JP2000355610A - Production of vinyl polymer having terminal functional group, and vinyl polymer having terminal functional group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method wherein a vinyl polymer having terminal functional groups can be easily and practically produced and provide a vinyl polymer which has terminal functional groups and is useful as a material for producing various functional materials. SOLUTION: In this production method, an iodine compound which has at least two iodine atoms bonded with carbon atoms attached to an aromatic ring is used as a chain transfer agent; a vinyl monomer is subjected to radical polymerization in a system containing the chain transfer agent to give a vinyl polymer having iodine atoms bonded to the molecular terminals; and the terminal iodine atomes are substituted by groups having functional groups to introduce functional groups into the terminals. A vinyl polymer having terminal functional groups and an Mn of 500-500,000 is obtained by this method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a vinyl polymer having a functional group at a terminal, and a vinyl polymer having a functional group at a terminal produced by the above-mentioned production method.

[0002]

2. Description of the Related Art A polymer having a functional group introduced into a terminal can be crosslinked by itself or in combination with a curing agent to obtain a cured product having excellent heat resistance, water resistance and durability. It is known that it can be done. By having a functional group at the terminal, not only networking due to cross-linking, but also chain elongation due to cross-linking between the terminals occurs efficiently, so that a high molecular weight product having a linear chain elongation can be formed, And a resin having excellent tensile strength can be obtained. As for the polymer having a functional group at the terminal, many examples of the synthesis of a rubber-based polymer by a living polymerization method have been reported to date, and the synthesis of a polybutadiene having a functional group at both ends by a living anionic polymerization has been reported. (Journal of the Rubber Association of Japan, 48 volumes,
5, p. 263, 1975), and the synthesis of polychloroprene having hydroxyl groups at both ends by the iniferter method (JP-A-3-287613). In addition, a hydroxyl group polymer having a polypropylene glycol skeleton at both ends is also used as a raw material for urethane adhesives and sealing materials, and as a modifier for epoxy-based adhesives. In addition, polyester resins such as polyethylene terephthalate and polycaprolactone are also used for many purposes. For resins other than these, particularly for highly polar vinyl monomers including (meth) acrylic acid esters and (meth) acrylonitrile, a method for producing a vinyl polymer having a functional group at a terminal has not yet been put to practical use. is the current situation.

As a method for producing such an acrylic polymer having a substituent introduced into a terminal, for example, Japanese Patent Application Laid-Open No.
No. 255415 discloses a method of synthesizing a (meth) acrylic polymer having alkenyl groups at both ends using an alkenyl group-containing disulfide as a chain transfer agent.

In Japanese Patent Application Laid-Open No. 5-262808, an acrylic polymer having hydroxyl groups at both ends is synthesized by using a disulfide having a hydroxyl group.
Furthermore, there is disclosed a method of synthesizing a (meth) acrylic polymer having an alkenyl group at a terminal by utilizing a hydroxyl group at the terminal. However, in these synthesis methods, it is difficult to reliably introduce functional groups at both ends in the above-described method, and in the method described below, when a polymer having a hydroxyl group is synthesized, Unless a large amount of a disulfide compound equal to or more than the monomer is used, there is a problem that a side reaction such as a termination reaction or a chain transfer reaction cannot be suppressed.

In recent years, polymerization by living polymerization methods such as living ion polymerization and living radical polymerization has been actively studied. In the synthesis of polymers performed by these polymerization methods, it is easy to control the molecular weight and molecular weight distribution, and it is also possible to produce a polymer having a functional group at the terminal by converting the active group at the living terminal into an arbitrary substituent. Can be performed relatively easily.

As a method for producing a polymer having a functional group at a terminal by using such a living polymerization method, for example, Japanese Patent Application Laid-Open No. 4-501883 discloses a method in which a functional group is added to a terminal using anionic polymerization. A method for synthesizing a (meth) acrylic acid macromonomer is disclosed. However, in the case of anionic polymerization, unless water-free conditions or low-temperature conditions are used, the termination reaction or chain transfer reaction cannot be controlled, and the reaction does not proceed in a living manner, so that terminal conversion becomes impossible and lacks practicality. There was a problem.

For example, living radical polymerization has attracted attention from the viewpoint of reaction conditions and simplicity of operation.
JP-A-272714 discloses a method for producing a (meth) acrylic polymer having an alkenyl group at a terminal using an organic halide or a sulfonyl halide compound as an initiator and a metal complex as a catalyst. . However, such a polymerization method using a metal complex as a catalyst has a problem in industrial production that it is difficult to wash a metal in a resin purification step.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above problems of the conventional method for producing a polymer having a functional group at a terminal, especially an acrylic polymer, and has been developed to provide a vinyl polymer having a functional group at a terminal. It is an object of the present invention to provide a manufacturing method that can be easily and practically manufactured. Another object of the present invention is to provide a vinyl polymer having a functional group at a terminal useful as a raw material for producing various functional materials.

[0009]

In order to achieve the above object, the present invention according to claim 1 contains at least two iodine atoms as a chain transfer agent, and the iodine atom is contained in an aromatic ring. Using an iodine compound having a structure bonded to a bonded carbon atom, performing a radical polymerization reaction in a system containing a vinyl monomer and the chain transfer agent, and synthesizing a vinyl polymer having an iodine atom at a terminal. The present invention also provides a method for producing a vinyl polymer having a functional group at a terminal, in which a functional group is introduced into a terminal by replacing an iodine atom at the terminal of the vinyl polymer with a group having a functional group.

The present invention according to claim 2 provides an iodine compound having at least two iodine atoms as a chain transfer agent, wherein the iodine atom is bonded to a carbon atom bonded to an aromatic ring. By performing a radical polymerization reaction in a system containing a vinyl-based monomer and the chain transfer agent, followed by a polymerization reaction of the styrene-based monomer, whereby styrene is added between the vinyl-based polymer and the terminal iodine atom. A method for producing a vinyl polymer having a functional group at a terminal by synthesizing a vinyl polymer having a functional polymer, and then substituting the iodine atom at the terminal of the vinyl polymer with a group having a functional group. provide.

Further, according to the present invention, the weight fraction of the styrene polymer in the vinyl polymer is 10%.
% Of the vinyl polymer having a functional group at a terminal according to claim 2. According to a fourth aspect of the present invention, the functional group introduced into the terminal is at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, a vinyl group and a silyl group. A method for producing a vinyl polymer having a functional group at a terminal according to any one of claims 1 to 3.

According to a fifth aspect of the present invention, the vinyl monomer is a (meth) acrylic acid ester, and the terminal functional group according to any one of the first to fourth aspects is characterized in that: Disclosed is a method for producing a vinyl polymer having a group. The present invention according to claim 6 is characterized in that the vinyl monomer is (meth) acrylonitrile.
5. A method for producing a vinyl polymer having a functional group at a terminal according to any one of items 4 to 4.

[0013] The present invention according to claim 7 is based on claim 1.
7. A vinyl polymer produced by using the production method according to any one of items 1 to 6, wherein the number average molecular weight is 500 to 5
The present invention provides a vinyl polymer having a terminal functional group, which has a terminal functional group introduction ratio of 90% or more. Hereinafter, the present invention will be described in detail.

In the production method of the present invention, first, a radical polymerization reaction is carried out in a system containing a vinyl monomer and a chain transfer agent to synthesize a vinyl polymer having an iodine atom at a terminal.

The vinyl monomers used in the present invention include:
(Meth) acrylic acid, (meth) acrylic ester, styrene derivative, (meth) acrylonitrile, (meth) acrylamide, vinyl halide, vinyl ester,
(Meth) acrolein, maleic acid derivatives, fumaric acid derivatives, and the like. These vinyl monomers may be used alone or in combination of two or more. Among these, the (meth) acrylate ester is a polymer,
(Meth) acrylonitrile is preferred in that the polymer becomes a resin having excellent oil resistance and gas barrier properties. In addition, for example, the above (meth) acrylic acid means acrylic acid or methacrylic acid.

The (meth) acrylate is not particularly restricted but includes, for example, methyl (meth) acrylate,
Ethyl (meth) acrylate, (meth) acrylic acid-n-
Propyl, isopropyl (meth) acrylate, (meth)
N-butyl acrylate, isobutyl (meth) acrylate, -tert-butyl (meth) acrylate, (meth)
Pentyl acrylate, n-hexyl (meth) acrylate, isohexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylate ) Nonyl acrylate, decyl (meth) acrylate,
Dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, stearyl (meth) acrylate, (meth)
2-hydroxyethyl acrylate, 3-methoxypropyl (meth) acrylate and the like. These (meth) acrylates may be used alone or in combination of two or more.

Further, in the production method of the present invention, a vinyl polymer having a styrene polymer between a terminal iodine atom and a vinyl polymer in order to increase the substitution reactivity between the terminal iodine and the functional group to be introduced. Combine. The polymerization is carried out by a method of performing a radical polymerization reaction in a system containing a vinyl monomer and a chain transfer agent, and subsequently synthesizing a styrene polymer.

The styrene monomer used in the present invention includes styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, 2,4
-Dimethylstyrene, 2,5-dimethylstyrene, p-
Ethyl styrene, p-isopropyl styrene, p-chloromethyl styrene, p- (2-chloroethyl) styrene and the like can be mentioned.

The styrene polymer in the vinyl polymer is
It is necessary that at least one styrene monomer is attached to at least both ends of the vinyl polymer, and preferably,
The weight fraction of the content of the styrene polymer in the vinyl polymer is 10% by weight or less. Beyond this,
For example, the performance of the vinyl polymer other than the styrene-based block portion is not sufficiently exhibited as shown in the good adhesion of the acrylate resin and the gas barrier property of the acrylonitrile resin.

As the chain transfer agent used in the present invention, an iodine compound containing at least two iodine atoms and having a structure in which the iodine atom is bonded to carbon bonded to an aromatic ring is used. By using such an iodine compound having the above structure, a vinyl polymer having an iodine atom at a terminal can be easily obtained. The aromatic ring is not particularly limited, and examples thereof include a benzene ring, a naphthalene ring, and an anthracene ring.

The aromatic ring may have one or more substituents, if necessary. The substituent is not particularly limited as long as it does not inhibit a radical polymerization reaction, and examples thereof include an alkyl group, an alkoxy group, an amino group, a hydroxyl group, a halogen group, a carbonyl group, a carboxyl group, and a thionyl group. . These substituents may be introduced alone, or two or more kinds may be introduced.

In addition, one or two substituents may be bonded to the iodine atom and the carbon atom to which the aromatic ring is bonded, if necessary. The substituent is not particularly limited as long as it does not inhibit a radical polymerization reaction, and examples thereof include an alkyl group, an alkoxy group, an amino group, a hydroxyl group, a halogen group, a carbonyl group, a carboxyl group, and a thionyl group. . These substituents are 1
Only the types may be combined, or two or more types may be combined.

Specific examples of such an iodine compound include 1,3-bis (iodomethyl) benzene, 1,4-bis (iodomethyl) benzene, 1,3,3
5-tris (iodomethyl) benzene, diphenyldiiodomethane, 4,4'-bis (iodomethyl) biphenyl, bis (4-iodomethylphenyl) methane, 4,
4'-bis (iodomethyl) diphenyl ether, 1,
5-bis (iodomethyl) naphthalene, 2,6-bis (iodomethyl) naphthalene, 2,4,6,8-tetrakis (iodomethyl) naphthalene, 2,6-bis (iodomethyl) anthracene, 9,10-bis (iodomethyl) And anthracene, 1,4,5,8-tetrakis (iodomethyl) anthracene.

Among these, a linear polymer is formed from an iodine compound having two iodine atoms in a molecule, and a star-shaped polymer is generated from an iodine compound having three or more iodine atoms in a molecule. Polymer is easy to form. Among these, an iodine compound having two iodine atoms in a molecule can polymerize a polymer in which an iodine atom is added to both ends of the molecule, and has a functional group at both ends by replacing it with a functional group. Because a linear polymer is obtained,
Using this as the main raw material is preferable in that the molecular weight can be efficiently increased by chain extension.

In order to synthesize the vinyl polymer having an iodine atom at the terminal, the method of radically polymerizing the vinyl monomer using the iodine compound as a chain transfer agent is not particularly limited. A method of using a radical polymerization initiator; a method of irradiating radiation, light, ultraviolet light, laser light, or the like; and a method of heating.

In the above method using a radical polymerization initiator, a compound that generates a radical by heat, light, radiation, an oxidation-reduction chemical reaction or the like can be used as the radical polymerization initiator.

As such a radical polymerization initiator,
For example, peroxycarbonate, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide (lauroyl peroxide,
Organic peroxides such as benzoyl peroxide, diacyl peroxide and peroxyester; 2,2'-
Azobisisobutyronitrile, 2,2'-azobis (2
-Methylbutyronitrile), 2,2'-azobis (2,
Azo compounds such as 4-dimethylvaleronitrile) and dimethyl 2,2'-azobisisobutyrate; inorganic peroxides such as potassium persulfate and ammonium persulfate; hydrogen peroxide-ferrous oxide; benzoyl peroxide-dimethylaniline; Redox initiators such as cerium (IV) salts-alcohols; organometallic compounds such as organotin and organolead; These polymerization initiators may be appropriately selected according to polymerization conditions such as a polymerization temperature. Further, they may be used alone or in combination of two or more.

The amount of the radical polymerization initiator is not particularly limited as long as the polymerization can be initiated.
If the amount is too small, the polymerization reaction may be slow and the conversion may be low. On the other hand, the amount of the radical polymerization initiator,
If the amount is too large, it may be difficult to control the polymerization reaction. For this reason, 0.1 mol per 1 mol of the iodine compound.
It is preferably from 02 to 20 mol, more preferably from 0.05 to 10 mol.

In the method of irradiating radiation, light, ultraviolet light, laser light or the like, if necessary, a photosensitizer such as an azo compound, a peroxide, a carbonyl compound, a sulfur compound or a dye may be added. Good. These photosensitizers may be used alone or in combination of two or more.

The specific method for synthesizing the vinyl polymer having an iodine atom at the terminal by the radical polymerization is not particularly limited, and a conventionally known polymerization method can be used. Synthetic methods, suspension polymerization methods, emulsion polymerization methods and the like can be used.

When a solution polymerization method is used among these polymerization methods, a solvent which does not inhibit radical polymerization is used as a polymerization solvent. Examples of such a polymerization solvent include ester solvents such as ethyl acetate, propyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone and cyclohexanone; aromatic solvents such as benzene, toluene and xylene; methyl cellosolve and ethyl cellosolve. And dimethylformamide, dimethylsulfoxide and the like. These polymerization solvents may be used alone or in combination of two or more.

The reaction temperature for synthesizing the vinyl polymer having an iodine atom at the terminal is not particularly limited, and a general temperature may be selected depending on the type of the vinyl monomer used and the type of the radical polymerization initiator. The reaction temperature may be appropriately selected. Preferably, it is -30 to 120 ° C.

The vinyl polymer having an iodine atom at the terminal obtained by the above method is not limited to those having an iodine atom directly bonded to the terminal of the polymer of the vinyl monomer, but also the vinyl polymer. Another monomer may be polymerized at the terminal of a polymer of the monomer, and an iodine atom may be further bonded to the terminal. The other monomer is not particularly limited as long as it can be polymerized at the terminal of the polymer of the vinyl monomer as described above, for example, a halogenated vinyl monomer,
(Meth) acrylic ester monomers, vinyl ester monomers, vinyl ether monomers, styrene monomers, acrylamide monomers, acrylonitrile, and the like. Among them, the styrene-based monomer can perform the reaction when substituting an iodine atom with a functional group under milder conditions. These other monomers may be used alone or in combination of two or more.

In the production method of the present invention, a vinyl polymer having an iodine atom is synthesized, and then the iodine atom at the terminal of the vinyl polymer is substituted with a group having a functional group to introduce a functional group into the terminal. I do.

The functional group to be introduced into the terminal of the vinyl polymer is not particularly limited as long as it is not released over time, and examples thereof include a halogen group, a hydroxyl group, an amino group, a carboxyl group, a thionyl group, and an epoxy group. Group, vinyl group, silyl group, ethynyl group, mercapto group, oxazoline group, maleimide group, azlactone group and the like.
Among these, a hydroxyl group, an amino group, a carboxyl group, a vinyl group, and a silyl group are preferred. In addition, the said silyl group shall include a hydrosilyl group, a hydroxysilyl group, and an alkoxysilyl group.

The method for introducing a functional group into the terminal of the vinyl polymer is not particularly limited, and a conventionally known chemical reaction can be used as long as the method does not deteriorate the resin. Specifically, for example, in the (1) iodine-amino substitution reaction, a hydroxyl group, an amino group, a carboxyl group, a vinyl group using aminoethanol, ethylenediamine, glycine, p-aminostyrene, 3-aminopropyltriethoxysilane or the like are used. Group, introduction of alkoxysilyl group,
(2) In the iodine-mercapto substitution reaction, a hydroxyl group using mercaptoethanol, mercaptopropionic acid, 3-mercaptopropyltrimethoxysilane, or the like,
Introduction of a carboxyl group or an alkoxysilyl group, (3) introduction of a hydroxyl group by direct substitution of terminal iodine using sodium hydroxide or the like, and (4) substitution of a terminal iodine with chlorosulfonic acid followed by hydrolysis of a carboxyl group. Introduction, (5) introduction of a vinyl group by a ligand exchange reaction using various organic metals having a vinyl group, and (6) 1,3,5,7,9-pentamethylcyclopentasiloxane at the terminal of the vinyl group And the introduction of a hydroxyl group by the addition of

Among them, an iodine-amino substitution reaction and an iodine-mercapto substitution reaction are preferably used, and the compounds (terminal treating agents) used for introducing the above functional groups include aminoethanol, ethylenediamine, and the like.
P-aminostyrene, 3-aminopropyltriethoxysilane, mercaptoethanol, mercaptopropionic acid and the like are preferably used.

By using the method for producing a vinyl polymer having a functional group at a terminal of the present invention described above, a vinyl polymer having a functional group at a terminal can be easily and practically produced.

The vinyl polymer having a functional group at a terminal produced by the production method of the present invention includes the following:
A vinyl polymer produced by using the production method according to any one of the above, wherein the number average molecular weight is 500 to 500.
It is preferable to use a vinyl-based polymer having a terminal functional group introduction ratio of 90% or more and having a functional group at the terminal.
If the average molecular weight is less than 500, a large amount of a cross-linking agent is required for chain extension, which is not practical.If the average molecular weight exceeds 500,000, chain extension becomes difficult to occur, and unreacted oligomers remain, resulting in a polymer. The heat resistance of the cured product deteriorates. When the terminal functional group introduction rate is less than 90%, when the vinyl polymer having a functional group at the terminal is used as a raw material for producing a functional material, desired properties cannot be imparted to the produced functional material. is there.

The terminal functional group introduction rate is defined as the number of functional groups actually introduced at the terminal of the vinyl polymer obtained by the production method of the present invention, and the number of functional groups introduced at the terminal of the vinyl polymer. It is a percentage of the theoretical value. The number of functional groups actually introduced into the terminal of the vinyl polymer can be calculated using a conventionally known measuring method.

Such a vinyl polymer having a functional group at a terminal is a resin such as polyester, polyurethane, or polycarbonate, an adhesive, an adhesive, a sealing material, a foam material, a paint, a powder paint, a thermoplastic elastomer, or a film material. It can be suitably used as a raw material for a molding material, a resin modifier, a coating agent, a vibration damping material, a semiconductor sealing agent, a water stopping agent, artificial marble and the like.

(Action) In the present invention, the iodine compound having the above structure used as a chain transfer agent has a carbon-iodine bond because an iodine atom is bonded to a carbon atom to which an electron-donating aromatic ring is bonded. It is considered that the radical dissociation of the carbon radical easily occurs, and after the radical dissociation occurs, the generated carbon radical has a high chain transfer property due to the radical stabilizing effect of the π electrons of the aromatic ring, and the reaction can be easily controlled. Therefore, as described in claim 1, a radical polymerization reaction is performed in a system containing a vinyl monomer and the chain transfer agent to synthesize a vinyl polymer having an iodine atom at a terminal, and then the vinyl polymer. By substituting the terminal iodine atom with a group having a functional group, it became possible to introduce a functional group into the terminal. Further, claim 2
After performing the polymerization reaction of the vinyl-based monomer by the above method as described above, and subsequently performing the polymerization reaction of the styrene-based monomer, the iodine atom at the terminal of the vinyl-based polymer is substituted with a group having a functional group. By adopting the method, the substitution reactivity between the iodine atom and the terminal functional group can be enhanced, and the introduction of the terminal functional group can be more reliably and easily performed.

[0043]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

(Example 1) 2,2'-
Using 0.82 g of azobis (isobutyronitrile), this polymerization initiator and the monomer, solvent and iodine compound shown in Table 1 were put into a 1-liter 4-neck separable flask, and a separable cover, a stirring blade, Three-way cock, cooling pipe,
After attaching the temperature probe, the inside of the container was replaced with nitrogen by bubbling. Then, while flowing nitrogen gas,
The mixture was stirred at 100 rpm, and polymerization was performed for 5 hours while maintaining the inside of the polymerization vessel at 70 ° C. After the completion of the polymerization, the terminal treating agents shown in Table 1 were added, and the mixture was boiled and refluxed for 18 hours to carry out a reaction to obtain a polymer A. After completion of the reaction, the unreacted monomer, unreacted terminal treating agent, and solvent were purified and removed, and a solution of the polymer A having a hydroxyl group at a terminal was taken out. In addition, the unit of the compounding amount described in Table 1 is part by weight.

For the obtained polymer A, the number average molecular weight (MN), weight average molecular weight (MW), molecular weight distribution, and terminal functional group introduction rate were measured by the following evaluation methods. Table 1 shows the measurement results of the number average molecular weight, the molecular weight distribution, and the terminal functional group introduction rate.

[Evaluation method] (1) Measurement of number average molecular weight and weight average molecular weight Polymer A was measured by gel permeation column chromatography using tetrahydrofuran as an eluent using the following columns to obtain a polystyrene standard product. The number average molecular weight and the weight average molecular weight were calculated using the calibration curve obtained from the above. Column: KF-80M x 2 columns, manufactured by Showa Denko KK (2) Molecular weight distribution Calculated from the ratio [(MW) / (MN)] between the weight average molecular weight and the number average molecular weight measured in (1).

(3) Terminal Functional Group Introduction Rate According to JIS K 1557, the polymer A is esterified with a pyridine solution of phthalic anhydride, and the excess reagent is titrated with a sodium hydroxide solution to obtain a hydroxyl group. The radix was calculated. The percentage of the number of introduced hydroxyl groups with respect to the theoretical value was calculated and defined as a terminal functional group introduction rate.

Example 2 A polymer B having a terminal hydroxyl group was obtained in the same manner as in Example 1 except that the compounds shown in Table 1 were used. About the obtained polymer B, the number average molecular weight (MN), the weight average molecular weight (MW), the molecular weight distribution, and the terminal functional group introduction rate were measured in the same manner as in Example 1. The results are shown in Table 1.

Example 3 A polymer C having a terminal carboxyl group was obtained in the same manner as in Example 1 except that the compounds shown in Table 1 were used. About the obtained polymer C, the number average molecular weight (MN), the weight average molecular weight (MW), the molecular weight distribution, and the terminal functional group introduction rate were measured using the following evaluation methods. The results are shown in Table 1.

[Evaluation Method] (1) Measurement of Number-Average Molecular Weight and Weight-Average Molecular Weight The following column was determined by gel permeation column chromatography using Polymer B as a eluent with a 5 mM lithium bromide / dimethylformamide solution. The number average molecular weight and the weight average molecular weight were calculated using a calibration curve obtained from a polyethylene oxide standard product. Column: KD-805 and KD-80, manufactured by Showa Denko KK
2.5 (2) Molecular weight distribution It was calculated from the ratio [(MW) / (MN)] between the weight average molecular weight and the number average molecular weight measured in (1).

(3) Terminal Functional Group Introduction Rate The number of carboxyl groups was calculated by titrating the polymer C with a sodium hydroxide solution in a pyridine solution. The percentage of the number of carboxyl groups introduced to the theoretical value was calculated and defined as the terminal functional group introduction rate.

Example 4 A polymer D having an amino group at the terminal was obtained in the same manner as in Example 1 except that the compounds shown in Table 1 were used. For the obtained polymer D, the number average molecular weight (MN), the weight average molecular weight (MW) and the molecular weight distribution were measured in the same manner as in Example 1, and the terminal functional group introduction rate was measured using the following evaluation method. . The results are shown in Table 1.

[Evaluation method] (1) Terminal functional group introduction rate According to JIS K 1557, polymer D is amidated with a pyridine solution of phthalic anhydride, and excess reagent is titrated with a sodium hydroxide solution. Thereby, the number of amino groups was calculated. The percentage of the number of introduced amino groups to the theoretical value was calculated and defined as the terminal functional group introduction rate.

Example 5 A polymer E having a vinyl group at a terminal was obtained in the same manner as in Example 1 except that the compounds shown in Table 1 were used. For the obtained polymer E, the number average molecular weight (MN), the weight average molecular weight (MW) and the molecular weight distribution were measured in the same manner as in Example 1, and the terminal functional group introduction rate was measured using the following evaluation method. . The results are shown in Table 1.

[Evaluation Method] (1) Terminal Functional Group Introduction Rate The number of vinyl groups was calculated by measuring the polymer E in deuterated chloroform by 1H-NMR. The percentage of the number of vinyl groups introduced to the theoretical value was calculated and defined as the terminal functional group introduction rate.

Example 6 A polymer F having a terminal triethoxysilyl group was obtained in the same manner as in Example 1 except that the compounds shown in Table 1 were used. For the obtained polymer F, the number average molecular weight (MN), the weight average molecular weight (MW) and the molecular weight distribution were measured in the same manner as in Example 1, and the terminal functional group introduction rate was measured using the following evaluation method. . The results are shown in Table 1.

[Evaluation Method] (1) Terminal Functional Group Introduction Rate The number of triethoxysilyl groups was calculated by measuring the polymer E in deuterated chloroform by 1H-NMR. The percentage of the number of triethoxysilyl groups introduced to the theoretical value was calculated and defined as the terminal functional group introduction rate.

Example 7 2,2'-
Polymerization was carried out for 5 hours while maintaining the inside of the polymerization vessel at 70 ° C. in the same manner as in Example 1 except that 1.6 g of azobis (isobutyronitrile) was used and the monomers 1 shown in Table 1 were used. After the completion of the polymerization, styrene as the monomer 2 shown in Table 1 was added, and the mixture was further polymerized at 70 ° C. for 3 hours. After the polymerization, Table 1
, And reacted at 120 ° C. for 4 hours to obtain a polymer G. About the obtained polymer G, the number average molecular weight (MN), the weight average molecular weight (MW), the molecular weight distribution, And the terminal functional group introduction rate was measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 8) Using the monomers 1 shown in Table 1, polymerization was carried out for 5 hours while maintaining the inside of the polymerization vessel at 70 ° C in the same manner as in Example 7. After completion of the polymerization, monomer 2 shown in Table 1
And further polymerized at 70 ° C. for 3 hours. After completion of the polymerization, the terminal treating agent shown in Table 1 was added, and 1
The reaction was carried out at 00 ° C. for 8 hours to obtain a polymer H. With respect to the obtained polymer H, the number average molecular weight (MN), the weight average molecular weight (MW), the molecular weight distribution, and the terminal functional group introduction rate were determined in Examples. It measured similarly to 1. The results are shown in Table 1.

Example 9 Using the monomers 1 shown in Table 1, polymerization was carried out for 5 hours while maintaining the inside of the polymerization vessel at 70 ° C. in the same manner as in Example 7. After completion of the polymerization, monomer 2 shown in Table 1
And further polymerized at 70 ° C. for 3 hours. After completion of the polymerization, the terminal treating agent shown in Table 1 was added, and 1
The reaction was carried out at 20 ° C. for 4 hours to obtain a polymer I. With respect to the obtained polymer I, the number average molecular weight (MN), the weight average molecular weight (MW), the molecular weight distribution, and the terminal functional group introduction rate were measured in Examples. It measured similarly to 1. The results are shown in Table 1.

(Example 10) In the same manner as in Example 7 except that the monomer 1 shown in Table 1 was used, while maintaining the inside of the polymerization vessel at 70 ° C, 5
Polymerization was carried out for hours. After the completion of the polymerization, styrene as the monomer 2 shown in Table 1 was added, and the mixture was further polymerized at 70 ° C. for 3 hours. After completion of the polymerization, the terminal treating agent shown in Table 1 was added,
The reaction was carried out at 120 ° C. for 4 hours to obtain a polymer J. With respect to the obtained polymer J, the number average molecular weight (MN), weight average molecular weight (MW), molecular weight distribution, and terminal functional group introduction rate were measured in Examples. It measured similarly to 3. The results are shown in Table 1.

Comparative Example 1 A polymer K having a terminal hydroxyl group was obtained in the same manner as in Example 1 except that the compounds shown in Table 2 were used. About the obtained polymer K, the number average molecular weight (MN), the weight average molecular weight (MW), the molecular weight distribution, and the terminal functional group introduction rate were measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 2 A polymer L having a terminal hydroxyl group was obtained in the same manner as in Example 1 except that the blends shown in Table 2 were used. About the obtained polymer L, the number average molecular weight (MN), the weight average molecular weight (MW), the molecular weight distribution, and the terminal functional group introduction rate were measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 3 A polymer M having a terminal carboxyl group was obtained in the same manner as in Example 1 except that the compounds shown in Table 2 were used. About the obtained polymer M, the number average molecular weight (MN), the weight average molecular weight (MW), the molecular weight distribution, and the terminal functional group introduction rate were measured in the same manner as in Example 3. The results are shown in Table 2.

Comparative Example 4 A polymer N having a terminal amino group was obtained in the same manner as in Example 1 except that the compounds shown in Table 2 were used. About the obtained polymer N, number average molecular weight (MN), weight average molecular weight (MW), molecular weight distribution,
And the terminal functional group introduction rate was measured in the same manner as in Example 4. The results are shown in Table 2.

Comparative Example 5 A polymer O having a vinyl group at a terminal was obtained in the same manner as in Example 1 except that the compounds shown in Table 2 were used. About the obtained polymer O, number average molecular weight (MN), weight average molecular weight (MW), molecular weight distribution,
And the terminal functional group introduction rate was measured in the same manner as in Example 5. The results are shown in Table 2.

Comparative Example 6 A polymer P having a terminal triethoxysilyl group was obtained in the same manner as in Example 1 except that the compounds shown in Table 2 were used. About the obtained polymer P, number average molecular weight (MN), weight average molecular weight (MW),
The molecular weight distribution and the terminal functional group introduction rate were measured in the same manner as in Example 6. The results are shown in Table 2.

(Comparative Example 7) 2,2'-
Polymerization was carried out for 5 hours while maintaining the inside of the polymerization vessel at 70 ° C. in the same manner as in Example 1 except that 1.6 g of azobis (isobutyronitrile) was used and the monomers 1 shown in Table 2 were used. After the completion of the polymerization, the terminal treating agent shown in Table 2 was added, and the reaction was carried out at 120 ° C. for 4 hours to obtain a polymer Q. The obtained polymer Q
, The number average molecular weight (MN), weight average molecular weight (M
W), molecular weight distribution and terminal functional group introduction rate in Example 1
The measurement was performed in the same manner as described above. The results are shown in Table 2.

Comparative Example 8 Polymerization was carried out in the same manner as in Comparative Example 7 except that the compounds shown in Table 2 were used. After completion of the polymerization, the terminal treating agent shown in Table 2 was added, and the mixture was added at 120 ° C for 5 minutes.
The reaction was carried out for an hour to obtain a polymer R. About the obtained polymer R, a number average molecular weight (MN) and a weight average molecular weight (M
W), molecular weight distribution and terminal functional group introduction rate in Example 1
The measurement was performed in the same manner as described above. The results are shown in Table 2.

[0070]

[Table 1]

[0071]

[Table 2]

[0072]

According to the process for producing a vinyl polymer having a functional group at the terminal of the present invention, since the iodine compound having the above specific structure is used as a chain transfer agent, the reaction proceeds in a living manner. Can be easily introduced. Further, the vinyl polymer having a functional group at the terminal of the present invention has a high terminal functional group introduction rate, so that not only reticulation by cross-linking, but also chain elongation due to cross-linking between the ends occurs efficiently, and It is possible to form a polymer having a chain-extended shape, and to obtain a cured product excellent in elongation and tensile strength, and excellent in heat resistance, water resistance, durability and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4J011 AA05 BA05 BB01 BB02 BB07 BB09 BB10 HA03 HA04 HB02 HB13 HB22 NA28 4J100 AB02P AC00P AF06P AG02P AJ02P AL03P AL04P AL05P AL08P AL09P AL11P AM02 BA04BA03 BA03 BA01 BA03H FA19 FA35 FA43 HA04 HA21 HA29 HA35 HA45 HC01 JA01 JA03 JA05 JA67

Claims (7)

[Claims] An iodine compound having at least two iodine atoms and having a structure in which the iodine atom is bonded to a carbon atom bonded to an aromatic ring is used as a chain transfer agent. By performing a radical polymerization reaction in a system containing the chain transfer agent and synthesizing a vinyl polymer having an iodine atom at a terminal, by replacing the iodine atom at the terminal of the vinyl polymer with a group having a functional group. A method for producing a vinyl polymer having a functional group at a terminal, characterized by introducing a functional group at the terminal. 2. An iodine compound containing at least two iodine atoms and having a structure in which the iodine atom is bonded to a carbon atom bonded to an aromatic ring, as a chain transfer agent,
By performing a radical polymerization reaction in a system containing a vinyl monomer and the chain transfer agent, and subsequently performing a polymerization reaction of a styrene monomer, a styrene polymer is interposed between the vinyl polymer and terminal iodine atoms. A vinyl polymer having a functional group at the terminal characterized by introducing a functional group at the terminal by replacing the iodine atom at the terminal of the vinyl polymer with a group having a functional group. A method for producing a vinyl polymer. 3. The method for producing a vinyl polymer having a terminal functional group according to claim 2, wherein the weight fraction of the styrene polymer in the vinyl polymer is 10% or less. . 4. The functional group to be introduced into the terminal is at least one functional group selected from the group consisting of a hydroxyl group, an amino group, an amino group, a carboxyl group, a vinyl group and a silyl group. Item 1. The method for producing a vinyl polymer having a terminal functional group according to any one of Items 1 to 3. 5. The method for producing a vinyl polymer having a terminal functional group according to claim 1, wherein the vinyl monomer is a (meth) acrylic acid ester. Method. 6. The method for producing a vinyl polymer having a terminal functional group according to claim 1, wherein the vinyl monomer is (meth) acrylonitrile. 7. A vinyl polymer produced by using the production method according to any one of claims 1 to 6, having a number average molecular weight of 500 to 500,000 and a terminal functional group introduction rate. A vinyl polymer having a functional group at a terminal, which is 90% or more.