocarbon groups having 3 to 13 carbon atoms, and -CH ₂ - contained in the hydrocarbon group is , —O— or —S—, the CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N, and the hydrogen contained in the hydrocarbon group is a hydroxyl group may be replaced with R ²⁸ is hydrogen or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be substituted with —O— or —S— , CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N.

Specific examples and preferred examples of monomers (conjugated dienes, aromatic vinyl compounds) that can be contained in P ⁶ to P ¹² as monomer units are described in the description of terminal polyfunctional group-modified polymer (A). is the same as for P ¹ .
The description of the polymer chains that become P ⁶ to P ¹² (preferred content of each monomer unit constituting the polymer chain, the form of the polymer chain, the Mn and vinyl content, etc.) is based on the terminal polyfunctional group-modified polymerization. It is the same as the case of P ¹ included in union (A).

Specific examples and preferred examples of the groups for R ²³ and R ²⁹ are the same as those for R ¹ in formula (I) above.
Specific examples and preferred examples of the group for R ²⁴ are the same as those for R ² , R ³ and R ⁴ in formula (I) above.
Specific examples and preferred examples of the groups for R ²⁵ , R ²⁶ , R ²⁷ , R ³⁰ , R ³¹ , R ³² and R ³³ are the same as those for R ⁵ in formula (I) above.
Specific examples and preferred examples of the group for R ²⁸ are the same as those for R ⁶ , R ⁷ and R ⁸ contained in the terminal polyfunctional group-modified polymer (A).

The unmodified polymer (E) is a polymer corresponding to P ¹ , which is a polymer chain contained in the terminal polyfunctional group-modified polymer (A) represented by the above formula (I).
Specific examples and preferred examples of the monomers (conjugated dienes and aromatic vinyl compounds) that can be contained in the unmodified polymer (E) can be found in P ¹ in the above formula (I). It is the same as the case.
The description of the polymer chain constituting the unmodified polymer (E) (preferred content of each monomer unit constituting the polymer chain, the form of the polymer chain, Mn, vinyl content, etc.) is given by the above formula It is the same as the case of P ¹ in (I).

The total content of the modified polymer (B), the modified polymer (C), the modified polymer having no epoxy group (D) and the unmodified polymer (E) in the polymer composition of the present invention is It is usually 20% by mass to 97% by mass or less, preferably 20% by mass to 96% by mass or less, more preferably 20% by mass to 85% by mass or less, and even more preferably 20% by mass to 55% by mass or less.

The vinyl content of the polymer composition is not particularly limited, but in one embodiment it is preferably 90 mol% or less, more preferably 0.01 to 90 mol%, and further preferably 0.1 to 80 mol%. Preferably, 1 to 70 mol % is even more preferable.
The vinyl content of the polymer composition can be designed according to the purpose. The fluidity and low temperature properties of the composition tend to be excellent.
When the polymer composition of the present invention is produced by, for example, the method described later, the vinyl content is determined by the type of solvent used in step (1), the polar compound used as necessary, A desired value can be obtained by controlling the polymerization temperature and the like.

The terminal polyfunctional group-modified polymer (A), the modified polymer (B), the modified polymer (C), the modified polymer (D) having no epoxy group, and the unmodified polymer ( The content of E) is, for example, when the polymer composition of the present invention is produced by the production method described later, the amount of unreacted polyfunctional compound calculated from gas chromatography (GC) measurement and the GPC chart Calculated from the area ratio. In the GPC chart, when the degree of peak separation is low, the peak is separated as a Gaussian distribution peak and the area ratio is calculated.

The content of the terminal polyfunctional group-modified polymer (A) in the polymer composition of the present invention is, for example, the amount of Lewis acid compound in the method for producing a polymer composition containing a terminal polyfunctional group-modified polymer described later. , the amount of the Lewis base compound, the amount of the polar compound, and the like.

As a method for producing a polymer composition containing the terminal polyfunctional group-modified polymer (A) of the present invention, a production method including the following steps (1), (2) and (3) is preferable.

[Step (1)]
Step (1): reacting an anionically polymerizable active metal or active metal compound with a monomer component containing at least one selected from conjugated dienes and aromatic vinyl compounds in a hydrocarbon solvent to form an active terminal polymer Step of producing (α)

Specific examples of monomers to be structural units derived from the monomers constituting the active terminal polymer (α), description of preferred embodiments, etc., and derived from the monomers contained in the active terminal polymer (α) Specific examples of structural units and explanations of preferred embodiments are at least one monomer selected from the group consisting of conjugated diene units and aromatic vinyl compound units represented by P ¹ to P ¹² in the polymer composition described above. It is the same as described for polymer chains containing units.

Examples of the solvent include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; and benzene. , toluene, and xylene.

The active terminal polymer (α) having an anionic polymerization active terminal can be produced using a known polymerization method. For example, in a solvent inert to the polymerization terminal, using an anionically polymerizable active metal or active metal compound as an initiator, optionally in the presence of a polar compound, by anionically polymerizing a monomer, the active terminal is polymerized. A coalescence (α) can be obtained.

As the anionically polymerizable active metal or active metal compound, an organic alkali metal compound is preferred, and an organic lithium compound is more preferred.

Examples of the active metal include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; and lanthanide rare earth metals such as lanthanum and neodymium. Among these, alkali metals and alkaline earth metals are preferred, and alkali metals are more preferred.

As the active metal compound, an organic alkali metal compound is preferable. Examples of organic alkali metal compounds include organic monolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, hexyllithium, phenyllithium, and stilbenelithium; polyfunctional organic lithium compounds such as dilithionaphthalene, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene; and sodium naphthalene, potassium naphthalene and the like. Among these organic alkali metal compounds, organic lithium compounds are preferred. Examples of the organic lithium compound include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and pentyllithium.

A polar compound may be added during the anionic polymerization. Polar compounds are commonly used in anionic polymerizations to control the microstructure (vinyl content) of the conjugated diene sites without quenching the reaction. Examples of polar compounds 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 generally used in an amount of 0.01 to 1000 mol per 1 mol of the organic alkali metal compound.

The temperature for the anionic polymerization 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. The mode of polymerization may be either a batchwise system or a continuous system.

[Step (2)]
Step (2); a step of mixing an active terminal polymer (α) with at least one selected from the group consisting of a Lewis acid compound (a) and a Lewis base compound (b).

By going through this step (2), in the step (3) described later, when the active terminal polymer (α) is reacted with a polyfunctional compound having 3 or more epoxy groups, it is derived from the polyfunctional compound It becomes easy to obtain a modified polymer having a larger number of epoxy groups. Polymer compositions containing such modified polymers are suitable for dissimilar material adhesives, and have high reactivity with various polar functional groups (e.g., excellent adhesion to dissimilar materials) and excellent storage stability (e.g., heat resistance).

The Lewis acid compound (a) used in step (2) is not particularly limited as long as it does not impair the activity of the anionic active terminal contained in the active terminal polymer (α) and can appropriately suppress its reactivity.
As the Lewis acid compound (a) which does not impair the activity of the anionic active terminal contained in the active terminal polymer (α) and which is easily coordinated to the terminal to appropriately suppress the reactivity, there is represented by the following formula (IV). (hereinafter also referred to as compound (IV)), alkylzinc compounds, alkylmagnesium compounds, and the like.
^MR233 ₍ IV)

In the above formula (IV), M is a group 13 element (boron, aluminum, gallium, indium, thallium or nihonium). Among these group 13 elements, boron and aluminum are preferable, and aluminum is more preferable.
In formula (IV) above, R ²³ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. Examples of such hydrocarbon groups include alkyl groups having 1 to 20 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-hexyl group and octyl group. Among these hydrocarbon groups, n-propyl group, n-butyl group, isobutyl group, n-hexyl group and octyl group are preferred, and isobutyl group is more preferred.

Examples of compounds represented by formula (IV) include alkylaluminum compounds and alkylborane compounds.
Examples of alkylaluminum compounds include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and trioctylaluminum.
Examples of alkylborane compounds include trimethylborane, triethylborane, tri-n-propylborane, tri-n-butylborane, triisobutylborane, tri-n-hexylborane, and trioctylborane.

Alkyl zinc compounds include dimethyl zinc, diethyl zinc, di-n-propyl zinc, diisobutyl zinc, and di-n-butyl zinc.
Examples of alkylmagnesium compounds include butylethylmagnesium, di-n-butylmagnesium, and di-n-hexylmagnesium.

Among these Lewis acid compounds (a), alkylaluminum compounds and alkylzinc compounds are preferred because they do not impair the activity of the anionic active terminal contained in the active terminal polymer (α) and tend to appropriately suppress its reactivity. , alkylaluminum compounds are more preferred, and triisobutylaluminum is particularly preferred.

These Lewis acid compounds (a) may be used alone or in combination of two or more.

When the Lewis acid compound (a) is used in the step (2), the Lewis acid compound (a) is preferably 0.01 to 10 mol, more than 1 mol of the active terminal polymer (α). It is preferably used in an amount of 0.1 to 2 mol. By adding the Lewis acid compound (a) to the active terminal in the above range, the Lewis acid compound (a) is easily coordinated to the active terminal, and the reactivity is easily suppressed appropriately.

The Lewis base compound (b) used in step (2) is capable of dissociating the association state of the terminal without impairing the activity of the anion-active terminal contained in the active-terminal polymer (α). It can be used without any particular limitation as long as the properties can be enhanced. Examples of the Lewis base compound (b), which can appropriately enhance the dissociation of the association of the anion active terminal of the active terminal polymer (α) and the reactivity of the anion active terminal, include ether compounds, amine compounds, and the like. mentioned.

The amine compound can be used without particular limitation as long as it can be used as the Lewis base compound (b) of the present application, but tertiary amines are preferred.
Examples of the ether compounds include aliphatic ethers and aromatic ethers. Among these ether compounds, aliphatic ethers are preferred.

As the tertiary amine, those having one or more nitrogen atoms in the molecule and all existing nitrogen atoms are preferably tertiary. For example, monovalent amines such as trimethylamine, triethylamine and methyldiethylamine; N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl-1,3-diaminopropane, N, Linear polyvalent amines such as N,N',N'-tetramethyl-1,6-diaminohexane, N,N,N',N'',N''-pentamethyldiethylenetriamine; 2,6,10 - azacrowns such as trimethyl-2,6,10-triazaundecane; branched chain polyvalent amines such as tris[2-(N,N-dimethylamino)ethyl]amine; N,N'-dimethylpiperazine, 1, Cyclic polyvalent amines such as 4-diazabicyclo[2.2.2]octane, 1,4,7-trimethyl-1,4,7-triazacyclononane; 1,3,5-trimethylhexahydro-1,3 ,5-triazine and other heterocyclic compounds, and 2,4,6-tris(dimethylaminomethyl)benzene and other aromatic amines. Among these tertiary amines, N,N,N',N'-tetramethylethylenediamine is preferred.

Aliphatic ethers include monoethers such as diethyl ether, diisopropyl ether, methyl ethyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, di-n-propyl ether, cyclopentyl methyl ether; 2-dimethoxyethane, ethylene glycol. polyethers such as dimethyl ether; cyclic monoethers such as tetrahydrofuran; and cyclic polyethers such as dioxane, 12-crown-4, 18-crown-6. Among these aliphatic ethers, tetrahydrofuran is preferred.

These Lewis base compounds (b) may be used alone or in combination of two or more.

When the Lewis base compound (b) is used in the step (2), the Lewis base compound (b) is preferably 0.5 to 10 mol, more than 1 mol of the active terminal polymer (α). It is preferably used in an amount of 0.5 to 2 mol. By adding the Lewis base compound (b) to the active terminal in the above range, it becomes easier to dissociate the association of the active terminal polymer (α) and to appropriately increase the reactivity.

In the step (2), the active terminal polymer (α) and at least one selected from the group consisting of the Lewis acid compound (a) and the Lewis base compound (b) may be mixed. It is preferable to mix the active terminal polymer (α), the Lewis acid compound (a), and the Lewis base compound (b), since this facilitates appropriate suppression of the reactivity of the active terminal.

When the Lewis acid compound (a) and Lewis base compound (b) are used together in step (2), the ratio is not particularly limited, but the molar ratio (a )/(b), preferably 1/5 to 5/1, more preferably 1/2 to 2/1. When the molar ratio (a)/(b) of the Lewis acid compound (a) and the Lewis base compound (b) is within the above range, the association of the active terminal polymer (α) is dissociated and the reactivity of the active terminal is improved. It becomes easier to appropriately suppress the

The temperature at which the active terminal polymer (α) in the step (2) and at least one selected from the group consisting of the Lewis acid compound (a) and the Lewis base compound (b) are mixed is usually -80 to 150°C. range, preferably 0-100°C, more preferably 10-90°C.

The reaction mode of step (2) may be either a batch system or a continuous system.
Moreover, step (2) is desirably performed after all the monomer components used in the step of producing the active terminal polymer (α) are added. Further, when the active terminal polymer (α) in step (1) contains units derived from a conjugated diene, from the viewpoint of minimizing the effect on the vinyl content, most of the monomer components are polymerized. Afterwards (typically after 80% by weight or more, preferably 95% by weight or more has been polymerized), it is desirable to carry out step (2). Furthermore, from the viewpoint of suppressing deactivation of the anion active terminal of the active terminal polymer (α), it is desirable not to leave the state for a long time after the completion of the polymerization of the monomer component. After the polymerization is approximately completed (typically 90% by mass or more, preferably 95% by mass or more) to 5 minutes after the polymerization of all the monomer components is completed (preferably immediately before the polymerization is completed). It is desirable to perform step (2) in between.

[Step (3)]
Step (3): a step of reacting the mixed active terminal polymer (α) with a polyfunctional compound having three or more epoxy groups.

As the polyfunctional compound, any polyfunctional compound having three or more epoxy groups capable of reacting with the anionic active terminal of the active terminal polymer (α) can be used without particular limitation. As such a polyfunctional compound, a polyfunctional compound having four epoxy groups is preferable.

Examples of the polyfunctional compound having four epoxy groups include polyfunctional compounds represented by the following formula (VII).

In formula (VII), R ³⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is substituted with —O— or —S—. CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N. R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are each a divalent hydrocarbon group having 1 to 10 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O— or —S— It may be substituted, and CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N. R ³⁹ , R ⁴⁰ , R ⁴¹ and R ⁴² are hydrogen or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O— or may be substituted with -S-, and CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N;

Specific examples and preferred examples of the group for R ³⁴ are the same as those for R ¹ in formula (I) above.

Specific examples and preferred examples of groups for R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are the same as those for R ² , R ³ and R ⁴ in formula (I) above.

Specific examples and preferred examples of groups for R ³⁹ , R ⁴⁰ , R ⁴¹ and R ⁴² are the same as for R ⁶ , R ⁷ and R ⁸ in formula (I) above.

Examples of the polyfunctional compound represented by the above formula (VII) include 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N', tetraglycidyl-m-xylenediamine, and the like. mentioned.

In the above step (3), the polyfunctional compound having 3 or more epoxy groups may be 1 mol or more with respect to 1 mol of the active terminal polymer (α). It is preferably in the range of 1 to 1.2 mol per 1 mol of the terminal polymer (α). Moreover, according to the method of the present invention, a modified polymer having more epoxy groups derived from a polyfunctional compound can be obtained without using an excess polyfunctional compound for the active terminal polymer (α). easier.

The temperature at which the active terminal polymer (α) in step (2) is reacted with the polyfunctional compound having 3 or more epoxy groups 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.

The reaction mode of step (3) may be either a batch system or a continuous system.

The polymer composition obtained by the production method of the present invention is recovered from the reaction product obtained in step (3) above. The method for recovering the polymer composition is not particularly limited. After mixing, washing with water, separation, and drying, the above polymer composition can be isolated and recovered.

The polymer composition obtained in the present invention is a material that has both excellent reactivity with various polar functional groups (e.g., excellent adhesion to different materials) and excellent storage stability (e.g., heat resistance). Therefore, the polymer composition of the present invention can be used as an adhesive composition as it is. Moreover, the adhesive composition containing the polymer composition of the present invention may contain various additives to the extent that the effects of the present invention are not impaired. Such additives include, for example, heat stabilizers, antioxidants, and the like. Moreover, the adhesive composition may contain a resin.
The above-mentioned adhesive composition can be suitably used, for example, as an adhesive for dissimilar materials because the polymer composition has the properties described above.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. In the following examples and comparative examples, the physical properties of polymer compositions were evaluated by the following methods.

(1) number average molecular weight (Mn)
By gel permeation chromatography (GPC), the polymer composition containing the modified polymer and the number average molecular weight (Mn) of the polymer at each stage of its production were determined in terms of standard polystyrene.
Apparatus: GPC apparatus "HLC-8220" manufactured by Tosoh Corporation
Separation column: Tosoh Corporation "TSKgel SuperMultiporeHZ-M (column diameter = 4.6 mm, column length = 15 cm)" (used by connecting two in series)
Eluent: Tetrahydrofuran Eluent flow rate: 0.35 mL/min Column temperature: 40°C
Detection method: Differential refractive index (RI)
Injection volume: 10 μl
Concentration: 1 mg/1 cc (sample polymer composition or polymer/tetrahydrofuran)

(2) vinyl content
By ¹ H-NMR, the terminal functional group-modified polymer and the vinyl content of the polymer at each stage of its production were calculated. Vinyl Content was calculated.
Apparatus: Nuclear magnetic resonance apparatus "JNM-ECX400" manufactured by JEOL Ltd.
Solvent: Heavy chloroform Measurement temperature: 50°C
Accumulated times: 1024 times

(3) Polymer ratio (% by mass) and terminal functional group introduction rate (% by mass)
Since the molecular weight increases in the order of terminal polyfunctional group-modified polymer (A), modified polymer (B), modified polymer (C), and modified polymer (D) having no epoxy group, gel permeation Each weight ratio was calculated from the area ratio obtained by chromatography (GPC). When the degree of peak separation was low, the peaks were separated as Gaussian distribution peaks and the area ratio was calculated. Furthermore, when the unmodified polymer (E) was contained, the reaction solution was sampled, filtered, and then analyzed by gas chromatography to quantify unreacted polyfunctional compounds using tridecane as an internal standard.

(Gas chromatography conditions)
Apparatus: GC-2014 (manufactured by Shimadzu Corporation)
Column: DB-10.25 mmφ×30 mm, film thickness 0.25 μm (manufactured by Agilent)
Injection temperature: 280°C
Column temperature: Hold at 50°C for 5 minutes, heat up to 280°C at 10°C/min, then hold for 3 minutes.
FID detector temperature: 280°C
Carrier gas: helium, column flow rate 1.5 mL/min Injection volume: 0.2 μL

(4) Adhesiveness Adhesiveness of the polymer composition was evaluated by applying 3 g of the polymer composition to a rubber surface having a width of 25 mm, a length of 200 mm, and a thickness of 1 mm, and then adhering nylon fibers to the rubber surface. After wiping off the composition, a peel strength test was performed after heating at 150° C. for 30 minutes for vulcanization treatment.
Apparatus: "Instron 5900R" manufactured by Instron
Pull speed: 10mm/min
The peel strength between the nylon fiber and the rubber was evaluated using the following indices.
A: Peel strength of 50 N/inch or more B: Peel strength of 20 N/inch or more and less than 50 N/inch C: Peel strength of less than 20 N/inch

(5) Heat resistance The heat resistance of the conjugated diene-based polymer was evaluated by visual observation based on changes in appearance during heating. A slide glass was coated with 1 g of the conjugated diene polymer, and after heating at 100° C. for 12 hours in the atmosphere, the heat resistance was evaluated according to the following index based on the appearance.
A: No change in appearance B: Gelation or yellowing

[Example 1]
(Step (1))
A sufficiently dried 2 L autoclave was purged with nitrogen, charged with 499 g of cyclohexane and 24.6 g of sec-butyllithium (10.5% by mass cyclohexane solution), heated to 50° C., and then polymerized at 50° C. under stirring conditions. 406 g of butadiene was successively added at 20 ml/5 minutes while controlling so that After the addition of butadiene, the mixture was heated for 1 hour to complete the polymerization, thereby obtaining a polymerization solution containing an active terminal polymer (α).

(Step (2))
After adding 38.8 g of triisobutylaluminum (20.0% by weight hexane solution) as Lewis acid compound (a) to the polymerization solution obtained in step (1) and stirring for 30 minutes, Lewis base compound (b) was added. 24.4 g of tetrahydrofuran was added.

(Step (3))
18.0 g of 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, which is a polyfunctional compound having four epoxy groups in the molecule, was added to the polymerization liquid that had undergone step (2), and Epoxy groups were introduced. An aqueous citric acid solution was added to the resulting polymer solution and stirred to acid wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase were separated, the polymer solution phase was recovered. Ion-exchanged water was added to the recovered polymer solution and stirred to wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase were separated, the polymer solution phase was collected and dried under reduced pressure at 90° C. for 12 hours to obtain polymer composition (1). Polymer composition (1) has a number average molecular weight Mn of 28,000, a terminal polyfunctional group-modified polymer (A) containing 3 epoxy groups at the molecular chain ends of 54% by mass, and 2 at the molecular chain ends. 17% by mass of the modified polymer (B) containing an epoxy group, 15% by mass of the modified polymer (C) containing one epoxy group at the molecular chain end, and a modified polymer (D ) was 14% by mass, and the vinyl content of the polymer composition (1) was 9 mol%.

[Example 2]
(Step (1))
A sufficiently dried 2 L autoclave was purged with nitrogen, charged with 841 g of cyclohexane and 8.6 g of sec-butyllithium (10.5% by mass cyclohexane solution), heated to 50°C, and then polymerized at 50°C under stirring conditions. 221 g of butadiene was successively added at 20 ml/5 minutes while controlling so that After the addition of butadiene, the mixture was heated for 1 hour to complete the polymerization, thereby obtaining a polymerization solution containing an active terminal polymer (α).

(Step (2))
26.8 g of tetrahydrofuran, which is the Lewis base compound (b), was added to the polymerization solution obtained in step (1) and stirred for 30 minutes.

(Step (3))
5.2 g of 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, which is a polyfunctional compound having four epoxy groups, is added to the polymerization liquid that has undergone step (2) to add epoxy groups to the polymerization terminals. introduced. An aqueous citric acid solution was added to the resulting polymer solution and stirred to acid wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase were separated, the polymer solution phase was collected. Ion-exchanged water was added to the recovered polymer solution and stirred to wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase were separated, the polymer solution phase was collected and dried under reduced pressure at 90° C. for 12 hours to obtain polymer composition (2). Polymer composition (2) has a number average molecular weight Mn of 62,000, a terminal polyfunctional group-modified polymer (A) containing 3 epoxy groups at the molecular chain ends of 10% by mass, and 2 at the molecular chain ends. 15% by mass of the modified polymer (B) containing an epoxy group, 39% by mass of the modified polymer (C) containing one epoxy group at the molecular chain end, and a modified polymer (D) having no epoxy group was 12% by weight, and the unmodified polymer (E) was 24% by weight, and the vinyl content of the polymer composition (2) was 9 mol%.

[Example 3]
(Step (1))
A sufficiently dried 2 L autoclave was purged with nitrogen, charged with 623 g of cyclohexane and 16.6 g of sec-butyllithium (10.5% by mass cyclohexane solution), heated to 50°C, and then polymerized at 50°C under stirring conditions. 431 g of butadiene was successively added at 20 ml/5 minutes while controlling so that After the addition of butadiene, the mixture was heated for 1 hour to complete the polymerization, thereby obtaining a polymerization solution containing an active terminal polymer (α).

(Step (2))
13.7 g of triisobutylaluminum (20.0% by weight hexane solution), which is the Lewis acid compound (a), was added to the polymerization solution obtained in step (1) and stirred for 30 minutes.

(Step (3))
10.2 g of 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, which is a polyfunctional compound having four epoxy groups, is added to the polymerization solution that has undergone step (2) to add epoxy groups to the polymerization terminals. introduced. An aqueous citric acid solution was added to the resulting polymer solution and stirred to acid wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase were separated, the polymer solution phase was recovered. Ion-exchanged water was added to the recovered polymer solution and stirred to wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase were separated, the polymer solution phase was collected and dried under reduced pressure at 90° C. for 12 hours to obtain a polymer composition (3). Polymer composition (3) has a number average molecular weight Mn of 87,000, a terminal polyfunctional group-modified polymer (A) containing 3 epoxy groups at the molecular chain ends of 4 mass%, and 2 at the molecular chain ends. 9% by mass of the modified polymer (B) containing an epoxy group, 52% by mass of the modified polymer containing one epoxy group (C) at the molecular chain end, and the modified polymer (D) having no epoxy group was 26% by weight, and the unmodified polymer (E) was 9% by weight, and the vinyl content of the polymer composition (3) was 10 mol%.

[Example 4]
(Step (1))
A sufficiently dried 2 L autoclave was purged with nitrogen, charged with 573 g of cyclohexane, 28.3 g of sec-butyllithium (10.5% by mass cyclohexane solution), and 5.3 g of tetrahydrofuran, heated to 50° C., and stirred. 467 g of butadiene was successively added at 20 ml/5 minutes while controlling the polymerization temperature to 50°C. After the addition of butadiene, the mixture was heated for 1 hour to complete the polymerization, thereby obtaining a polymerization solution containing an active terminal polymer (α).

(Step (2))
After adding 44.6 g of triisobutylaluminum (20.0% by weight hexane solution) as the Lewis acid compound (a) to the polymerization liquid obtained in step (1) and stirring for 30 minutes, the Lewis base compound (b) was added. 22.8 g of tetrahydrofuran was added.

(Step (3))
20.7 g of 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, which is a polyfunctional compound having four epoxy groups, is added to the polymerization solution that has undergone step (2) to add epoxy groups to the polymerization terminals. introduced. An aqueous citric acid solution was added to the resulting polymer solution and stirred to acid wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase were separated, the polymer solution phase was recovered. Ion-exchanged water was added to the recovered 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 collected and dried under reduced pressure at 90° C. for 12 hours to add 0 to 3 epoxy groups to the ends of the molecular chains. A modified polymer composition (4) containing Polymer composition (4) has a number average molecular weight Mn of 28,000, a terminal polyfunctional group-modified polymer (A) containing 3 epoxy groups at the molecular chain ends of 49% by mass, and 2 at the molecular chain ends. 20% by mass of the modified polymer (B) containing an epoxy group, 19% by mass of the modified polymer (C) containing one epoxy group at the molecular chain end, and a modified polymer (D ) was 12 mass %, and the vinyl content of the polymer composition (4) was 42 mol %.

[Example 5]
(Step (1))
A sufficiently dried 2 L autoclave was purged with nitrogen, charged with 498 g of cyclohexane and 96.3 g of sec-butyllithium (10.5% by mass cyclohexane solution), heated to 50°C, and then polymerized at 50°C under stirring conditions. 344 g of butadiene was successively added at 20 ml/5 minutes while controlling so that the After the addition of butadiene, the mixture was heated for 1 hour to complete the polymerization, thereby obtaining a polymerization solution containing an active terminal polymer (α).

(Step (2))
After adding 13.7 g of tetrahydrofuran, which is the Lewis base compound (b), to the polymerization solution obtained in step (1) and stirring for 30 minutes, triisobutylaluminum (20.0% by weight), which is the Lewis acid compound (a), was added. hexane solution) was added.

(Step (3))
8.2 g of 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, which is a polyfunctional compound having four epoxy groups, is added to the polymerization solution that has undergone step (2) to add epoxy groups to the polymerization terminals. introduced. An aqueous citric acid solution was added to the resulting polymer solution and stirred to acid wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase were separated, the polymer solution phase was recovered. Ion-exchanged water was added to the recovered 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 collected and dried under reduced pressure at 90° C. for 12 hours to add 0 to 3 epoxy groups to the ends of the molecular chains. A modified polymer composition (5) containing Polymer composition (5) has a number average molecular weight Mn of 4,200, 51% by mass of terminal polyfunctional group-modified polymer (A) containing 3 epoxy groups at the molecular chain terminals, and 2 at the molecular chain terminals. 19% by mass of the modified polymer (B) containing an epoxy group, 20% by mass of the modified polymer (C) containing one epoxy group at the molecular chain end, and a modified polymer (D ) was 10 mass %, and the vinyl content of the polymer composition (5) was 11 mol %.

[Example 6]
(Step (1))
A sufficiently dried 2 L autoclave was purged with nitrogen, charged with 467 g of cyclohexane and 5.0 g of sec-butyllithium (10.5% by mass cyclohexane solution), heated to 50°C, and then polymerized at 50°C under stirring conditions. 344 g of butadiene was successively added at 20 ml/5 minutes while controlling so that the After the addition of butadiene, the mixture was heated for 1 hour to complete the polymerization, thereby obtaining a polymerization solution containing an active terminal polymer (α).

(Step (2))
After adding 7.8 g of triisobutylaluminum (20.0% by weight hexane solution) as the Lewis acid compound (a) to the polymerization solution obtained in step (1) and stirring for 30 minutes, the Lewis base compound (b) was added. 12.2 g of tetrahydrofuran was added.

(Step (3))
3.6 g of 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, which is a polyfunctional compound having four epoxy groups, is added to the polymerization solution that has undergone step (2) to add epoxy groups to the polymerization terminals. introduced. An aqueous citric acid solution was added to the resulting polymer solution and stirred to acid wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase were separated, the polymer solution phase was collected. Ion-exchanged water was added to the recovered 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 collected and dried under reduced pressure at 90° C. for 12 hours to add 0 to 3 epoxy groups to the ends of the molecular chains. A modified polymer composition (6) containing Polymer composition (6) has a number average molecular weight Mn of 90,000, a terminal polyfunctional group-modified polymer (A) containing 3 epoxy groups at the molecular chain ends of 47% by mass, and 2 at the molecular chain ends. 21% by mass of the modified polymer (B) containing an epoxy group, 19% by mass of the modified polymer (C) containing one epoxy group at the molecular chain end, and a modified polymer (D ) was 13 mass %, and the vinyl content of the polymer composition (6) was 9 mol %.

[Comparative Example 1]
(Step (1))
A sufficiently dried 2 L autoclave was purged with nitrogen, charged with 623 g of cyclohexane and 16.6 g of sec-butyllithium (10.5% by mass cyclohexane solution), heated to 50°C, and then polymerized at 50°C under stirring conditions. 431 g of butadiene was successively added at 20 ml/5 minutes while controlling so that After the addition of butadiene, the mixture was heated for 1 hour to complete the polymerization, thereby obtaining a polymerization solution containing an active terminal polymer (α).

(Step (2))
24.0 g of epichlorohydrin was added to the polymerization solution obtained in step (1) to introduce an epoxy group at the polymerization terminal. An aqueous citric acid solution was added to the resulting polymer solution and stirred to acid wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase were separated, the polymer solution phase was collected. Ion-exchanged water was added to the recovered polymer solution and stirred to wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase were separated, the polymer solution phase was collected and dried under reduced pressure at 90°C for 12 hours to obtain a polymer composition (7). The polymer composition (7) has a number average molecular weight Mn of 38,000, a modified polymer containing one epoxy group at the molecular chain end of 65% by mass, and an unmodified polymer of 35% by mass. The vinyl content of polymer composition (7) was 10 mol %.

[Comparative Example 2]
(Step (1))
A sufficiently dried 2 L autoclave was purged with nitrogen, charged with 405 g of cyclohexane and 13.1 g of sec-butyllithium (10.5% by mass cyclohexane solution), heated to 50°C, and then under stirring conditions, the polymerization temperature was reduced to 50°C. 306 g of butadiene was successively added at 20 ml/5 minutes while controlling so that the After the addition of butadiene, the mixture was heated for 1 hour to complete the polymerization, thereby obtaining a polymerization solution containing an active terminal polymer (α).

(Step (2))
3.1 g of 1,2,7,8-diepoxyoctane was added to the polymerization solution obtained in step (1) to introduce an epoxy group at the polymerization terminal. An aqueous citric acid solution was added to the resulting polymer solution and stirred to acid wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase were separated, the polymer solution phase was collected. Ion-exchanged water was added to the recovered polymer solution and stirred to wash the polymer solution. After confirming that the polymer solution phase and the aqueous phase were separated, the polymer solution phase was collected and dried under reduced pressure at 90°C for 12 hours to obtain a polymer composition (8). The polymer composition (8) has a number average molecular weight Mn of 33,000, a modified polymer containing one epoxy group at the molecular chain end of 66% by mass, and an unmodified polymer of 34% by mass. The vinyl content of polymer composition (8) was 9 mol %.

Table 1 shows the physical properties of the polymer compositions obtained in Examples 1-6 and Comparative Examples 1-2.

From Table 1, as shown in Examples 1, 4, 5, and 6, a Lewis acid compound (a) and a Lewis base compound (b) coexist to control the association of anions while controlling the reactivity. It can be seen that a polymer composition containing a polyfunctionally modified terminal polymer (A) having three epoxy groups can be obtained at a content rate (high yield). It is also found that the polymer composition has excellent reactivity (adhesion to different materials).
In Examples 2 and 3, although the content of the terminal polyfunctional modified polymer (A) in the polymer composition was lower than in Examples 1, 4, 5 and 6, the modified polymer having three epoxy groups was used. It can be seen that the reactivity (adhesiveness to different materials) is excellent because the polymer composition contains the coalesced (A) and the (B) having two epoxy groups.
On the other hand, in the polymer composition, the terminal polyfunctional modified polymer (A) and the modified polymer (B) are not included at all, and the modified polymer (C) having only one epoxy group and the unmodified polymer In Comparative Examples 1 and 2, which contained only coalescence (E) and had a relatively high content of unmodified polymer (E), the polymer compositions were inferior in reactivity (adhesion to different materials). was

According to the production method of the present invention, a polymer composition containing a high content of a terminal polyfunctional group-modified polymer suitable for an adhesive for dissimilar materials can be easily obtained. In addition, the polymer composition containing the terminal polyfunctional group-modified polymer obtained in the present invention has excellent reactivity to various polar functional groups (e.g., excellent adhesion to different materials) and excellent storage stability (e.g., , heat resistance). Therefore, adhesive compositions containing such polymer compositions can be used for automobile interior and exterior parts, electrical and electronic parts, packaging materials, sporting goods, daily commodities, laminated materials, elastic materials, various rubber products, medical supplies, and various other materials. It can be effectively used in a wide range of fields such as adhesives and various coating primers.

Claims (8)

A polymer composition containing 3 to 80% by mass of a terminal polyfunctional group-modified polymer (A) represented by the following formula (I) and having a number average molecular weight of 3,000 or more and less than 100,000.

(In the above formula, P ¹ represents a polymer chain containing at least one monomer unit selected from the group consisting of a monomer unit derived from a conjugated diene and a monomer unit derived from an aromatic vinyl compound,
R ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be substituted with —O— or —S—; CH containing a tertiary carbon contained in a hydrogen group may be substituted with N;
R ² , R ³ and R ⁴ are a divalent hydrocarbon group having 1 to 10 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is substituted with —O— or —S— CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N;
R ⁵ is a divalent hydrocarbon group having 3 to 13 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be substituted with —O— or —S—; CH containing a tertiary carbon contained in the hydrogen group may be substituted with N, and the hydrogen contained in the hydrocarbon group may be substituted with a hydroxyl group;
R ⁶ , R ⁷ and R ⁸ are hydrogen or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O— or —S— and CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N. ) The claim further comprises at least one modified polymer (B) selected from the group consisting of a modified polymer (B1) represented by the following formula (II) and a modified polymer (B2) represented by the following formula (III). 2. The polymer composition according to 1.

(In the above formula, P ² , P ³ , P ⁴ and P ⁵ are at least one monomer unit selected from the group consisting of monomer units derived from conjugated dienes and monomer units derived from aromatic vinyl compounds. shows a polymer chain containing
R ⁹ and R ¹⁶ are divalent hydrocarbon groups having 1 to 20 carbon atoms, and -CH ₂ - contained in the hydrocarbon groups may be substituted with -O- or -S- , CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N;
R ¹⁰ , R ¹¹ , R ¹⁷ and R ¹⁸ are divalent hydrocarbon groups having 1 to 10 carbon atoms, and —CH ₂ — contained in the hydrocarbon groups is —O— or —S— optionally substituted, CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N;
R ¹² , R ¹³ , R ¹⁹ and R ²⁰ are divalent hydrocarbon groups having 3 to 13 carbon atoms, and —CH ₂ — contained in the hydrocarbon groups is —O— or —S— optionally substituted, CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N, and hydrogen contained in the hydrocarbon group may be substituted with a hydroxyl group;
R ¹⁴ , R ¹⁵ , R ²¹ and R ²² are hydrogen or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O— or — may be substituted with S—, and CH containing a tertiary carbon contained in the hydrocarbon group may be substituted with N; ) In a hydrocarbon solvent, an anionically polymerizable active metal or active metal compound is reacted with a monomer component containing at least one selected from conjugated dienes and aromatic vinyl compounds to produce an active terminal polymer (α). the process of
a step of mixing an active terminal polymer (α) with at least one selected from the group consisting of a Lewis acid compound (a) and a Lewis base compound (b), and the active terminal polymer (α) subjected to the mixing; Including the step of reacting with a polyfunctional compound having 3 or more epoxy groups,
A method for producing a polymer composition containing a terminal polyfunctional group-modified polymer. 4. The method for producing a polymer composition according to claim 3, wherein in the mixing step, the Lewis acid compound (a) and the Lewis base compound (b) are mixed. The polymer composition according to claim 3 or 4, wherein the Lewis acid compound (a) is at least one selected from the group consisting of a compound represented by the following formula (IV), an alkylzinc compound, and an alkylmagnesium compound. Production method.
^MR233 ₍ IV)
(In the above formula, M is a Group 13 element, and R ²³ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms.) 6. The method for producing a polymer composition according to claim 5, wherein the compound represented by formula (IV) is an alkylaluminum compound. The method for producing a polymer composition according to any one of claims 3 to 6, wherein the Lewis base compound (b) is at least one selected from the group consisting of ether compounds and amine compounds. The method for producing a polymer composition according to any one of claims 3 to 7, wherein the polyfunctional compound has four epoxy groups in the molecule.