WO2019189276A1 - Method for manufacturing polymer, polymer and polymer composition - Google Patents

Abstract

Provided is a method for manufacturing a polymer whereby a thiocarbonylthio group bound to an end of a polymer can be easily and highly selectively replaced by a hydrogen atom without using a metal. A polymer is produced by a method that comprises: step A for polymerizing a monomer in the presence of a thiocarbonylthio compound to give polymer T having a group [-SC(=S)R¹] (wherein R¹ represents a monovalent organic group) at one end; and step B for contacting polymer T with a thiol group-containing compound without adding a radical generator to thereby replace the group [-SC(=S)R¹] in polymer T by a hydrogen atom.

Description

Production method of polymer, polymer and polymer composition Cross-reference of related applications

This application is based on Japanese Patent Application No. 2018-62480 filed on March 28, 2018, the contents of which are incorporated herein by reference.

The present disclosure relates to a method for producing a polymer, a polymer, and a polymer composition.

Since reversible addition-fragmentation chain transfer (RAFT) polymerization can precisely control the polymerization reaction of monomers, it has been attempted to be applied to various applications such as resist technology, dispersants, adhesives and the like. A thiocarbonylthio group derived from the RAFT agent is bonded to the end of the polymer produced by RAFT polymerization. For this reason, when a radical generate | occur | produces by irradiating a polymer with an ultraviolet-ray, there exists a concern that coloring etc. may arise. In order to avoid such inconveniences, various methods for inactivating the thiocarbonylthio group bonded to the terminal of the polymer obtained by RAFT polymerization by removing or converting it have been proposed (for example, patents). Documents 1 to 3 and Non-Patent Documents 1 and 2).

Patent Document 1 discloses a method of bringing a metal having a thiocarbonylthio group at a terminal into contact with a metal phosphite salt and a radical generator. Non-Patent Document 1 discloses a method for removing a thiocarbonylthio group at a polymer terminal using a tin compound as a metal catalyst. In Patent Document 2, a free radical source (radical generator) is added to a polymer having a thiocarbonylthio group at the end, thereby replacing the thiocarbonylthio group with a partial structure derived from the free radical source. A method is disclosed. Patent Document 3 discloses a method for converting a terminal structure of a polymer by adding a chain transfer agent and a free radical source to a polymer having a thiocarbonylthio group at the terminal. Non-Patent Document 2 discloses that a polymer having a thiocarbonylthio group at the terminal is reacted with a thiol compound and azobisisobutyronitrile (AIBN).

Special Table 2007-537341 Japanese Patent Laid-Open No. 2005-226051 JP 2006-2096 A

In the conventional method, a structure derived from a compound used for deactivation of a polymer terminal is introduced into the polymer terminal, and the thiocarbonylthio group at the polymer terminal is replaced with a hydrogen atom (hydrogenation). The efficiency is not high enough. Further, as in Patent Document 1 and Non-Patent Document 1, when a metal is used as a radical generator or together with a radical generator to remove or convert the thiocarbonylthio group at the end of the polymer to inactivate it, There is a concern that its use will be limited. A polymer obtained by replacing the terminal of a polymer obtained by RAFT polymerization with a hydrogen atom is expected to be applied to various uses in addition to electric materials.

The present disclosure has been made in view of the above problems, and provides a method for producing a polymer capable of easily and highly selectively replacing a thiocarbonylthio group bonded to a polymer terminal with a hydrogen atom. For one purpose.

According to the present disclosure, the following means are provided.
[1] A polymer T having a group “—SC (═S) R ¹ ” (where R ¹ is a monovalent organic group) polymerized by polymerizing a monomer in the presence of a thiocarbonylthio compound. Obtaining step A;
A step B in which the polymer T is brought into contact with the thiol group-containing compound without adding a radical generator to replace the group “—SC (═S) R ¹ ” of the polymer T with a hydrogen atom; A method for producing a polymer, comprising:
[2] A radical generator is added to the polymer T having a group “—SC (═S) R ¹ ” (where R ¹ is a monovalent organic group) and a thiol group-containing compound. The group “—SC (═S) R ¹ ” of the polymer T is replaced with a hydrogen atom without contact.
[3] A polymer obtained by the production method of [1] above.
[4] A polymer composition containing the polymer of [3] above.

According to the production method of the present disclosure, the polymer having the group “—SC (═S) R ¹ ” at the terminal and the thiol group-containing compound are contacted without adding a radical generator, The group “—SC (═S) R ¹ ” at the end of the polymer can be replaced with a hydrogen atom with high selectivity. Moreover, it is not necessary to use a metal for deactivation of the polymer terminal, which is preferable in that it is difficult to limit the use of the polymer terminal.

FIG. 1 is a diagram showing an analysis result of a polymer terminal structure by pyrolysis gas chromatography mass spectrometry. FIG. 2 is a diagram showing the analysis results of the polymer terminal structure by matrix-assisted laser desorption / ionization time-of-flight mass spectrometry.

[Method for producing polymer]
Hereinafter, a method for producing the polymer of the present disclosure will be described. This manufacturing method includes the following step A and step B.
Step A: a step of polymerizing a monomer in the presence of a thiocarbonylthio compound to obtain a polymer having a group “—SC (═S) R ¹ ” at its terminal (hereinafter also referred to as “polymer T”).
Step B: A step of bringing the polymer “T” and the thiol group-containing compound into contact with each other without adding a radical generator and replacing the group “—SC (═S) R ¹ ” of the polymer T with a hydrogen atom.

≪Process A≫
<Monomer>
The monomer used for polymerization is not particularly limited as long as it can be polymerized, but a compound having a radical polymerizable unsaturated bond (hereinafter also referred to as “polymerizable unsaturated compound”) can be preferably used. Among these, it is more preferable to include at least one selected from the group consisting of (meth) acrylic compounds and aromatic vinyl compounds, and it is more preferable to include at least a (meth) acrylic compound. In the present specification, the (meth) acrylic compound means to include an acrylic compound and a methacrylic compound.

Specific examples of the (meth) acrylic compound include, for example, (meth) acrylic acid, (meth) acrylic acid ω-carboxypolycaprolactone, crotonic acid, α-ethylacrylic acid, α-n-propylacrylic acid, maleic acid, Unsaturated carboxylic acids such as fumaric acid, citraconic acid, mesaconic acid, itaconic acid, vinyl benzoic acid;
Methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, isopropyl (meth) acrylate, allyl (meth) acrylate, (meth) acrylate-n-butyl, (meth ) Acrylic acid-isobutyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid-1-methylcyclopentyl, (meth) acrylic acid-2-methyl-2-adamantyl, (meth) ) -2-ethyl-2-adamantyl acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, (meth) acrylic acid-α-hydroxy-γ-butyrolactone, norbornanecarbolactyl (meth) acrylate, α- (Meth) acryloxy-γ-butyrolactone, β- (meth) acryloxy-γ-butyrolactone 3- (2,2-bis (trifluoromethyl) -2-hydroxyethyl) -endo-2- (2-methylpropenoyl) -bicyclo [2.2.1] -heptane, phenyl (meth) acrylate , Benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, lauryl (meth) acrylate, glycidyl (meth) acrylate, (meth ) Trimethoxysilylpropyl acrylate, methoxyethyl (meth) acrylate, (N) N-dimethylaminoethyl (meth) acrylate, (N) N-diethylaminoethyl (meth) acrylate, methoxypolyethylene (meth) acrylate Glycol, octoxypolyethylene glycol (meth) acrylate, α-methoxyacrylate Α, β-unsaturated carboxylic acid ester compounds such as methyl oxalate, methyl α-ethoxyacrylate, 3-methoxyacrylic acid ester, methyl crotonic acid, ethyl crotonic acid, dialkyl fumarate;
Α, β-unsaturated carboxylic acid amide compounds such as N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, etc. ;
Α, β-unsaturated carbonyl compounds such as methyl vinyl ketone, ethyl vinyl ketone, methyl isopropenyl ketone, ethyl isopropenyl ketone; vinyl carboxylates such as vinyl acetate, vinyl butyrate, vinyl benzoate; maleic anhydride, itaconic anhydride Cyclic vinyl compounds such as acids, N-butylmaleimide, N-phenylmaleimide; N-vinyl compounds such as N-vinylpyrrolidone, vinylcarbazole, vinylimidazole; ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) Examples thereof include compounds having two or more carbon-carbon double bonds such as acrylate; (meth) acrylonitrile and the like. In addition, a monomer (B) can be used individually by 1 type or in combination of 2 or more types. (Meth) acryl in this specification indicates acrylic and methacrylic.

As the aromatic vinyl compound, a styrene compound can be preferably used. Specifically, for example, styrene, hydroxystyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butyl. Examples thereof include styrene, m-ethylstyrene, p-ethylstyrene, t-butoxystyrene, vinylbenzyldimethylamine, N, N-dimethylaminomethylstyrene, 4-vinylbenzylglycidyl ether, and p-acetoxystyrene. In addition, as an aromatic vinyl compound, 1 type may be used independently and 2 or more types may be used in combination.

In the polymerization, the proportion of the (meth) acrylic compound used is preferably 20% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more, based on the total amount of monomers used for the polymerization. More preferably. The use ratio of the aromatic vinyl compound is preferably less than 50% by mass, more preferably 40% by mass, and still more preferably 20% by mass with respect to the total amount of monomers used for the polymerization.

In the polymerization, other monomers other than the (meth) acryl compound and the aromatic vinyl compound may be used. Examples of other monomers include ethylene, propylene, 1,3-butadiene, isoprene, 1,3-pentadiene and the like. The proportion of other monomers used is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total amount of monomers used for polymerization.

<Thiocarbonylthio compound>
In this step, the monomer is polymerized in the presence of the thiocarbonylthio compound to introduce the monovalent group “—SC (═S) R ¹ ” derived from the thiocarbonylthio compound at the end of the polymer. .
Examples of the monovalent organic group for R ¹ include alkyl groups having 1 to 30 carbon atoms, cycloalkyl groups, aryl groups, aralkyl groups, alkylthio groups, aralkylthio groups, heterocyclyl groups, —NR ¹¹ R ¹² , —NR ¹¹ —. NR ¹² R ¹³ , —COOR ¹¹ , —OCOR ¹¹ , —CONR ¹¹ R ¹² , —P (═O) (OR ¹¹ ) ₂ or —O—P (═O) R ¹¹ R ¹² (where R ¹¹ , R ¹² and R ¹³ each independently represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and the same shall apply hereinafter. R ¹ may be a monovalent group in which one or more hydrogen atoms bonded to the carbon atom in each of the above groups are substituted with a cyano group, a carboxy group, or the like.

The thiocarbonylthio compound can be appropriately selected from chain transfer agents (RAFT agents) used in RAFT polymerization according to the type of monomer. When a (meth) acrylic compound is used as a monomer, a bis (thiocarbonyl) disulfide compound (compound represented by the following formula (s-1)), a dithioester compound (represented by the following formula (s-2)) Compound) and at least one selected from the group consisting of trithiocarbonate compounds (compounds represented by the following formula (s-3)) can be preferably used. Of these, at least one selected from the group consisting of bis (thiocarbonyl) disulfide compounds and trithiocarbonate compounds can be used more preferably.

(In the formulas (s-1) to (s-3), Z ¹ to Z ⁶ are each independently a monovalent organic group.)

Examples of the monovalent organic group in Z ¹ to Z ⁶ in the above formulas (s-1) to (s-3) include, for example, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, Alkylthio group, aralkylthio group, heterocyclyl group, —NR ¹¹ R ¹² , —NR ¹¹ —NR ¹² R ¹³ , —COOR ¹¹ , —OCOR ¹¹ , —CONR ¹¹ R ¹² , —P (═O) (OR ¹¹ ) ₂ Alternatively, —O—P (═O) R ¹¹ R ^{12 and the} like can be given. R ¹ may be a monovalent group in which one or more hydrogen atoms bonded to the carbon atom in each of the above groups are substituted with a cyano group, a carboxy group, or the like.
Z ⁴ in the above formula (s-2) is preferably an aromatic group such as a phenyl group, and Z ⁶ in the above formula (s-3) is preferably an alkyl group.

Specific examples of thiocarbonylthio compounds include bis (thiocarbonyl) disulfide compounds such as tetraethylthiuram disulfide, tetramethylthiuram disulfide, bis (n-octylmercapto-thiocarbonyl) disulfide, bis (n-dodecylmercapto-thiocarbonyl). ) Disulfide, bis (benzylmercapto-thiocarbonyl) disulfide, bis (n-butylmercapto-thiocarbonyl) disulfide, bis (t-butylmercapto-thiocarbonyl) disulfide, bis (n-heptylmercapto-thiocarbonyl) disulfide, bis (N-hexyl mercapto-thiocarbonyl) disulfide, bis (n-pentyl mercapto-thiocarbonyl) disulfide, bis (n-nonyl mercapto-thio) Carbonyl) disulfide, bis (n-decylmercapto-thiocarbonyl) disulfide, bis (t-dodecylmercapto-thiocarbonyl) disulfide, bis (n-tetradecylmercapto-thiocarbonyl) disulfide, bis (n-hexadecylmercapto-thio) Carbonyl) disulfide, bis (n-octadecylmercapto-thiocarbonyl) disulfide and the like;
Examples of dithioester compounds include 2-phenyl-2-propylbenzothioate, 4-cyano-4- (phenylthiocarbonylthio) pentanoic acid, 2-cyano-2-propylbenzodithioate and the like;
Examples of trithiocarbonate compounds include S- (2-cyano-2-propyl) -S-dodecyltrithiocarbonate, 4-cyano-4-[(dodecylsulfanyl-thiocarbonyl) sulfanyl] pentanoic acid, cyanomethyldodecyltri Examples thereof include thio-carbonate, 2- (dodecylthiocarbonothiolthio) -2-methylpropionic acid, and the like.

The ratio of the thiocarbonylthio compound used in the above polymerization is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, with respect to 100 parts by mass of the total amount of monomers. Moreover, the usage-amount of a thiocarbonylthio compound becomes like this. Preferably it is 20 mass parts or less with respect to a total of 100 mass parts of a monomer, More preferably, it is 10 mass parts or less. In addition, as a thiocarbonylthio compound, 1 type can be used individually or in combination of 2 or more types.

<Radical generator>
The polymerization is preferably performed in the presence of a radical generator from the viewpoint of productivity. The radical generator can be appropriately selected from radical polymerization initiators generally used in conventionally known radical polymerization. Specifically, it is a compound that generates radicals by heat or light. For example, a compound that generates radicals by heating, such as peroxides, azo compounds, or redox initiators, or a compound that generates radicals by irradiation with radiation. Can be mentioned.

Specific examples of compounds that generate radicals upon heating include peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxyoctanoate, peroxy T-butyl neodecanoate, t-butyl peroxyisobutyrate, lauroyl peroxide, t-amyl peroxypivalate, t-butyl peroxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate, etc .;
Examples of the azo compound include azobisisobutyronitrile (AIBN), 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-butanenitrile), 4,4′-azobis (4- Pentanoic acid), 1,1′-azobis (cyclohexanecarbonitrile), 2- (t-butylazo) -2-cyanopropane, 2,2′-azobis [2-methyl-N- (1,1) -bis ( Hydroxymethyl) -2-hydroxyethyl] propionamide, 2,2′-azobis (2-methyl-N-hydroxyethyl) propionamide, 2,2′-azobis (N, N′-dimethyleneisobutylamidine) dichloride, 2,2′-azobis (2-amidinopropane) dichloride, 2,2′-azobis (N, N-dimethyleneisobutyramide), 2,2′-azobis (2-methyl) -N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide), 2,2'-azobis (2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide) ), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (isobutyramide) dihydrate and the like;

Examples of redox initiators include a combination of sulfite, acidic sodium sulfite and ferrous sulfate, a combination of t-butyl hydroperoxide, acidic sodium sulfite and ferrous sulfate, and p-menthane hydroperoxide. And a combination of ferrous sulfate, sodium ethylenediaminetetraacetate and sodium formaldehyde sulfoxylate; As the compound that generates radicals upon heating, an azo compound is preferable in that a side reaction product due to oxygen or the like is not easily generated, and azobisisobutyronitrile is particularly preferable.

Specific examples of compounds that generate radicals upon irradiation with radiation include, for example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, benzaldehyde, Fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, benzoin propyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethylthioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2- Ruphorino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like.

When the polymerization is carried out in the presence of a radical generator, the proportion of the radical generator used is preferably 1 part by mass or more, more preferably 10 parts by mass with respect to 100 parts by mass of the thiocarbonylthio compound used in the polymerization. More than a part. Moreover, the usage-amount of a radical generator becomes like this. Preferably it is 1,000 mass parts or less with respect to 100 mass parts of thiocarbonylthio compounds used in superposition | polymerization, More preferably, it is 100 mass parts or less. In addition, as a radical generator, 1 type can be used individually or in combination of 2 or more types.

The polymerization is preferably performed by solution polymerization. As the polymerization method, either a batch type or a continuous type may be used. The solvent to be used may be an organic solvent inert to the reaction, and examples thereof include alcohols, ethers, ketones, esters, and mixtures thereof.
Specific examples of the solvent used for the polymerization include alcohols such as ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, 1-methoxy-2-propanol, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol and the like;
Examples of ethers include 1,4-dioxane, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like;
Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-methylcyclohexanone, diisobutyl ketone and the like;
Examples of esters include methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, and the like. In addition, as a solvent, 1 type can be used individually or in combination of 2 or more types.

The ratio of the solvent used in the solution polymerization may be appropriately set according to the solubility of the monomer in the solvent, etc., but from the viewpoint of reaction efficiency, it is 30 to 1,000 parts by mass with respect to 100 parts by mass of the total amount of monomers. It is preferably 50 to 800 parts by mass.

The polymerization temperature is not particularly limited as long as the polymerization can proceed, but is preferably 0 ° C. or more from the viewpoint of productivity, and more preferably in the range of 0 ° C. to 140 ° C., A range of 20 ° C to 100 ° C is more preferable, and a range of 50 ° C to 90 ° C is particularly preferable. The polymerization temperature is preferably set considering that the polymerization reaction is an exothermic reaction. The polymerization temperature can be controlled by adjusting the feed rate and temperature of the radical generator, monomer and solvent, and cooling and heating from the outside of the reactor. The polymerization reaction is preferably carried out under a pressure sufficient to keep the monomer in a substantially liquid phase. The polymerization reaction time is preferably 30 minutes to 20 hours, more preferably 1 to 10 hours. By the above polymerization reaction, a polymer solution containing a polymer T having a group “—SC (═S) R ¹ ” derived from a thiocarbonylthio compound at its terminal is obtained.

Polymer T may be isolated from the polymer solution after completion of the polymerization. For isolation of the polymer T, a conventionally known method can be employed. Specifically, for example, the solvent is separated by, for example, steam stripping, and then the polymer is filtered and further dehydrated and dried to obtain the polymer; the polymer is concentrated in a flushing tank, and further removed by a vent extruder or the like. A method of volatilizing; a method of directly devolatilizing with a drum dryer or the like;

≪Process B≫
In the subsequent step B, the polymer T obtained in the step A is brought into contact with the thiol group-containing compound after the polymerization in the step A without adding a radical generator. By this operation, the terminal group “—SC (═S) R ¹ ” of the polymer T is replaced with a hydrogen atom. In this production method, the radical generator is not added in Step B, and the radical generator used in Step A is usually decomposed by heating or radiation irradiation for generating radicals. However, in step B, an undecomposed radical generator may be present among the radical generators used in step A as long as the effects of the present invention are not impaired.

<Thiol group-containing compound>
The thiol group-containing compound to be used is not particularly limited as long as it has a function of a chain transfer agent. As the thiol group-containing compound, a compound represented by the following formula (1) can be preferably used.
R ² -SH (1)
(In the formula (1), R ² represents a monovalent hydrocarbon group having 1 to 30 carbon atoms, or —C (═O) O— between carbon-carbon bonds of a hydrocarbon group having 2 to 30 carbon atoms. And at least one hydrogen atom may be substituted with a hydroxyl group, a carboxy group or —SO ₃ Na.)

In the above formula (1), examples of the monovalent hydrocarbon group for R ² include 1 to 30 alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Among these, R ² is preferably a monovalent hydrocarbon group, more preferably an alkyl group having 1 to 30 carbon atoms, and still more preferably an alkyl group having 4 to 30 carbon atoms.
Specific examples of the thiol group-containing compound include, for example, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, mercaptoacetic acid, methyl mercaptoacetate, ethyl mercaptoacetate, 2-ethylhexyl mercaptoacetate, 3-mercaptopropionic acid. , Methyl-3-mercaptopropionate, hexyl 3-mercaptopropionate, cyclohexyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, octyl 3-mercaptopropionate, dodecyl 3-mercaptopropionate Narate, tridecyl 3-mercaptopropionate, octadecyl 3-mercaptopropionate, mercaptosuccinic acid, sodium 2-mercaptoethanesulfonate, 1-ethanethiol, 1- Lopanthiol, 1-butanethiol, 2-butanethiol, 1-pentanethiol, 1-hexanethiol, 1-heptanethiol, 1-octanethiol, 1-decanethiol, 1-dodecanethiol, 1-hexadecanethiol, 1 -Octadecanethiol, 2-methyl-1-propanethiol, t-dodecyl mercaptan, cyclohexanethiol, thiophenol and the like.

The ratio of the thiol group-containing compound used in Step B is preferably 0.1% by mass or more based on the total amount of the polymer T used when the thiol group-containing compound and the polymer T are brought into contact with each other. More preferably 3% by mass or more. Moreover, it is preferable to set it as 20 mass% or less with respect to the whole quantity of the polymer T to be used, and, as for the usage-amount of a thiol group containing compound, it is more preferable to set it as 15 mass% or less. In addition, as a thiol group containing compound, 1 type can be used individually or in combination of 2 or more types.

The contact between the polymer T obtained in the above step A and the thiol group-containing compound is preferably carried out in an organic solvent. As an organic solvent used, the organic solvent illustrated as a solvent which can be used for superposition | polymerization can be mentioned. From the viewpoint of productivity, it is preferable to use the polymer solution obtained in the above step A as it is and add a thiol group-containing compound to the polymer solution. In that case, the use ratio of the thiol group-containing compound is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass with respect to 100 parts by mass of the polymer. It is desirable to set the usage ratio of the monomer and the usage ratio of the thiol group-containing compound in this step.

The temperature at which the polymer T and the thiol group-containing compound are brought into contact with each other (hereinafter also referred to as “modification temperature”) is a value obtained by replacing the group “—S—C (═S) R ¹ ” with a hydrogen atom. It is preferably 40 ° C. or higher in that it can be performed with high selectivity. The modification temperature is more preferably 50 ° C. or higher, still more preferably 60 ° C. or higher, and particularly preferably 70 ° C. or higher. The denaturation temperature is preferably 130 ° C. or less, more preferably 120 ° C. or less, and even more preferably 110 ° C. or less, from the viewpoint that the effect of suppressing a decrease in reactivity due to heat is high. The reaction time is preferably 15 minutes to 15 hours, more preferably 30 minutes to 8 hours.

In Step B, the polymer T and the thiol group-containing compound are preferably contacted in an organic solvent without adding a radical generator into the system after the completion of the polymerization in Step A. In addition, when using the polymer solution obtained by the said process A as it is and making a thiol group containing compound and the polymer T contact in the polymer solution, reaction of terminal hydrogenation of the polymer T by a thiol group containing compound As long as the mechanism is not hindered, the undecomposed component of the radical generator added as the polymerization initiator in Step A is slightly contained in the system containing the polymer T and the thiol group-containing compound in Step B. It is permissible. In this case, the content ratio of the undecomposed radical generator in the system is preferably 1% by mass or less based on the total amount of the thiol group-containing compounds used when the polymer T and the thiol group-containing compound are brought into contact with each other. More preferably, it is 0.5 mass% or less.

When the polymer T and the thiol group-containing compound are brought into contact with each other in a solution, a solution containing a polymer obtained by the reaction (hereinafter also referred to as “polymer P”) can be isolated by, for example, steam. It can be performed by a known desolvation method such as stripping and a drying operation such as heat treatment. In this step B, since the thiocarbonylthio group at the terminal of the polymer T is hydrogenated without adding a metal, the polymer P is suitable in that it is difficult to limit the use of the polymer P for electric materials.

The conversion efficiency from the group “—SC (═S) R ¹ ” to a hydrogen atom at the terminal of the polymer T (hereinafter also referred to as “terminal conversion efficiency”) is preferably 40% or more, more preferably 50%. More preferably, it is 60% or more. The terminal conversion efficiency (%) is a value calculated using ¹ H-NMR measurement data, and is represented by the following formula (3).
Terminal conversion efficiency = 100 − [{(A1 / R1) / (A2 / R2)} × 100]
... (3)
(In Formula (3), A1 is the integrated value of the peak derived from the terminal group after the contact between the polymer T and the thiol group-containing compound, and A2 is before the contact between the polymer T and the thiol group-containing compound. R1 is the integral value of the peak of the whole polymer excluding the terminal group after contact between the polymer T and the thiol group-containing compound, and R2 is the polymer T and the thiol. (This is the peak integrated value of the entire polymer excluding the end groups before contact with the group-containing compound.)

The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the obtained polymer P may be appropriately selected according to the use of the polymer, etc., but preferably 1.0 × 10 ³ to 2.0 × 10 ⁶ , more preferably 1.0 × 10 ³ to 1.0 × 10 ⁵ . Further, the molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 3 or less, more preferably 2.5 or less. .

[Polymer composition]
The polymer composition of the present disclosure includes, as a polymer component, a polymer in which a polymer terminal group “—SC (═S) R ¹ ” is substituted with a hydrogen atom by the production method of the present disclosure. The polymer and polymer composition obtained by the production method of the present disclosure are used for various applications. Specifically, for example, various resin compositions such as a photoresist composition, a liquid immersion composition, an upper layer film-forming composition, an adhesive, a dispersant, a compatibilizing agent, a surfactant, a footwear material, various It can be applied to various uses such as automobile parts, industrial articles, asphalt compositions, paints, and biomaterials.

Hereinafter, although it demonstrates concretely based on an Example, the content of this indication is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. The measuring method of various physical property values of the polymer is as follows.
[Mass average molecular weight Mw and number average molecular weight Mn]
It calculated | required in polystyrene conversion from the retention time corresponded to the peak peak of the GPC curve obtained using gel permeation chromatography (Brand name "HLC-8120GPC", the Tosoh company make) on the following conditions.
Column: Two brand names “GMHXL” (manufactured by Tosoh Corporation) Column temperature: 40 ° C.
Mobile phase; tetrahydrofuran flow rate; 1.0 ml / min sample concentration; 10 mg / 20 ml
[Terminal conversion efficiency]
Terminal conversion efficiency (%) was calculated by the above formula (3) using measurement data by ¹ H-NMR.
[Pyrolysis gas chromatograph mass spectrometry]
Polymer end groups were analyzed using a pyrolysis gas chromatograph mass spectrometer under the following conditions. About the sample, it wrapped in the pyrofoil and measured.
(Measurement condition)

[Example 1]
To a 50 ml flask under a nitrogen atmosphere, 2.9 g of 2-cyano-2-propyldodecyltrithiocarbonate, 16 g of p-acetoxystyrene, and 0.080 g of 1-methoxy-2-propanol as a polymerization solvent were added and stirred. Subsequently, 7.7 g of a 1-methoxy-2-propanol solution of azobisisobutyronitrile (0.1 mol / L) was added, and then the flask temperature was raised to 80 ° C. to initiate polymerization. After performing the polymerization reaction for 3 hours, the polymer powder A was obtained by reprecipitation in a hexane solvent.
Next, in a 30 ml flask under nitrogen atmosphere, 3.2 g of polymer powder A was dissolved in 2.1 g of 1-methoxy-2-propanol, 1.7 g of t-dodecyl mercaptan was added, and the reaction was performed at a temperature of 80 ° C. for 1 hour. I let you. The obtained polymer Ap was reprecipitated and purified, and polymer analysis was performed by ¹ H-NMR. As a result, a decrease in the peak derived from the polymer terminal end was confirmed (terminal conversion efficiency was 78%).

[Example 2]
To a 50 ml flask under a nitrogen atmosphere, 2.9 g of 2-cyano-2-propyldodecyltrithiocarbonate, 17 g of 1-methylcyclopentyl methacrylate, and 0.37 g of 1-methoxy-2-propanol as a polymerization solvent were added and stirred. . Subsequently, 7.7 g of a 1-methoxy-2-propanol solution of azobisisobutyronitrile (0.1 mol / L) was added, and then the flask temperature was raised to 80 ° C. to initiate polymerization. After reacting for 3 hours, polymer powder B was obtained by reprecipitation in a hexane solvent.
Next, in a 30 ml flask under nitrogen atmosphere, 3.4 g of the polymer powder B was dissolved in 2.2 g of 1-methoxy-2-propanol, 1.7 g of t-dodecyl mercaptan was added, and the modification temperature was 80 ° C. The reaction was carried out for 1 hour. The obtained polymer Bp was reprecipitated and purified, and polymer analysis was conducted by ¹ H-NMR. As a result, a decrease in the peak derived from the polymer terminal end was confirmed (terminal conversion efficiency was 86%).

[Example 3]
To a 50 ml flask under a nitrogen atmosphere, 0.86 g of 2-cyano-2-propyldodecyltrithiocarbonate, 8.4 g of methyl methacrylate, and 1.7 g of 1-methoxy-2-propanol as a polymerization solvent were added and stirred. Next, 2.5 g of a 1-methoxy-2-propanol solution of azobisisobutyronitrile (0.1 mol / L) was added, and the temperature was raised to 80 ° C. to initiate polymerization. Polymer solution C was obtained by reacting for 3 hours.
Next, 6.7 g of polymer solution C (polymer concentration 66% by mass) and 1.0 g of t-dodecyl mercaptan were added to a 30 ml flask under a nitrogen atmosphere and reacted at 80 ° C. for 3 hours. The obtained polymer Cp was reprecipitated and purified, and polymer analysis was performed by ¹ H-NMR. As a result, a decrease in the peak derived from the polymer terminal end was confirmed (terminal conversion efficiency was 42%).

[Example 4]
In a 100 ml flask under a nitrogen atmosphere, 2.2 g of 2-cyano-2-propyldodecyltrithiocarbonate, 13 g of p-acetoxystyrene, 20 g of 1-methylcyclopentyl methacrylate, 1-methoxy-2-propanol as a polymerization solvent 9. 8 g was added and stirred. Subsequently, 5.9 g of a 1-methoxy-2-propanol solution of azobisisobutyronitrile (0.1 mol / L) was added, and then the flask temperature was raised to 80 ° C. to initiate polymerization. On the way, a polymer solution was obtained by reacting for 6 hours while adding 5.3 g of a 1-methoxy-2-propanol solution (0.1 mol / L) of azobisisobutyronitrile. Further, the obtained polymer solution was purified by reprecipitation in a hexane solvent to obtain a polymer powder D.
Next, 4.4 g of polymer powder D was dissolved in 2.6 g of 1-methoxy-2-propanol in a 30 ml flask under a nitrogen atmosphere, 0.80 g of t-dodecyl mercaptan was added, and the mixture was reacted at 80 ° C. for 1 hour. The obtained polymer Dp was reprecipitated and purified, and polymer analysis was performed by ¹ H-NMR. As a result, a decrease in peak derived from the polymer terminal end was confirmed (terminal conversion efficiency was 63%).

[Example 5]
Polymer powder D was obtained by performing the same operation as in Example 4. Next, 4.4 g of the polymer powder D obtained in Example 4 was dissolved in 2.6 g of 1-methoxy-2-propanol in a 30 ml flask under a nitrogen atmosphere, and 0.80 g of t-dodecyl mercaptan was added. And reacted at 80 ° C. for 3 hours. The obtained polymer Ep was reprecipitated and purified, and polymer analysis was performed by ¹ H-NMR. As a result, a decrease in the peak derived from the polymer terminal end was confirmed (terminal conversion efficiency was 80%).

[Comparative Example 1]
Polymer powder B was obtained by performing the same operation as in Example 2. Next, in a 30 ml flask under nitrogen atmosphere, 3.2 g of polymer powder B was dissolved in 36 g of 1-methoxy-2-propanol, and 7.9 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added. And reacted at a temperature of 80 ° C. for 1 hour. The resulting polymer B1 was reprecipitated and purified.
[Comparative Example 2]
Polymer powder B was obtained by performing the same operation as in Example 2. Next, in a 30 ml flask under a nitrogen atmosphere, 3.2 g of polymer powder B was dissolved in 9.0 g of 1-methoxy-2-propanol, and 2,2′-azobis (2,4-dimethylvaleronitrile) was 1. 6 g and 1.6 g of t-dodecyl mercaptan were added and reacted at a temperature of 80 ° C. for 1 hour. The resulting polymer B2 was reprecipitated and purified.

(Identification of polymer end groups)
1. Thermal decomposition gas chromatograph mass spectrometry About the terminal hydrogen-modified polymer Bp obtained in Example 2, the terminal structure was analyzed by a thermal decomposition gas chromatograph mass spectrometer (pyGCMS). The measurement results are shown in FIG. In FIG. 1, the inverted triangle mark in the upper graph is a peak derived from the vicinity of the hydrogen terminal structure obtained by the modification reaction.
2. Matrix Assisted Laser Desorption / Ionization Time-of-Flight Mass Spectrometry Matrix Assisted Laser Desorption / Ionization Time-of-Flight Mass Spectrometer for Polymer Bp, Polymer B1, and Polymer B2 obtained in Example 2, Comparative Example 1 and Comparative Example 2, respectively. The polymer molecular weight was measured by (MALDI-TOF-MS), and the terminal structure was analyzed. The measurement results are shown in FIG. In FIG. 2, the inverted triangle mark is a peak of a polymer having an azo compound-derived terminal structure (structure represented by the following formula (2)), and the circle mark is a hydrogen terminal (following formula (3). It is a peak derived from a polymer structure converted into (represented structure).

From these measurement results, it was confirmed that the terminal structure of the polymer Bp of Example 2 was replaced with a hydrogen atom. In addition, the polymer Bp of Example 2 was not selectively mixed with an azo compound-derived terminal structure and was highly selectively substituted with hydrogen atoms with respect to the polymer B1 of Comparative Example 1 and the polymer B2 of Comparative Example 2. confirmed.

From the above results, the polymer having the functional group derived from the RAFT agent and the thiol group-containing compound are brought into contact with each other without adding a radical generator after the polymerization, whereby the functional group derived from the RAFT agent is brought into a hydrogen atom. It was found that it was replaced. Moreover, the terminal conversion efficiency was also a high numerical value. From these, according to the method in which the polymer having a functional group derived from the RAFT agent and the thiol group-containing compound are brought into contact with each other without adding a radical generator after the polymerization, the functional group derived from the RAFT agent is It became clear that it can be easily and highly selectively removed and replaced with hydrogen atoms without using metal.

Claims (8)

1. A step of polymerizing a monomer in the presence of a thiocarbonylthio compound to obtain a polymer T having a group “—SC (═S) R ¹ ” (where R ¹ is a monovalent organic group) as a terminal. A and
   A step B in which the polymer T is brought into contact with the thiol group-containing compound without adding a radical generator to replace the group “—SC (═S) R ¹ ” of the polymer T with a hydrogen atom; A method for producing a polymer, comprising:
2. The method for producing a polymer according to claim 1, wherein in the step B, the polymer T and the thiol group-containing compound are contacted at 40 ° C or higher and 130 ° C or lower.
3. The method for producing a polymer according to claim 1 or 2, wherein the monomer contains at least one selected from the group consisting of (meth) acrylic compounds and aromatic vinyl compounds.
4. The method for producing a polymer according to any one of claims 1 to 3, wherein the conversion efficiency from the group "-SC (= S) R ¹ " to a hydrogen atom is 40% or more.
5. The method for producing a polymer according to any one of claims 1 to 4, wherein the thiol group-containing compound is a compound represented by the following formula (1).
   R ² -SH (1)
   (In the formula (1), R ² represents a monovalent hydrocarbon group having 1 to 30 carbon atoms, or —C (═O) O— between carbon-carbon bonds of a hydrocarbon group having 2 to 30 carbon atoms. And at least one hydrogen atom may be substituted with a hydroxyl group, a carboxy group or —SO ₃ Na.)
6. The polymer T having the group “—SC (═S) R ¹ ” (where R ¹ is a monovalent organic group) and the thiol group-containing compound are contacted without adding a radical generator. Then, the group “—SC (═S) R ¹ ” of the polymer T is replaced with a hydrogen atom.
7. A polymer obtained by the production method according to any one of claims 1 to 5.
8. A polymer composition containing the polymer according to claim 7.

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