JP7435477B2 - Method for producing terminally functionalized polymer, method for producing curable resin composition, and method for producing cured product - Google Patents

Description

The present invention relates to a method for producing a terminally functionalized polymer, a method for producing a curable resin composition, and a method for producing a cured product.

As a curable resin used for industrial purposes, a vinyl copolymer having a crosslinkable functional group obtained by radical polymerization of a vinyl monomer having a crosslinkable functional group is well known. Such vinyl copolymers are used as curable resin compositions, and are widely used, for example, in the field of cured products such as paints, adhesives, sealants, molding materials, and rubber sheets.

In a vinyl copolymer having a crosslinkable functional group obtained by general radical polymerization, the crosslinkable functional group is randomly introduced into the molecular chain. Therefore, a cured product obtained from a curable resin composition containing this vinyl copolymer may have insufficient physical properties because the molecular weight between crosslinking points is not uniform.

On the other hand, so-called telechelic polymers have crosslinkable functional groups at both ends of their molecular chains. Therefore, a cured product obtained from a curable resin composition containing a telechelic polymer has a uniform molecular weight between crosslinking points, and therefore has excellent physical properties.

Patent Document 1 discloses a curable resin composition containing a telechelic polymer having crosslinkable silyl groups at both ends, obtained by an atom transfer radical polymerization method (ATRP method), which is living radical polymerization. This telechelic polymer also has a narrow molecular weight distribution, and it is described that the tensile properties of its cured product are superior to those of cured products made of general radical copolymers.

Here, examples of living radical polymerization include, in addition to the ATRP method, a reversible addition-fragmentation chain transfer polymerization method (RAFT method), a nitroxy radical method (NMP method), a polymerization method using an organic tellurium compound (TERP method), etc. Various polymerization methods are known.

Among these, the RAFT method has attracted attention as a metal-free polymerization method that can be applied to the widest range of vinyl monomers, and methods for producing telechelic polymers using the RAFT method have been developed.

Non-Patent Document 1 discloses a method for producing a telechelic polymer by a RAFT method using a monofunctional trithiocarbonate-based RAFT agent having a crosslinkable functional group.

Additionally, in Non-Patent Document 2, a nucleophile, a radical generator, etc. are applied to the terminal thiocarbonylthio group of a RAFT polymer obtained using a monofunctional RAFT agent to convert the terminal structure. A method is disclosed.

Japanese Patent Application Publication No. 11-130931

Macromolecules 2005, 38, 9518-9525 Macromolecules 2007, 40, 4446-4455

However, the method described in Non-Patent Document 1 lacks versatility because it is necessary to prepare a monofunctional RAFT agent having a desired crosslinkable functional group in advance. Further, according to studies by the present inventors, there was a problem in that a cured product of a curable resin composition containing a telechelic polymer obtained using the RAFT agent had poor heat resistance at high temperatures.

On the other hand, in the method described in Non-Patent Document 2, without producing in advance a monofunctional RAFT agent having a desired crosslinkable functional group as described in Non-Patent Document 1, By reacting the group with a nucleophile, it can be converted to a mercapto group (-SH). However, this method is limited to the production of polymers having a mercapto group at one end, and the problem is that it is impossible to obtain polymers in which two or more terminals are functionalized (for example, telechelic polymers, etc.).

In view of the above problems, an object of the present invention is to provide a new method for producing a polymer (including a telechelic polymer) in which two or more terminals are functionalized using the RAFT method. The present invention also provides a method for producing a curable resin composition containing the terminally functionalized polymer obtained by the production method, and a method for producing a cured product by curing the curable resin composition. That is the issue.

In order to solve the above problems, the present inventor conducted intensive studies and discovered that RAFT polymerization was carried out using a bifunctional RAFT agent, and a thiocarbonylthio group (-C(=S)-S We discovered that by synthesizing a polymer with -) and then carrying out a specific terminal conversion reaction, it is possible to produce a telechelic polymer with desired crosslinkable functional groups at both ends, regardless of the structure of the RAFT agent. Ta.
Furthermore, it has been found that by using a trifunctional or more functional RAFT agent as a raw material and treating it in the same manner, it is also possible to produce a polymer having three or more crosslinkable functional groups at the terminals.
Furthermore, it has been found that a cured product obtained by curing the curable resin composition containing the polymer functionalized at two or more terminals obtained above has excellent heat resistance at high temperatures.
Based on this knowledge, the present invention was completed by further investigation.

（式中、Ｚは、－Ｒ^Ａ、－ＳＲ^Ａ、－ＯＲ^Ａ、又は－ＮＲ^ＡＲ^Ｂで示される基であり、Ｒ^Ａ及びＲ^Ｂは、同一又は異なって、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいヘテロアリール基、又は置換基を有していてもよいアラルキル基を示す。Ｚが－ＮＲ^ＡＲ^Ｂで示される基のとき、Ｒ^Ａ及びＲ^Ｂは互いに結合して隣接する窒素原子と共に環を形成していてもよく、当該環は置換基を有していてもよい。）
で表される基を有するＲＡＦＴ剤である、前記［１］に記載の製造方法。
［３］前記ＲＡＦＴ剤が、式（１）：

（式中、Ｒは、酸素原子、窒素原子及び硫黄原子からなる群より選択される１種以上のヘテロ原子を有していてもよいｎ価の有機基を示し、ｎは２以上の整数を示し、Ｚは前記に同じ。２以上のＺは、同一又は異なっていてもよい。）
で表される化合物又はその塩である、前記［２］に記載の製造方法。
［４］前記Ｒが、－Ｓ－Ｃ（＝Ｓ）－Ｚで示される基と結合する炭素原子を有するｎ価の有機基である、前記［３］に記載の製造方法。
［５］前記ＲＡＦＴ剤が、式（１Ａ）～式（１Ｃ）：

（式中、環Ａは、置換基を有していてもよい芳香環又は置換基を有していてもよいヘテロ芳香環を示し、Ｒ^ａ及びＲ^ｂは、同一又は異なって、水素原子、アルキル基、又はシアノ基を示し、ｐは２以上の整数を示し、ｑは０又は１を示し、ｒは１以上の整数を示す。Ｒ^Ａ及びＺは前記に同じ。２以上のＲ^Ａは、同一又は異なっていてもよく、２以上のＺは、同一又は異なっていてもよい。）
からなる群より選択される１種である、前記［２］～［４］のいずれかに記載の製造方法。
［６］前記ビニル系単量体が、式（２）：

（式中、Ｕ及びＷは、同一又は異なって、－ＣＯ_２Ｈ、－ＣＯ_２Ｒ^１、－Ｃ（＝Ｏ）Ｒ^１、－Ｃ（＝Ｓ）Ｒ^１、－Ｃ（＝Ｓ）ＯＲ^１、－Ｃ（＝Ｏ）ＳＲ^１、－Ｃ（＝Ｏ）ＮＨ_２、－Ｃ（＝Ｏ）ＮＨＲ^１、－Ｃ（＝Ｏ）Ｎ（Ｒ^１）_２、水素原子、ハロゲン原子、又は置換基を有していてもよいアルキル基を示す。或いは、Ｕ及びＷが互いに結合して、隣接する－Ｃ＝Ｃ－と共に環を形成していてもよく、当該環は置換基を有していてもよい。
Ｖは、水素原子、Ｒ^１、－ＣＯ_２Ｈ、－ＣＯ_２Ｒ^１、－Ｃ（＝Ｏ）Ｒ^１、－Ｃ（＝Ｓ）Ｒ^１、－Ｃ（＝Ｓ）ＯＲ^１、－Ｃ（＝Ｏ）ＳＲ^１、－Ｃ（＝Ｏ）ＮＨ_２、－Ｃ（＝Ｏ）ＮＨＲ^１、－Ｃ（＝Ｏ）Ｎ（Ｒ^１）_２、－ＯＲ^１、－ＳＲ^１、－ＯＣ（＝Ｏ）Ｒ^１、－ＳＣ（＝Ｏ）Ｒ^１、又は－ＯＣ（＝Ｓ）Ｒ^１を示す。
Ｒ^１は、同一又は異なって、置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、置換基を有していてもよいアリール基、置換基を有していてもよいヘテロアリール基、置換基を有していてもよいシクロアルキル基、置換基を有していてもよいヘテロシクロアルキル基、置換基を有していてもよいアラルキル基、置換基を有していてもよいヘテロアリールアルキル基、又は置換基を有していてもよいポリマー鎖を示す。）
で表される化合物又はその塩である、前記［１］～［５］のいずれかに記載の製造方法。
［７］前記求核剤が、第１級アミン化合物及び第２級アミン化合物からなる群より選択される少なくとも１種である、前記［１］～［６］のいずれかに記載の製造方法。
［８］前記メルカプト基と反応性を有する化合物が、（メタ）アクリロイル基含有化合物、エポキシ基含有化合物、イソシアネート基含有化合物、及びアルケニル基含有化合物からなる群より選択される少なくとも１種である、前記［１］～［７］のいずれかに記載の製造方法。
［９］前記メルカプト基と反応性を有する化合物が、架橋性官能基を有する、前記［８］に記載の製造方法。
［１０］前記架橋性官能基が、水酸基、カルボキシル基、（メタ）アクリロイル基、エポキシ基、及び架橋性シリル基からなる群より選択される少なくとも１種である、前記［９］に記載の製造方法。
［１１］硬化性樹脂組成物の製造方法であって、前記［１］～［１０］のいずれかに記載の製造方法で得られた２以上の末端が官能基化されたポリマー、硬化触媒、及び必要に応じ硬化剤を混合する工程を含む、製造方法。
［１２］硬化物の製造方法であって、前記［１１］に記載の製造方法で得られた硬化性樹脂組成物を硬化する工程を含む、製造方法。 That is, the present invention provides a method for producing a terminally functionalized polymer, a method for producing a curable resin composition, a method for producing a cured product, etc. shown below.
[1] A method for producing a polymer in which two or more terminals are functionalized, the method comprising:
(i) A polymer (P1) having two or more thiocarbonylthio groups is obtained by polymerizing a vinyl monomer using a polymerization control agent (especially a RAFT agent) having two or more thiocarbonylthio groups. The process of obtaining
(ii) a step of reacting the polymer (P1) obtained in step (i) with a nucleophile to obtain a polymer (P2) having two or more mercapto groups (-SH); and (iii) ) The polymer (P2) obtained in step (ii) is reacted with a compound that is reactive with the mercapto group to produce a polymer (P3) in which two or more terminals are functionalized. A manufacturing method that includes a process.
[2] The polymerization control agent having two or more thiocarbonylthio groups has two or more formula (1a) in the molecule:

(In the formula, Z is a group represented by -R ^A , -SR ^A , -OR ^A , or -NR ^A R ^B , and R ^A and R ^B are the same or different and have a substituent. represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or an aralkyl group which may have a substituent.Z is -NR In the case of a group represented by ^A R ^B , R ^A and R ^B may be bonded to each other to form a ring with the adjacent nitrogen atom, and the ring may have a substituent.)
The manufacturing method according to the above [1], which is a RAFT agent having a group represented by the following.
[3] The RAFT agent has formula (1):

(In the formula, R represents an n-valent organic group which may have one or more heteroatoms selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom, and n represents an integer of 2 or more. (Z is the same as above. Two or more Z's may be the same or different.)
The manufacturing method according to the above [2], which is a compound represented by or a salt thereof.
[4] The production method according to [3] above, wherein the R is an n-valent organic group having a carbon atom bonded to a group represented by -SC(=S)-Z.
[5] The RAFT agent has formulas (1A) to (1C):

(In the formula, ring A represents an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent, and R ^a and R ^b are the same or different and are a hydrogen atom, It represents an alkyl group or a cyano group, p represents an integer of 2 or more, q represents 0 or 1, and r represents an integer of 1 or more. R ^A and Z are the same as above. R ^A of 2 or more , may be the same or different, and two or more Z's may be the same or different.)
The manufacturing method according to any one of [2] to [4] above, which is one selected from the group consisting of.
[6] The vinyl monomer has formula (2):

(In the formula, U and W are the same or different, -CO ₂ H, -CO ₂ R ¹ , -C(=O)R ¹ , -C(=S)R ¹ , -C(=S)OR ¹ , -C(=O)SR ¹ , -C(=O)NH ₂ , -C(=O)NHR ¹ , -C(=O)N(R ¹ ) ₂ , hydrogen atom, halogen atom, or substitution Indicates an alkyl group that may have a group. Alternatively, U and W may be bonded to each other to form a ring with the adjacent -C=C-, and the ring has a substituent. It's okay.
V is a hydrogen atom, R ¹ , -CO ₂ H, -CO ₂ R ¹ , -C(=O)R ¹ , -C(=S)R ¹ , -C(=S)OR ¹ , -C( =O)SR ¹ , -C(=O)NH ₂ , -C(=O)NHR ¹ , -C(=O)N(R ¹ ) ₂ , -OR ¹ , -SR ¹ , -OC(=O )R ¹ , -SC(=O)R ¹ , or -OC(=S)R ¹ .
R ¹ is the same or different and is an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, or an alkyl group that may have a substituent; Aryl group which may have a substituent, heteroaryl group which may have a substituent, cycloalkyl group which may have a substituent, heterocycloalkyl group which may have a substituent, Indicates an aralkyl group that may have an optional aralkyl group, a heteroarylalkyl group that may have a substituent, or a polymer chain that may have a substituent. )
The manufacturing method according to any one of [1] to [5] above, which is a compound represented by or a salt thereof.
[7] The production method according to any one of [1] to [6] above, wherein the nucleophile is at least one selected from the group consisting of primary amine compounds and secondary amine compounds.
[8] The compound having reactivity with the mercapto group is at least one selected from the group consisting of (meth)acryloyl group-containing compounds, epoxy group-containing compounds, isocyanate group-containing compounds, and alkenyl group-containing compounds. The manufacturing method according to any one of [1] to [7] above.
[9] The production method according to [8] above, wherein the compound reactive with the mercapto group has a crosslinkable functional group.
[10] The production according to [9] above, wherein the crosslinkable functional group is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a (meth)acryloyl group, an epoxy group, and a crosslinkable silyl group. Method.
[11] A method for producing a curable resin composition, comprising: a polymer functionalized at two or more terminals obtained by the production method according to any one of [1] to [10], a curing catalyst, and a step of mixing a curing agent as necessary.
[12] A method for producing a cured product, comprising a step of curing the curable resin composition obtained by the production method according to [11] above.

According to the production method of the present invention, a polymer having thiocarbonylthio groups at multiple terminals is produced by RAFT polymerization using a multifunctional RAFT agent (RAFT agent having two or more thiocarbonylthio groups). After synthesizing, by performing a specific terminal conversion reaction, it is possible to produce a desired polymer in which a plurality of terminals are functionalized with a crosslinkable functional group or the like. According to this production method, a polymer having two or more terminals functionalized can be produced without depending on the structure of the RAFT agent as a raw material. Further, by curing the functionalized polymer, a cured product having excellent heat resistance at high temperatures can be obtained.

The present invention will be explained in detail below.

1. Method for producing a polymer (P3) functionalized at two or more terminals The method for producing a polymer functionalized at two or more terminals of the present invention is as follows:
(i) A polymer (P1) having two or more thiocarbonylthio groups is obtained by polymerizing a vinyl monomer using a polymerization control agent (especially a RAFT agent) having two or more thiocarbonylthio groups. The process of obtaining
(ii) a step of reacting the polymer (P1) obtained in step (i) with a nucleophile to obtain a polymer (P2) having two or more mercapto groups (-SH); and (iii) ) The polymer (P2) obtained in step (ii) is reacted with a compound that is reactive with the mercapto group to produce a polymer (P3) in which two or more terminals are functionalized. It is characterized by having a process. Steps (i) to (iii) will be explained below.

Process (i):
In step (i), vinyl monomers are polymerized (living radical polymerization) using a polymerization control agent having two or more thiocarbonylthio groups in the presence of a polymerization initiator to form two or more thiocarbonylthio groups. A polymer (P1) having the following is obtained. This reaction can be carried out in the presence or absence of a solvent.

When using a solvent, a known solvent commonly used in polymerization reactions can be used. Examples include nitrile solvents, aromatic hydrocarbon solvents, ether solvents, ketone solvents, ester solvents, orthoester solvents, dimethylformamide, dimethyl sulfoxide, alcohol, and water.
Specific examples of nitrile solvents include acetonitrile, isobutyronitrile, and benzonitrile.
Specific examples of aromatic hydrocarbon solvents include benzene, toluene, and xylene.
Specific examples of ether solvents include anisole, dibutyl ether, and tetrahydrofuran.
Specific examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
Specific examples of ester solvents include methyl acetate, ethyl acetate, propyl acetate, and butyl acetate.
Specific examples of orthoester solvents include trimethyl orthoformate, triethyl orthoformate, tri(n-propyl) orthoformate, tri(isopropyl) orthoformate, trimethyl orthoacetate, triethyl orthoacetate, triethyl orthopropionate, and n-orthoformate. Examples include trimethyl butyrate and trimethyl orthoisobutyrate.
One type of solvent or a combination of two or more types can be used.
This reaction may be carried out in a manner such as bulk polymerization without using a solvent.

The vinyl monomer used for polymerization is not particularly limited as long as it is capable of living radical polymerization (particularly RAFT polymerization), and examples thereof include the compound represented by formula (2) or a salt thereof. The vinyl monomer (particularly the compound represented by formula (2) or a salt thereof) may contain one or more types of monomers.

In the above formula (2), U and W are the same or different and are -CO ₂ H, -CO ₂ R ¹ , -C(=O)R ¹ , -C(=S)R ¹ , -C( =S)OR ¹ , -C(=O)SR ¹ , -C(=O)NH ₂ , -C(=O)NHR ¹ , -C(=O)N(R ¹ ) ₂ , hydrogen atom, halogen Indicates an atom or an alkyl group that may have a substituent. Alternatively, U and W may be bonded to each other to form a ring with adjacent -C=C-, and the ring may have a substituent.

（式中、記号は前記に同じ。）
当該環が有していてもよい置換基としては、水酸基、－ＣＯ_２Ｈ、－ＣＯ_２Ｒ^１、－Ｃ（＝Ｏ）Ｒ^１、－Ｃ（＝Ｓ）Ｒ^１、－ＣＳ（＝Ｏ）Ｒ^１、－Ｃ（＝Ｏ）ＳＲ^１、－ＣＮ、－Ｃ（＝Ｏ）ＮＨ_２、－Ｃ（＝Ｏ）ＮＨＲ¹、－Ｃ（＝Ｏ）ＮＲ^１ _２、－ＯＲ^１、－ＳＲ^１、－ＯＣ（＝Ｏ）Ｒ^１、－ＳＣ（＝Ｏ）Ｒ^１、－ＯＣ（＝Ｓ）Ｒ¹等が挙げられる。 When U and W combine with each other to form a ring with adjacent -C=C-, examples of the ring include cyclic esters (lactone rings), cyclic acid anhydrides, and cyclic imides. Examples of the compound represented by formula (2) having the ring include the following compounds or salts thereof. The ring may have a substituent.

(In the formula, the symbols are the same as above.)
Examples of substituents that the ring may have include a hydroxyl group, -CO ₂ H, -CO ₂ R ¹ , -C(=O)R ¹ , -C(=S)R ¹ , -CS(=O )R ¹ , -C(=O)SR ¹ , -CN, -C(=O)NH ₂ , -C(=O)NHR ¹ , -C(=O)NR ¹ ₂ , -OR ¹ , -SR ¹ , -OC(=O)R ¹ , -SC(=O)R ¹ , -OC(=S)R ¹ and the like.

V is a hydrogen atom, R ¹ , -CO ₂ H, -CO ₂ R ¹ , -C(=O)R ¹ , -C(=S)R ¹ , -C(=S)OR ¹ , -C( =O)SR ¹ , -C(=O)NH ₂ , -C(=O)NHR ¹ , -C(=O)N(R ¹ ) ₂ , -OR ¹ , -SR ¹ , -OC(=O )R ¹ , -SC(=O)R ¹ , or -OC(=S)R ¹ .

R ¹ is the same or different and is an alkyl group that may have a substituent (especially a C1 to C20 alkyl group), an alkenyl group that may have a substituent (especially a C2 to C20 alkenyl group) , an alkynyl group that may have a substituent (especially a C2 to C20 alkynyl group), an aryl group that may have a substituent (especially a C6 to C10 aryl group), an alkynyl group that may have a substituent (especially a C6 to C10 aryl group), a heteroaryl group (especially a C3 to C18 heteroaryl group) that may have a substituent, a cycloalkyl group that may have a substituent (especially a C3 to C18 cycloalkyl group), a heterocyclo that may have a substituent Alkyl groups (especially C2-C18 heterocycloalkyl groups), aralkyl groups that may have substituents (especially C7-C22 aralkyl groups), heteroarylalkyl groups that may have substituents (especially , C4-C22 heteroarylalkyl group), or a polymer chain that may have a substituent (eg, polyalkylene oxide, polyarylene ether, etc.).

One embodiment of R ¹ includes a C1 to C6 alkyl group which may have a substituent, a C6 to C20 alkyl group which may have a substituent, and the like.

Examples of the substituents that R ¹ may have include epoxy groups, hydroxyl groups, alkyl groups (C1 to C6 alkyl groups, etc.), aryl groups (phenyl groups, tolyl groups, etc.), and alkoxy groups (C1 to C6 alkyl groups, etc.). alkoxy groups, etc.), formyl groups, alkylcarbonyl groups ((C1-C6 alkyl) carbonyl groups, etc.), arylcarbonyl groups (benzoyl groups, etc.), carboxyl groups, sulfonic acid groups, alkoxycarbonyl groups ((C1-C6 alkoxy) carbonyl ), aryloxycarbonyl groups (phenoxycarbonyl groups, etc.), isocyanate groups, cyano groups, crosslinkable silyl groups, halogen atoms, amino groups, and the like.

Examples of crosslinkable silyl groups include trialkoxysilyl groups (triC1-C6 alkoxysilyl groups, etc.), alkyl(dialkoxy)silyl groups (C1-C6 alkyl(di-C1-C6 alkoxy)silyl groups, etc.), dialkyl( alkoxy)silyl group (diC1-C6 alkyl (C1-C6 alkoxy)silyl group, etc.), and the like.

Examples of the compound represented by formula (2) or a salt thereof include maleic anhydride, N-alkylmaleimide, N-arylmaleimide, dialkyl fumarate, (meth)acrylic ester (the ester has a crosslinkable silyl ), (meth)acrylic acid or a salt thereof, styrene, (meth)acrylamide, (meth)acrylonitrile, and mixtures of these monomers.

Specific examples of the compound represented by formula (2) or its salt include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylate. 2-ethylhexyl acid, isobornyl (meth)acrylate, (meth)acrylic acid, benzyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylonitrile, alpha-methylstyrene, styrene, glycidyl (meth)acrylate , 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylamino (meth)acrylate Ethyl, triethylene glycol (meth)acrylate, itaconic anhydride, itaconic acid, (meth)acrylamide, N-methyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-tert-butyl (meth) Acrylamide, N-butyl (meth)acrylamide, N-(hydroxymethyl)(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N-tert-butyl(meth)allylamide, N-n- Butyl (meth)allylamide, N-(hydroxymethyl)(meth)allylamide, N-(2-hydroxyethyl)(meth)allylamide, vinyl benzoate, diethylaminostyrene, vinyl alpha-methylbenzoate, diethylamino alpha-methylstyrene, p-vinylbenzenesulfonic acid, p-vinylbenzenesulfonic acid sodium salt, trimethoxysilylpropyl (meth)acrylate, triethoxysilylpropyl (meth)acrylate, triisopropoxysilylpropyl (meth)acrylate, (meth)acrylate Tributoxysilylpropyl acrylate, dimethoxymethylsilylpropyl (meth)acrylate, diethoxymethylsilylpropyl (meth)acrylate, diisopropoxymethylsilylpropyl (meth)acrylate, dibutoxymethylsilylpropyl (meth)acrylate , vinyl acetate, butyl butyrate, vinyl benzoate, vinyl chloride, vinyl fluoride, vinyl bromide, maleic anhydride, N-phenylmaleimide, N-butylmaleimide, N-vinylpyrrolidone, N-vinylcarbazole, and the like. In addition, when a group contained in each compound includes an isomer, the group is interpreted as including all isomers.

Preferred examples of the compound represented by formula (2) include (meth)acrylic acid, C1-C20 alkyl (meth)acrylate such as tetradecyl (meth)acrylate; trimethoxysilylpropyl (meth)acrylate, (meth)acrylate; Trialkoxysilylpropyl (meth)acrylate such as triethoxysilylpropyl acrylate, triisopropoxysilylpropyl (meth)acrylate, tributoxysilylpropyl (meth)acrylate; dimethoxymethylsilylpropyl (meth)acrylate, ( Di(C1 to C3 alkoxy)methylsilylpropyl (meth)acrylate, such as diethoxymethylsilylpropyl (meth)acrylate, diisopropoxymethylsilylpropyl (meth)acrylate, dibutoxymethylsilylpropyl (meth)acrylate, etc. can be mentioned.

The salt of the compound represented by formula (2) is not particularly limited as long as it does not adversely affect the reaction of the present invention. For example, salts with alkali metals such as lithium, sodium, and potassium; salts with alkaline earth metals such as magnesium and calcium; salts with amines such as ammonia, monoalkylamines, dialkylamines, and trialkylamines; tetrabutylammonium Examples include salts with tetraalkylammonium such as .

The vinyl monomer used in the present invention may contain the compound represented by the above formula (2) or a salt thereof, and other monomers as necessary.

The polymerization initiator is not particularly limited as long as it generates free radicals that are normally used in RAFT polymerization. Examples include thermal polymerization initiators (peroxides, peroxyesters, azo compounds, etc.); photopolymerization initiators; redox polymerization initiators, and the like. Alternatively, free radical generating means using high-energy radiation such as electron beams, X-rays, and gamma rays may be used.

Examples of the thermal polymerization initiator include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-cyanobutane), dimethyl 2,2'-azobis(isobutyrate), 4,4'- Azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexanecarbonitrile) (ACHN), 2,2'-azobis(2-methylbutyronitrile) (ABN-E), 2-(t-butylazo )-2-cyanopropane, 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2,2'-azobis[2-methyl -N-(2-hydroxyethyl)propionamide] (AMHP), 4,4'-azobis(4-cyanopentanoic acid) (ACPA), 2,2'-azobis(5-hydroxy-2methylpentanenitrile) ( AHPN), 2,2'-azobis(N,N'-dimethyleneisobutyramidine) dihydrochloride, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis(N,N'- dimethyleneisobutyramidine), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2,2'-azobis{2-methyl- N-[1,1-bis(hydroxymethyl)-2-ethyl]propionamide}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis (isobutyramide) dihydrate, 2,2'-azobis(2,2,4-trimethylpentane), 2,2'-azobis(2-methylpropane), t-butylperoxyacetate, t-butylperoxyacetate Oxybenzoate, t-butylperoxyneodecanoate, t-butylperoxyisobutyrate, t-amylperoxypivalate, t-butylperoxypivalate, diisopropylperoxydicarbonate, dicyclohexylperoxydicarbonate, Dicumyl peroxide, dibenzoyl peroxide (BPO), dilaurolyl peroxide (LPO), potassium peroxydisulfate, ammonium peroxydisulfate, tert-butyl 2-ethylhexane peroxoate, di-t -Butyl hyponitrite, dicumyl hyponitrite, etc. One or a combination of two or more of these can be selected.

As photopolymerization initiators, for example, benzene derivatives, benzophenones, acylphosphine oxides and photoredox systems are selected.

Examples of redox polymerization initiators include the following oxidants (potassium, peroxydisulfate, hydrogen peroxide, t-butyl hydroperoxide, etc.) and reductants (iron (II), titanium (III), thio (potassium sulfate, potassium hydrogen sulfite, etc.).

Other suitable polymerization initiators and methods may be those known in the art.

Examples of polymerization initiators that are easily soluble in hydrophilic solvents include 4,4-azobis(cyanovaleric acid), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)- 2-hydroxyethyl]propionamide}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(N,N'-dimethyleneisobutyramidine), 2,2'-azobis(N,N'-dimethyleneisobutyramidine) dihydrochloride, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis{2-methyl-N-[1 , 1-bis(hydroxymethyl)-2-ethyl]propionamide}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(isobutyramide) Examples include, but are not limited to, dihydrates and derivatives thereof.

Polymerization initiators that are easily soluble in hydrophobic solvents include azo compounds, such as the known substance 2,2'-azobisisobutyronitrile.
Other suitable initiator compounds include acyl peroxides such as acetyl peroxide, benzoyl peroxide, and alkyl peroxides such as t-butyl α-cumyl peroxide. Hydroperoxides such as t-butyl hydroperoxide and cumyl hydroperoxide can also be used.

The amount of the polymerization initiator to be used can be appropriately set depending on various conditions such as the type and amount of the vinyl monomer and is not particularly limited. For example, in order to obtain a polymer with a smaller molecular weight distribution, the amount of the radical polymerization initiator used per mole of the polymerization control agent (especially the RAFT agent) having two or more thiocarbonylthio groups is 0.5 mole or less. The amount is preferably 0.2 mol or less, and more preferably 0.2 mol or less. In addition, from the viewpoint of stably performing the polymerization reaction, the amount of the radical polymerization initiator to be used per 1 mol of the polymerization control agent is preferably 0.001 mol or more, more preferably 0.005 mol or more. . Therefore, the amount of the radical polymerization initiator to be used per mole of the polymerization control agent is preferably in the range of 0.001 mol or more and 0.5 mol or less, and more preferably in the range of 0.005 mol or more and 0.2 mol or less.

The reaction temperature during the polymerization reaction by the RAFT method is preferably 30°C or more and 120°C or less, more preferably 40°C or more and 110°C or less, and still more preferably 50°C or more and 100°C or less. When the reaction temperature is 30°C or higher, the polymerization reaction can proceed smoothly. On the other hand, if the reaction temperature is 120° C. or lower, side reactions can be suppressed and restrictions regarding usable initiators and solvents are relaxed.

（式中、Ｚは、－Ｒ^Ａ、－ＳＲ^Ａ、－ＯＲ^Ａ、又は－ＮＲ^ＡＲ^Ｂで示される基であり、Ｒ^Ａ及びＲ^Ｂは、同一又は異なって、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいヘテロアリール基、又は置換基を有していてもよいアラルキル基を示す。Ｚが－ＮＲ^ＡＲ^Ｂで示される基のとき、Ｒ^Ａ及びＲ^Ｂは互いに結合して隣接する窒素原子と共に環を形成していてもよく、当該環は置換基を有していてもよい。）
で表される基を有するＲＡＦＴ剤が挙げられる。 As a polymerization control agent having two or more thiocarbonylthio groups, for example, two or more of formula (1a) in the molecule:

(In the formula, Z is a group represented by -R ^A , -SR ^A , -OR ^A , or -NR ^A R ^B , and R ^A and R ^B are the same or different and have a substituent. represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or an aralkyl group which may have a substituent.Z is -NR In the case of a group represented by ^A R ^B , R ^A and R ^B may be bonded to each other to form a ring with the adjacent nitrogen atom, and the ring may have a substituent.)
A RAFT agent having a group represented by:

The "alkyl group" of the "alkyl group which may have a substituent" represented by R ^A and R ^B includes straight chain or branched C1 to C20 (furthermore C1 to C15, even more C1 to C10, especially C1 to C10). Examples include C1 to C6) alkyl groups. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, Examples include undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, lauryl group, and stearyl group. When the "alkyl group" has a substituent, examples of the substituent include an epoxy group, a hydroxyl group, an alkoxy group, an acyl group, an acyloxy group, a formyl group, an alkylcarbonyl group, a carboxyl group, a sulfonic acid group, and an alkoxycarbonyl group. , an aryloxycarbonyl group, an isocyanate group, a cyano group, a silyl group, a halogen atom, an amino group, and the like. The "alkyl group" may have one or more substituents selected from these substituents.

The "aryl group" in the "aryl group which may have a substituent" represented by R ^A and R ^B means a monovalent group obtained by removing one hydrogen atom from an aromatic hydrocarbon, such as , a C6 to C20 aryl group having a single ring or two or more rings condensed together. Examples of the aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group, and 1-anthracenyl group. When the "aryl group" has a substituent, examples of the substituent include an epoxy group, a hydroxyl group, an alkoxy group, an acyl group, an acyloxy group, a formyl group, an alkylcarbonyl group, a carboxyl group, a sulfonic acid group, and an alkoxycarbonyl group. , an aryloxycarbonyl group, an isocyanate group, a cyano group, a silyl group, a halogen atom, an amino group, and the like. The "aryl group" may have one or more substituents selected from these substituents.

The "heteroaryl group" of the "heteroaryl group which may have a substituent" represented by R ^A and R ^B means a monovalent group obtained by removing one hydrogen atom from a heteroaromatic hydrocarbon. Examples include C5 to C20 heteroaryl groups having a single ring or two or more fused rings. Examples of the heteroaryl group include a pyridyl group, a quinolyl group, an isoquinolyl group, and a pyrimidinyl group. When the "heteroaryl group" has a substituent, examples of the substituent include an epoxy group, a hydroxyl group, an alkoxy group, an acyl group, an acyloxy group, a formyl group, an alkylcarbonyl group, a carboxyl group, a sulfonic acid group, and an alkoxycarbonyl group. group, aryloxycarbonyl group, isocyanate group, cyano group, silyl group, halogen atom, amino group and the like. The "heteroaryl group" may have one or more substituents selected from these substituents.

The "aralkyl group" of the "aralkyl group which may have a substituent" represented by R ^A and R ^B is one in which one or more hydrogen atoms on the above "alkyl group" is substituted with the above "aryl group". means base. When the "aralkyl group" has a substituent, examples of the substituent include those listed as the substituents for the "alkyl group" and "aryl group" above.

When Z is a group represented by -NR ^A R ^B , R ^A and R ^B are bonded to each other to form a ring with adjacent nitrogen atoms, and the nitrogen atoms constituting the ring are neutral and cationic. Examples include pyrrole ring, pyrazole ring, imidazole ring, pyrrolidine ring, piperidine ring, piperazine ring, pyridine ring, pyrimidine ring, pyrazine ring, oxazole ring, thiazole ring, morpholine ring, thiazine ring, triazole ring, etc. It will be done. When the ring has a substituent, examples of the substituent include an alkyl group (such as a C1 to C6 alkyl group), an oxo group (=O), an epoxy group, a hydroxyl group, an alkoxy group, an acyl group, an acyloxy group, and a formyl group. group, an alkylcarbonyl group, a carboxyl group, a sulfonic acid group, an alkoxycarbonyl group, an aryloxycarbonyl group, an isocyanate group, a cyano group, a silyl group, a halogen atom, an amino group, and the like. The ring may have one or more substituents selected from these substituents.

Z is preferably a group represented by -SR ^A.

（式中、Ｒは、酸素原子、窒素原子及び硫黄原子からなる群より選択される１種以上のヘテロ原子を有していてもよいｎ価の有機基を示し、ｎは２以上の整数を示し、Ｚは前記に同じ。２以上のＺは、同一又は異なっていてもよい。）
で表される化合物又はその塩が挙げられる。 As a specific example of the RAFT agent having two or more groups represented by formula (1a) in the molecule, formula (1):

(In the formula, R represents an n-valent organic group which may have one or more heteroatoms selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom, and n represents an integer of 2 or more. (Z is the same as above. Two or more Z's may be the same or different.)
Examples include compounds represented by: or salts thereof.

The n-valent organic group represented by R has a carbon atom bonded to the group represented by -S-C(=S)-Z (the group represented by formula (1a)), and the The atom can serve as a base point for a living radical polymerization (particularly RAFT polymerization) reaction with a vinyl monomer. From the viewpoint of reactivity in RAFT polymerization, the carbon atom is preferably bonded to an sp ² hybridized orbital carbon or an sp hybridized orbital carbon included in R. Examples of the sp ^2- hybridized orbital carbon or sp-hybridized orbital carbon include a carbon atom on an aromatic ring, a carbon atom on a heteroaromatic ring, a carbon atom of a carbonyl group (C=O), a carbon atom of a cyano group, etc. It will be done.

The RAFT agent represented by formula (1) can be prepared by a known method, for example, Macromolecules 2003, 36, 2273-2283, Macromolecules 2005, 38, 9518-9525, Macromolecules 2007, 40, 4446-4455, Macromolecules 2012, 45, 4205-4215, J. Am. Chem. Soc. 2008, 130, 12242-12243, J. Am. Chem. Soc. 2011, 133, 15707-15713, Patent No. 6174036, etc. can.

（式中、環Ａは、置換基を有していてもよい芳香環又は置換基を有していてもよいヘテロ芳香環を示し、Ｒ^ａ及びＲ^ｂは、同一又は異なって、水素原子、アルキル基、又はシアノ基を示し、ｐは２以上の整数を示し、ｑは０又は１を示し、ｒは１以上の整数を示す。Ｒ^Ａ及びＺは前記に同じ。２以上のＲ^Ａは、同一又は異なっていてもよく、２以上のＺは、同一又は異なっていてもよい。） Specific examples of embodiments of the RAFT agent represented by formula (1) include compounds represented by the following formulas (1A) to (1C) or salts thereof.

(In the formula, ring A represents an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent, and R ^a and R ^b are the same or different and are a hydrogen atom, It represents an alkyl group or a cyano group, p represents an integer of 2 or more, q represents 0 or 1, and r represents an integer of 1 or more. R ^A and Z are the same as above. R ^A of 2 or more , may be the same or different, and two or more Z's may be the same or different.)

The "aromatic ring" of the "aromatic ring which may have a substituent" represented by ring A includes a monocyclic ring or a C6 to C20 aromatic ring in which two or more rings are condensed. Examples of the aromatic ring include benzene, naphthalene, anthracene, and the like. When the "aromatic ring" has a substituent, examples of the substituent include an epoxy group, a hydroxyl group, an alkoxy group, an acyl group, an acyloxy group, a formyl group, an alkylcarbonyl group, a carboxyl group, a sulfonic acid group, and an alkoxycarbonyl group. , an aryloxycarbonyl group, an isocyanate group, a cyano group, a silyl group, a halogen atom, an amino group, and the like. The "aromatic ring" may have one or more substituents selected from these substituents.

The "hetero aromatic ring" of the "hetero aromatic ring which may have a substituent" represented by ring A is a monocyclic ring or a fused ring of two or more rings, consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. C6 to C20 heteroaromatic rings having at least one heteroatom selected from the group. Examples of the heteroaromatic ring include a pyridine ring, a pyrazine ring, a pyrimidine ring, and a thiazine ring. When the "heteroaromatic ring" has a substituent, examples of the substituent include an epoxy group, a hydroxyl group, an alkoxy group, an acyl group, an acyloxy group, a formyl group, an alkylcarbonyl group, a carboxyl group, a sulfonic acid group, and an alkoxycarbonyl group. group, aryloxycarbonyl group, isocyanate group, cyano group, silyl group, halogen atom, amino group and the like. The "heteroaromatic ring" may have one or more substituents selected from these substituents.

Examples of the "alkyl group" represented by R ^a and R ^b include linear or branched C1 to C10 (and C1 to C6, particularly C1 to C3) alkyl groups. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, dodecyl group, lauryl group, stearyl group, and the like.

p is preferably an integer of 2 to 10, more preferably an integer of 2 to 4. p is the same as the definition of n above. q is preferably 1. r is preferably an integer of 1 to 20, more preferably an integer of 1 to 10.

The amount of the polymerization control agent (RAFT agent) having two or more thiocarbonylthio groups is not particularly limited, and can be appropriately set depending on the target number average molecular weight (Mn).

This living radical polymerization reaction is preferably carried out under an oxygen-free inert gas atmosphere. The reaction temperature during the polymerization reaction is preferably 40°C or higher and 100°C or lower, more preferably 45°C or higher and 90°C or lower, and still more preferably 50°C or higher and 80°C or lower. When the reaction temperature is 40° C. or higher, the polymerization reaction can proceed smoothly. On the other hand, if the reaction temperature is 100° C. or lower, side reactions can be suppressed and restrictions regarding usable initiators and solvents are relaxed.

（式中、ｋは１以上を示し、他の記号は前記に同じ。） One form of step (i) can be expressed as follows. That is, by polymerizing the vinyl monomer represented by formula (2) using the RAFT agent represented by formula (1) in the presence of a polymerization initiator, the vinyl monomer represented by formula (3) is obtained. Polymer (P1) can be produced.

(In the formula, k represents 1 or more, and the other symbols are the same as above.)

k can be arbitrarily set depending on the degree of polymerization (target number average molecular weight (Mn)). U, V and W can be converted into the desired functional groups during step (i) or by additional steps.

After the reaction is completed, the polymer (P1) having two or more thiocarbonylthio groups can be obtained by isolation or purification using a known treatment method such as reprecipitation treatment or vacuum drying.

（式中、Ｙは脱離基を示し、他の記号は前記に同じ。） Note that the compounds represented by the above formulas (1A) to (1C) can all be produced by known methods. For example, it can be manufactured as follows.

(In the formula, Y represents a leaving group, and the other symbols are the same as above.)

Examples of the leaving group represented by Y include halogen atoms (chlorine atom, bromine atom, etc.).
The compound represented by formula (1A) can be produced by reacting the compound represented by formula (6), the compound represented by formula (7), and carbon disulfide (CS ₂ ). For example, it can be produced according to or analogously to Preparation Examples 1 and 2.

The compound represented by formula (1B) can be produced by subjecting the compound represented by formula (8) and the compound represented by formula (9) to a condensation reaction. For example, it can be produced according to or analogously to a known dehydration esterification reaction.

The compound represented by formula (1C) can be produced by subjecting the compound represented by formula (8) and the compound represented by formula (10) to a condensation reaction. For example, it can be produced according to or analogously to a known dehydration esterification reaction.

Step (ii):
In step (ii), the polymer (P1) obtained in step (i) is usually reacted with a nucleophile in the presence of a solvent to remove the thiocarbonyl group and form two or more mercapto groups ( -SH) to obtain a polymer (P2).

As the solvent, known solvents commonly used in nucleophilic reactions can be used. Examples include nitrile solvents, aromatic hydrocarbon solvents, ether solvents, ketone solvents, ester solvents, orthoester solvents, dimethylformamide, dimethyl sulfoxide, alcohol, and water.
Specific examples of nitrile solvents include acetonitrile, isobutyronitrile, and benzonitrile.
Specific examples of aromatic hydrocarbon solvents include benzene, toluene, and xylene.
Specific examples of ether solvents include anisole, dibutyl ether, and tetrahydrofuran.
Specific examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
Specific examples of ester solvents include methyl acetate, ethyl acetate, propyl acetate, and butyl acetate.
Specific examples of orthoester solvents include trimethyl orthoformate, triethyl orthoformate, tri(n-propyl) orthoformate, tri(isopropyl) orthoformate, trimethyl orthoacetate, triethyl orthoacetate, triethyl orthopropionate, and n-orthoformate. Examples include trimethyl butyrate and trimethyl orthoisobutyrate.
These can be used alone or in combination of two or more.

The nucleophile is not particularly limited as long as it can convert a thiocarbonylthio group into a mercapto group. Examples include nucleophilic reagents such as ammonia, amine compounds, metal alkoxides (sodium methoxide, sodium ethoxide, etc.), and thiol compounds. Among these, amine compounds such as primary or secondary amine compounds are preferred. Specific examples include ethylamine, n-propylamine, isopropylamine, butylamine, hexylamine, octylamine, benzylamine, ethylenediamine, hydrazine, piperidine, aminoethanol, and combinations thereof.

The amount of the nucleophile to be used can usually be appropriately selected depending on the equivalent weight of the thiocarbonylthio group contained in the polymer (P1). The molar equivalent of the nucleophile to the thiocarbonylthio group is preferably 1 molar equivalent or more, more preferably 10 molar equivalent or more, particularly preferably 20 molar equivalent or more, from the viewpoint of reaction efficiency. Further, from the viewpoint of having little influence of odor due to unreacted nucleophilic agents, the amount is preferably 70 molar equivalents or less, more preferably 60 molar equivalents or less, and particularly preferably 50 molar equivalents or less.

Such a reaction in which a thiocarbonyl group is removed from a polymer (P1) having two or more thiocarbonylthio groups using an amine compound is sometimes referred to as aminolysis.

When removing a thiocarbonyl group by aminolysis, it is preferable to remove oxygen from the reaction system so that the mercapto group produced is not oxidized to form disulfide (SS). For example, in addition to removing oxygen, a reducing agent can be supplied to the solution of the polymer (P1) to suppress disulfide formation.

Examples of reducing agents include tributylphosphine, tris(2-carboxyethyl)phosphine (TCEP), borohydride such as NaBH ₄ used with tributylphosphine, LiBH(C ₂ H ₅ ) _3, dimethylphenylphosphine (DMPP), Examples include sodium dithionate (Na ₂ S ₂ O ₄ ), sodium bisulfite (NaHSO ₃ ), ethylenediaminetetra(acetic acid) (EDTA), and combinations thereof.

From the viewpoint of reaction efficiency, the reaction temperature is preferably 10°C or higher, more preferably 15°C or higher, and particularly preferably 25°C or higher. In addition, from the viewpoint that side reactions such as nucleophilic reactions to the polymer main chain are unlikely to occur, the temperature is preferably 80°C or lower, more preferably 60°C or lower, and particularly preferably 50°C or lower.

From the viewpoint of reaction efficiency, the reaction time is preferably 1 hour or more, more preferably 2 hours or more, and particularly preferably 3 hours or more. In addition, from the viewpoint that side reactions such as nucleophilic reactions to the polymer main chain are unlikely to occur, the heating time is preferably 48 hours or less, more preferably 36 hours or less, and particularly preferably 24 hours or less.

The progress of the reaction can be monitored, for example, as follows. A sample was prepared by extracting a part of the solution, purifying the solution by reprecipitation and vacuum drying, and ¹ H-NMR measurement of the sample revealed that a peak derived from the proton on the carbon to which the RAFT group (thiocarbonylthio group) is bonded was detected. was observed to disappear, and a peak derived from the proton on the carbon to which the generated SH group was bonded appeared. The number of SH groups per molecule can be confirmed from this peak integral value and the peak integral value derived from a characteristic proton (for example, a hydrogen atom on a benzene ring) present at the starting end.

（式中、記号は前記に同じ。） One form of step (ii) can be expressed as follows. That is, the polymer (P2) represented by formula (4) can be produced by reacting the polymer (P1) represented by formula (3) with a nucleophile.

(In the formula, the symbols are the same as above.)

After the reaction is completed, a polymer (P2) having two or more mercapto groups can be obtained by isolation or purification using a known treatment method such as reprecipitation treatment or vacuum drying, and then proceed to step (iii). can be provided. Alternatively, the solution containing the polymer (P2) having two or more mercapto groups obtained in this reaction can be used in step (iii) without isolation or purification.

Step (iii):
In step (iii), the polymer (P2) obtained in step (ii) is usually reacted with a compound that is reactive with the mercapto group in a solvent to functionalize two or more terminals. A polymer (P3) is produced.

A known solvent can be used as the solvent. Examples include nitrile solvents, aromatic hydrocarbon solvents, ether solvents, ketone solvents, ester solvents, orthoester solvents, dimethylformamide, dimethyl sulfoxide, alcohol, and water.
Specific examples of nitrile solvents include acetonitrile, isobutyronitrile, and benzonitrile.
Specific examples of aromatic hydrocarbon solvents include benzene, toluene, and xylene.
Specific examples of ether solvents include anisole, dibutyl ether, and tetrahydrofuran.
Specific examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
Specific examples of ester solvents include methyl acetate, ethyl acetate, propyl acetate, and butyl acetate.
Specific examples of orthoester solvents include trimethyl orthoformate, triethyl orthoformate, tri(n-propyl) orthoformate, tri(isopropyl) orthoformate, trimethyl orthoacetate, triethyl orthoacetate, triethyl orthopropionate, and n-orthoformate. Examples include trimethyl butyrate and trimethyl orthoisobutyrate.
These can be used alone or in combination of two or more.

Examples of the compound having reactivity with a mercapto group include (meth)acryloyl group-containing compounds, epoxy group-containing compounds, isocyanate group-containing compounds, and alkenyl group-containing compounds. This compound preferably has a crosslinkable functional group, and examples of the crosslinkable functional group include a hydroxyl group, a carboxyl group, a (meth)acryloyl group, an epoxy group, and a crosslinkable silyl group. Examples of the crosslinkable silyl group include alkoxysilyl groups (trialkoxysilyl group, dialkoxyalkylsilyl group, etc.), and specifically, triC1-C4 alkoxysilyl group, diC1-C4 alkoxy (C1-C4 alkoxysilyl group, etc.). C4 alkyl) silyl group, etc. The compound may have one or more crosslinkable functional groups.

Specific examples of compounds that are reactive with mercapto groups include compounds with two (meth)acryloyl groups in the molecule, such as 1,4-butanediol di(meth)acrylate and 1,6-hexanediol di(meth)acrylate. Compounds having (meth)acryloyl group and isocyanate group in the molecule such as 2-isocyanatoethyl (meth)acrylate and 2-isocyanatoethyl (meth)acrylate; ) Compounds having an acryloyl group and an epoxy group; Compounds having a (meth)acryloyl group and an alkenyl group in the molecule such as allyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 3-hydroxy (meth)acrylate Compounds having a (meth)acryloyl group and a hydroxyl group in the molecule such as propyl; Compounds having a (meth)acryloyl group and a carboxyl group in the molecule such as (meth)acrylic acid; γ-(meth)acryloxypropyltrimethoxysilane , γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, etc. Compounds having a (meth)acryloxy group and a crosslinkable silyl group in the molecule; 1,4-butanediol di Glycidyl ether, 1,6-hexanediol diglycidyl ether Compounds having two or more epoxy groups in the molecule; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyl Compounds that have an epoxy group and a crosslinkable silyl group in the molecule such as methyldimethoxysilane; Compounds with isocyanate groups and crosslinkable silyl groups; compounds with alkenyl groups and hydroxyl groups in the molecule, such as vinyl alcohol and 3-buten-1-ol; alkenyl groups in the molecule, such as vinyl acetic acid, allyl acetic acid, and 6-heptenoic acid. Examples include compounds having a group and a carboxyl group.

The amount of the compound reactive with a mercapto group can be selected appropriately depending on the equivalent weight of the mercapto group contained in the polymer (P2). It is usually 0.1 to 50 molar equivalents, preferably 0.5 to 20 molar equivalents per 1 molar equivalent.

In this reaction, it is preferable that oxygen be removed from the reaction system so that the mercapto groups contained in the polymer (P2) are not oxidized to form disulfide (SS). For example, the reducing agent described in step (ii) above can also be included.

This reaction can be carried out usually at 0 to 200°C, preferably at room temperature to 150°C, for 1 to 24 hours. After the reaction is completed, it can be isolated or purified using a known treatment method such as reprecipitation treatment or vacuum drying to obtain a polymer (P3) in which two or more terminals have been functionalized.

The molecular weight of the polymer (P3) is determined by GPC (gel permeation chromatography) measurement (in terms of polystyrene), and the number average molecular weight (Mn) is usually 2,000 to 1,000,000, particularly 5,000 to 500,000, and the weight average molecular weight (Mw) is usually 2,000 to 1,000,000, especially 5,000 to 500,000, and the polydispersity (Mw/Mn) is usually 1 to 5, especially 1.02 to 3.

（式中、Ｘは、前記メルカプト基と反応性を有する化合物に由来する基であり、当該基は架橋性官能基を含むことが好ましい。他の記号は前記に同じ。）
基Ｘに含まれる架橋性官能基としては、例えば、上述した（メタ）アクリロイル基、エポキシ基、水酸基、カルボキシル基、架橋性シリル基等が挙げられる。 One form of step (iii) can be expressed as follows. That is, by reacting the polymer (P2) represented by formula (4) with a compound having reactivity with a mercapto group, a polymer (P3) having a crosslinkable functional group represented by formula (5) is obtained. can be manufactured.

(In the formula, X is a group derived from a compound that is reactive with the mercapto group, and the group preferably contains a crosslinkable functional group.Other symbols are the same as above.)
Examples of the crosslinkable functional group contained in the group X include the above-mentioned (meth)acryloyl group, epoxy group, hydroxyl group, carboxyl group, crosslinkable silyl group, and the like.

2. Curable resin composition and cured product The polymer (P3) in which two or more terminals are functionalized obtained in step (iii) is made into a curable resin composition by containing other components as necessary. be able to. Other components contained in the composition include a curing catalyst, a crosslinking agent, and the like. It is preferable that the terminal (specifically, the group X of the above formula (5)) contained in the polymer (P3) contains a crosslinkable functional group.

A cured product can be obtained by curing the polymer (P3) and the curable resin composition obtained in the above step (iii) using a curing catalyst, respectively. When curing, a crosslinking agent may be used depending on the type of terminal crosslinkable functional group contained in the polymer (P3).

Examples of the curing catalyst include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethyl maleate, dibutyltin diethyl maleate, dibutyltin dibutyl maleate, Dibutyltin diisooctyl maleate, dibutyltin ditridecyl maleate, dibutyltin dibenzyl maleate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethyl maleate, dioctyltin diisooctyl Tetravalent tin compounds such as malate; titanate esters such as tetrabutyl titanate and tetrapropyl titanate; organic aluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, and diisopropoxyaluminum ethylacetoacetate; zirconium tetra Chelate compounds such as acetylacetonate and titanium tetraacetylacetonate; lead octylate; butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, Benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1 , 8-diazabicyclo(5,4,0)undecene-7 (DBU); or salts of these amine compounds with carboxylic acids, etc.; low molecular weight obtained from excess polyamine and polybasic acid; Polyamide resin; reaction product of excess polyamine and epoxy compound; silanol condensation of silane coupling agents having amino groups such as γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)aminopropylmethyldimethoxysilane, etc. Catalyst; Other known silanol condensation catalysts such as acidic catalysts and basic catalysts; Known quaternary ammonium salts such as tetrabutylammonium bromide; Peroxide compounds such as benzoyl peroxide; Dialkyl such as zinc diethyldithiocarbamate. Zinc dithiocarbamate; dialkyldithiocarbamate iron (III) such as dimethyldithiocarbamate iron (III), and the like.
The amount of the curing catalyst used is not particularly limited, and is usually 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight, per 100 parts by weight of the polymer (P3).

When using a crosslinking agent, the crosslinking agent can be appropriately selected depending on the type of crosslinkable functional group at the terminal of the polymer (P3).

When the terminal crosslinkable functional group contained in the polymer (P3) is a (meth)acryloyl group, it is generally preferable to cure it by irradiation with active energy rays such as ultraviolet rays, visible rays, and electron beams, or by heat.
In the case of a curable resin composition that is cured by active energy rays, it is preferable to contain a known photopolymerization initiator as a curing catalyst, and in the case of a curable resin composition that is cured by heat, the curing It is preferable to contain a known thermal polymerization initiator as a catalyst.
As a crosslinking agent, dithiol compounds such as 1,2-ethanedithiol, 1,4-butanethiol, 1,10-decanethiol, 1,4-benzenethiol, or ethane-1,1,1-trithiol, 1,3 By using a polyvalent thiol such as a trithiol compound such as , 5-benzene trithiol, the ene-thiol reaction can be utilized.

When the terminal crosslinkable functional group contained in the polymer (P3) is an epoxy group, organic carboxylic acid ammonium salts, dithiocarbamates, polyhydric carboxylic acids, or anhydrides are preferably used as the crosslinking agent.
Examples of the organic carboxylic acid ammonium salt include ammonium benzoate and the like.
Examples of dithiocarbamates include zinc salts, iron salts, tellurium salts, etc. of dimethyldithiocarbamic acid, diethyldithiocarbamic acid, dibenzyldithiocarbamic acid, and the like.
Examples of polycarboxylic acids include malonic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, citric acid, tartaric acid, phthalic acid, and the like.

When the terminal crosslinkable functional group contained in the polymer (P3) is a carboxyl group, polyvalent amines, polyfunctional isocyanates, polyfunctional epoxy compounds, etc. are preferably used as the crosslinking agent.
Examples of polyvalent amines include aliphatic diamine compounds such as hexamethylene diamine, hexamethylene diamine carbamate, and N,N'-dicinnamylidene-1,6-hexane diamine; alicyclic diamine compounds such as 4,4'-methylenebiscyclohexylamine carbamate; Diamine compounds; 4,4'-methylene dianiline, m-phenylene diamine, 4,4'-diaminodiphenyl ether, 4,4'-(m-phenylene diisopropylidene) dianiline, 4,4'-(p-phenylene dianiline) isopropylidene) dianiline, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-diaminobenzanilide, m-xylylenediamine, p-xylylenediamine, 1,3,5 Examples include aromatic diamine compounds such as -benzenetriamine and 1,3,5-benzenetriaminomethyl.
Examples of the polyfunctional isocyanate include hexamethylene diisocyanate, dimethyldiphenylene diisocyanate, isophorone diisocyanate, and the like.
Examples of polyfunctional epoxy compounds include aromatic epoxy compounds such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, phenol novolac type epoxy resin, and cresol novolac type epoxy resin; dicyclopentadiene dioxide, 3,4-epoxy Alicyclic epoxy compounds such as cyclohexylmethyl(3,4-epoxy)cyclohexanecarboxylate; aliphatic compounds such as diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol Examples include epoxy compounds.

When the terminal crosslinkable functional group contained in the polymer (P3) is a hydroxyl group, examples of the crosslinking agent include polyfunctional isocyanates, aminoplast resins such as methylolated melamine and alkyl ethers or low condensates thereof, and polyfunctional Carboxylic acids and their halides are preferably used.

When the terminal crosslinkable functional group contained in the polymer (P3) is a crosslinkable silyl group, crosslinking reactivity occurs due to moisture, so there is no need to add a crosslinking agent or the like.
When a crosslinking agent is used, the amount of the crosslinking agent used is not particularly limited, and is usually 0.01 to 30 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the polymer (P3).

The curing catalyst, reaction temperature, and reaction time of the main curing reaction may be appropriately set according to the type of terminal crosslinkable functional group contained in the polymer (P3), and can be easily set by a person skilled in the art. can.

The obtained cured product has excellent heat resistance at high temperatures. The cured product can be used in a wide range of fields such as automobile parts, home appliance/OA equipment parts, medical equipment parts, packaging materials, civil engineering and construction materials (sealing materials, exterior tile adhesives, etc.), electric wires, and miscellaneous goods. It can be suitably used for materials, etc.

EXAMPLES The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following, "parts" and "%" mean parts by mass and % by mass unless otherwise specified.
Methods for analyzing the polymers obtained in Production Examples, Examples, and Comparative Examples will be described below.

<Molecular weight measurement>
The obtained polymer was subjected to gel permeation chromatography (GPC) measurement under the conditions described below to obtain the number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene. Furthermore, the molecular weight distribution (Mw/Mn) was calculated from the obtained values.
○Measurement conditions Column: Tosoh TSKgel SuperMultiporeHZ-M x 4 Solvent: Tetrahydrofuran Temperature: 40°C
Detector: RI
Flow rate: 600μL/min

Next, evaluation methods for Examples and Comparative Examples will be described below.
<Initial tensile properties>
Tensile strength at break and elongation at break were measured in accordance with JIS K 6251 under normal conditions (25°C).

<Heat resistance test>
A cured product with the same initial tensile properties was used as the sample.
A dumbbell-shaped sample was placed in an explosion-proof dryer at 150° C., and the sample was taken out after 4 hours. Next, the tensile strength at break and elongation at break were measured in accordance with JIS K 6251 under normal conditions (25°C).

1. Synthesis of RAFT agent
Preparation Example 1 (Synthesis of bifunctional RAFT agent: DLBTTC)
(Synthesis of 1,4-bis(n-dodecylsulfanylthiocarbonylsulfanylmethyl)benzene)
Add 1-dodecanethiol (42.2 g), 20% KOH aqueous solution (63.8 g), and trioctylmethylammonium chloride (1.5 g) to an eggplant-shaped flask, cool in an ice bath, and add carbon disulfide (15.9 g). ) and tetrahydrofuran (hereinafter also referred to as "THF") (38 ml) were added and stirred for 20 minutes. A THF solution (170 ml) of α,α'-dichloro-p-xylene (16.6 g) was added dropwise over 30 minutes. After reacting at room temperature for 1 hour, the mixture was extracted from chloroform, washed with pure water, dried over anhydrous sodium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified by column chromatography and then recrystallized from ethyl acetate to obtain 1,4-bis(n-dodecylsulfanylthiocarbonylsulfanylmethyl)benzene represented by the following formula (I). (hereinafter also referred to as "DLBTTC") was obtained in a yield of 80%. ¹ H-NMR measurement confirmed peaks of the target product at 7.2 ppm, 4.6 ppm, and 3.4 ppm.

Preparation example 2 (synthesis of tetrafunctional RAFT agent: TLBTTC)
(Synthesis of 1,2,4,5-tetrakis(n-dodecylsulfanylthiocarbonylsulfanylmethyl)benzene)
Add 1-dodecanethiol (7.2 g), 20% KOH aqueous solution (10.9 g), and trioctylmethylammonium chloride (0.13 g) to an eggplant-shaped flask, cool in an ice bath, and add carbon disulfide (2.7 g). ) and THF (57 ml) were added and stirred for 20 minutes. A THF solution (80 ml) of 1,2,4,5-tetra(bromomethyl) (3.6 g) was added dropwise over 30 minutes. After reacting at room temperature for 1 hour, the mixture was extracted from chloroform, washed with pure water, dried over anhydrous sodium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified by column chromatography and then recrystallized from hexane to obtain 1,2,4,5-tetrakis(n-dodecylsulfanylthiocarbonylsulfanyl) represented by the following formula (II). Methyl)benzene (hereinafter also referred to as "TLBTTC") was obtained in a yield of 88%. ¹ H-NMR measurement confirmed peaks of the target product at 7.2 ppm, 4.6 ppm, and 3.4 ppm.

2. Polymer synthesis (RAFT polymerization)
Synthesis Example 1 (Production of Polymer A)
In a 1 L flask equipped with a stirrer and a thermometer, add DLBTTC (4.2 g), 2,2'-azobis(2-methylbutyronitrile) (hereinafter also referred to as "ABN-E") (0.25 g), and acrylic acid n. -Butyl (hereinafter also referred to as "BA") (410.1 g) and anisole (276.4 g) were charged, thoroughly degassed by nitrogen bubbling, and polymerization was started in a constant temperature bath at 60°C. After 4 hours, the reaction was stopped by cooling to room temperature. Polymer A was obtained by purifying the above polymerization solution by reprecipitation from methanol and vacuum drying. The molecular weight of the obtained polymer A was determined by GPC (gel permeation chromatography) measurement (in terms of polystyrene) to be Mn 42,000, Mw 47,500, and Mw/Mn 1.13.

Synthesis example 2 (manufacture of polymer B)
A 1 L flask equipped with a stirrer and a thermometer was charged with TLBTTC (7.9 g), ABN-E (0.25 g), n-butyl acrylate (BA) (410.1 g), and anisole (278.9 g), and then heated with nitrogen. After sufficient deaeration by bubbling, polymerization was started in a constant temperature bath at 60°C. After 4 hours, the reaction was stopped by cooling to room temperature. Polymer B was obtained by purifying the above polymerization solution by reprecipitation from methanol and vacuum drying. The molecular weight of the obtained polymer B was determined by GPC (gel permeation chromatography) measurement (in terms of polystyrene) to be Mn 36,000, Mw 42,800, and Mw/Mn 1.19.

Synthesis example 3 (manufacture of polymer C)
In a 1 L flask equipped with a stirrer and a thermometer, add DLBTTC (4.2 g), ABN-E (0.25 g), BA (307.0 g), ethyl acrylate (hereinafter also referred to as "EA") (20.5 g), Tetradecyl acrylate (hereinafter also referred to as "TDA") (82.0 g), 3-(methyldimethoxysilyl)propyl methacrylate (0.6 g) and anisole (276.4 g) were charged, thoroughly degassed with nitrogen bubbling, and heated to 60 g. Polymerization was started in a constant temperature bath at ℃. After 4 hours, the reaction was stopped by cooling to room temperature. Polymer C was obtained by purifying the above polymerization solution by reprecipitation from methanol and vacuum drying. The molecular weight of the obtained polymer C was determined by GPC (gel permeation chromatography) measurement (in terms of polystyrene) to be Mn 43,200, Mw 49,300, and Mw/Mn 1.14. The number of crosslinkable silyl groups per block contained in Polymer C, calculated from the amount of 3-(methyldimethoxysilyl)propyl methacrylate introduced and Mn, was 0.4.

Synthesis example 4 (manufacture of polymer D)
DLBTTC (4.2 g), ABN-E (0.25 g), BA (295.5 g), EA (20.5 g), TDA (82.0 g), 3-( Methyldimethoxysilyl)propyl methacrylate (12.1 g) and anisole (276.4 g) were charged, sufficiently degassed by nitrogen bubbling, and polymerization was started in a constant temperature bath at 60°C. After 4 hours, the reaction was stopped by cooling to room temperature. Polymer D was obtained by purifying the above polymerization solution by reprecipitation from methanol and vacuum drying. The molecular weight of the obtained polymer D was determined by GPC (gel permeation chromatography) measurement (in terms of polystyrene) to be Mn 43,100, Mw 50,400, and Mw/Mn 1.17. The number of crosslinkable silyl groups per block contained in Polymer D, calculated from the amount of 3-(methyldimethoxysilyl)propyl methacrylate introduced and Mn, was 8.0.

3. Dethiocarbonyl group and functionalization
Production Example 1 (Production of Polymer 1)
Polymer A (100 parts) obtained in Synthesis Example 1 and anisole (168.2 parts) were placed in a 500 ml flask equipped with a stirrer and a thermometer, and the mixture was sufficiently dissolved by heating to 40 degrees Celsius in a constant temperature bath. . After adding n-propylamine (2.8 parts) to this solution and stirring for 30 minutes, a portion of the solution was taken out, purified by reprecipitation from methanol, and dried in vacuum. ¹ H-NMR measurement revealed that the peak (4.9 ppm) derived from the proton on the carbon to which the RAFT group is bonded almost completely disappeared, and was replaced by a peak (4.9 ppm) derived from the proton on the carbon to which the SH group is bonded. 3.4 ppm) appeared. From this peak integral value and the peak integral value derived from the hydrogen atom on the benzene ring, which is the starting terminal, it was confirmed that the number of SH groups per molecule was 2.0.

Thereafter, 1,4-butanediol diacrylate (hereinafter also referred to as "1,4-BDDA") (9.4 parts) was added and reacted for 5 hours. Polymer 1 was obtained by purifying the obtained solution by reprecipitation from methanol and vacuum drying. The molecular weights of the obtained polymer 1 were Mn 41,000, Mw 47,200, and Mw/Mn 1.15, as determined by GPC (gel permeation chromatography) measurement (in terms of polystyrene). From ¹ H-NMR measurement, it was confirmed that the peak (3.4 ppm) derived from the proton on the carbon to which the SH group was bonded had almost completely disappeared.

Production Examples 2 to 9 (Production of Polymers 2 to 9)
Polymers 2 to 9 were obtained by carrying out the same operation as in Production Example 1, except that the amount of nucleophile used, the amount of solvent used, and the type and amount of reactant used were changed as described in Table 2. . Table 2 shows the molecular weight of each polymer.
・1,4-BDDGE: 1,4-butanediol diglycidyl ether ・KBM-5103: 3-acryloxypropyltrimethoxysilane, Shin-Etsu Silicone "KBE-5103" manufactured by Shin-Etsu Chemical Co., Ltd.
・KBE-403: 3-glycidoxypropyltriethoxysilane, Shin-Etsu Silicone "KBE-403" manufactured by Shin-Etsu Chemical Co., Ltd.
・KBE-9007N: 3-Isocyanatepropyltriethoxysilane, Shin-Etsu Silicone "KBE-9007N" manufactured by Shin-Etsu Chemical Co., Ltd.

Production Examples 10 to 12 (Production of Polymers 10 to 12)
The same operation as in Production Example 1 was carried out except that the type of polymer, the amount of nucleophile used, the amount of solvent used, and the type and amount of reactant used were changed as shown in Table 1. I got 12. The molecular weights of Polymers 10 to 12 are shown in Table 2.
In addition, in Production Examples 10 to 12, the same ¹ H-NMR measurement as in Production Example 1 revealed that the number of SH groups per polymer molecule in Polymer 10 was 4.0 after aminolysis with a nucleophile. , and Polymers 11 and 12, it was confirmed that the number of SH groups per polymer molecule was 2.0, and after the reaction with the reactant, the number of SH groups derived from the proton on the carbon to which the SH group was bonded was confirmed to be 2.0. It was confirmed that the peak had almost completely disappeared.

Comparative Production Example 1 (Production of Polymer 13)
In a 1 L flask equipped with a stirrer and a thermometer, add bis[4-(2-hydroxyethoxycarbonyl)benzyl]trithiocarbonate (hereinafter also referred to as "OHDBTTC") (3.0 g), ABN-E (0.25 g), n-Butyl acrylate (BA) (410.1 g) and anisole (275.6 g) were charged, thoroughly degassed by nitrogen bubbling, and polymerization was started in a constant temperature bath at 60°C. After 4 hours, the reaction was stopped by cooling to room temperature. Polymer 13 was obtained by purifying the above polymerization solution by reprecipitation from methanol and vacuum drying. The molecular weight of the obtained polymer 13 was determined by GPC (gel permeation chromatography) measurement (in terms of polystyrene) to be Mn 36,300, Mw 43,900, and Mw/Mn 1.21. The molecular weight of Comparative Production Example 1 is shown in Table 2.

Example 1 (terminal crosslinkable functional group: acryloyl group)
Polymer 1 (100 parts) and antioxidant Irganox 1010 (manufactured by BASF) (0.3 parts) were dissolved in tetrahydrofuran (THF) to prepare a solution with a polymer concentration of 10%. Niper BW (1 part) was added to this and dissolved. This was poured into a mold and the THF was dried and distilled off to create a cast film with a thickness of about 1 mm. The obtained film was reacted for 10 minutes in a blow dryer at 150°C to obtain a cured product. Table 3 shows the initial tensile properties and heat resistance test results of the cured product.
・Niper BW: Benzoyl peroxide, “Niper BW” manufactured by NOF Corporation

Example 2 (terminal crosslinkable functional group: epoxy group)
Polymer 2 (100 parts) and antioxidant Irganox 1010 (manufactured by BASF) (0.3 parts) were dissolved in tetrahydrofuran (THF) to prepare a solution with a polymer concentration of 10%. Noxeler PZ (2 parts) and Noxeler TTFE (2 parts) were added thereto and dissolved. This was poured into a mold and the THF was dried and distilled off to create a cast film with a thickness of about 1 mm. The obtained film was reacted for 10 minutes in a blow dryer at 170°C to obtain a cured product. Table 3 shows the initial tensile properties and heat resistance test results of the cured product.
・Noxela PZ: Zinc dimethyldithiocarbamate, "Noxela PZ" manufactured by Ouchi Shinko Kagaku Co., Ltd.
・Noxeler TTFE: Ferric dimethyldithiocarbamate, “Noxeler TTFE” manufactured by Ouchi Shinko Kagaku Co., Ltd.

Examples 3, 4, 10 and Comparative Example 1 (terminal crosslinkable functional group: hydroxyl group)
Polymers 3, 4, 10, or 13 (100 parts each) and the antioxidant Irganox 1010 (manufactured by BASF) (0.3 parts) were dissolved in tetrahydrofuran (THF), and then Duranate TPA-100 (1 part) was dissolved in tetrahydrofuran (THF). ) was added to prepare a solution with a polymer concentration of 10%. Neostane U-220H (0.1 part) was added thereto as a curing catalyst and dissolved. This was poured into a mold and the THF was dried and distilled off to create a cast film with a thickness of about 1 mm. The obtained film was cured in a blow dryer at 40° C. for 5 days to obtain a cured product. Table 3 shows the initial tensile properties and heat resistance test results of the cured product.
・Duranate TPA-100: An isocyanurate of hexamethylene diisocyanate, “Duranate TPA-100” manufactured by Asahi Kasei Corporation
・Neostan U-220H: Dibutyltin diacetylacetonate, "Neostan U-220H" manufactured by Nitto Kasei Co., Ltd.

Examples 5 and 6 (terminal crosslinkable functional group: carboxyl group)
After dissolving the polymer 5 or 6 (100 parts) and the antioxidant Irganox 1010 (manufactured by BASF) (0.3 parts) in tetrahydrofuran (THF), jER-152 (1 part) was added to adjust the polymer concentration. A 10% solution was prepared. Tetrabutylammonium bromide (TBAB) (0.2 parts) was added thereto as a curing catalyst and dissolved. This was poured into a mold and the THF was dried and distilled off to create a cast film with a thickness of about 1 mm. The obtained film was cured at 175° C. for 4 hours to obtain a cured product. Table 3 shows the initial tensile properties and heat resistance test results of the cured product.
・jER-152: Phenol novolac type epoxy resin, “jER-152” manufactured by Mitsubishi Chemical Corporation

Examples 7 to 9, 11 and 12 (terminal crosslinkable functional group: crosslinkable silyl group)
Polymers 7 to 9, 11 or 12 (100 parts each) and the antioxidant Irganox 1010 (manufactured by BASF) (0.3 parts) were dissolved in tetrahydrofuran (THF) to prepare a solution with a polymer concentration of 10%. did. Neostan U-220H (manufactured by Nitto Kasei Co., Ltd.) (1.0 part) was added thereto as a curing catalyst and dissolved. This was poured into a mold and the THF was dried and distilled off to create a cast film with a thickness of about 1 mm. The obtained film was cured for 6 days at 23° C. and 50% RH, and then for 1 day at 50° C. in a saturated steam atmosphere to obtain a cured product. Table 3 shows the initial tensile properties and heat resistance test results of the cured product.

Evaluation Results As is clear from the results of Examples 1 to 12, a terminal-functionalized polymer was produced using a di- or tetra-functional RAFT agent, and a curable resin composition containing the polymer was cured. I got something. It was confirmed that this cured product had excellent heat resistance.
On the other hand, as is clear from Comparative Example 1, the cured product of the curable resin composition containing the telechelic polymer produced using the monofunctional RAFT agent was found to be significantly inferior in heat resistance. .

Claims (11)

A method for producing a polymer functionalized at two or more terminals, the method comprising:
(i) A step of polymerizing a vinyl monomer using a polymerization control agent having two or more thiocarbonylthio groups to obtain a polymer (P1) having two or more thiocarbonylthio groups, where: The polymerization control agent having two or more thiocarbonylthio groups has two or more formula (1a) in the molecule:

(In the formula, Z is a group represented by -SR ^A , and R ^A is an alkyl group that may have a substituent, an aryl group that may have a substituent, or an aryl group that may have a substituent. Indicates an optionally substituted heteroaryl group or an optionally substituted aralkyl group.)
A RAFT agent having a group represented by
(ii) a step of reacting the polymer (P1) obtained in step (i) with a nucleophile to obtain a polymer (P2) having two or more mercapto groups (-SH); and (iii) ) The polymer (P2) obtained in step (ii) is reacted with a compound that is reactive with the mercapto group to produce a polymer (P3) in which two or more terminals are functionalized. A manufacturing method that includes a process. The RAFT agent has the formula (1):

(In the formula, R represents an n-valent organic group which may have one or more heteroatoms selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom, and n represents an integer of 2 or more. (Z is the same as above. Two or more Z's may be the same or different.)
The manufacturing method according to claim 1 , which is a compound represented by or a salt thereof. The manufacturing method according to claim 2 , wherein the R is an n-valent organic group having a carbon atom bonded to a group represented by -SC(=S)-Z. The RAFT agent has formulas (1A) to (1C):

(In the formula, ring A represents an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent, and R ^a and R ^b are the same or different and are a hydrogen atom, It represents an alkyl group or a cyano group, p represents an integer of 2 or more, q represents 0 or 1, and r represents an integer of 1 or more. R ^A and Z are the same as above. R ^A of 2 or more , may be the same or different, and two or more Z's may be the same or different.)
The manufacturing method according to any one of claims 1 to 3 , which is one selected from the group consisting of. The vinyl monomer has the formula (2):

(In the formula, U and W are the same or different, -CO ₂ H, -CO ₂ R ¹ , -C(=O)R ¹ , -C(=S)R ¹ , -C(=S)OR ¹ , -C(=O)SR ¹ , -C(=O)NH ₂ , -C(=O)NHR ¹ , -C(=O)N(R ¹ ) ₂ , hydrogen atom, halogen atom, or substitution Indicates an alkyl group that may have a group. Alternatively, U and W may be bonded to each other to form a ring with the adjacent -C=C-, and the ring has a substituent. It's okay.
V is a hydrogen atom, R ¹ , -CO ₂ H, -CO ₂ R ¹ , -C(=O)R ¹ , -C(=S)R ¹ , -C(=S)OR ¹ , -C( =O)SR ¹ , -C(=O)NH ₂ , -C(=O)NHR ¹ , -C(=O)N(R ¹ ) ₂ , -OR ¹ , -SR ¹ , -OC(=O )R ¹ , -SC(=O)R ¹ , or -OC(=S)R ¹ .
R ¹ is the same or different and is an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, or an alkyl group that may have a substituent; Aryl group which may have a substituent, heteroaryl group which may have a substituent, cycloalkyl group which may have a substituent, heterocycloalkyl group which may have a substituent, Indicates an aralkyl group that may have an optional aralkyl group, a heteroarylalkyl group that may have a substituent, or a polymer chain that may have a substituent. )
The manufacturing method according to any one of claims 1 to 4 , which is a compound represented by or a salt thereof. The manufacturing method according to any one of claims 1 to 5 , wherein the nucleophile is at least one selected from the group consisting of primary amine compounds and secondary amine compounds. Claim 1, wherein the compound having reactivity with the mercapto group is at least one selected from the group consisting of (meth)acryloyl group-containing compounds, epoxy group-containing compounds, isocyanate group-containing compounds, and alkenyl group-containing compounds. - 6. The manufacturing method according to any one of 6 . The manufacturing method according to claim 7 , wherein the compound having reactivity with the mercapto group has a crosslinkable functional group. The manufacturing method according to claim 8 , wherein the crosslinkable functional group is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a (meth)acryloyl group, an epoxy group, and a crosslinkable silyl group. A method for producing a curable resin composition, comprising a polymer functionalized at two or more terminals obtained by the production method according to any one of claims 1 to 9 , a curing catalyst, and, if necessary, a curing agent. A manufacturing method including the step of mixing. A method for producing a cured product, the method comprising a step of curing a curable resin composition obtained by the production method according to claim 10 .