TW201942147A - 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 to Related Applications]
This application is based on Japanese Patent Application No. 2018-62480 filed on March 26, 2018, and the content thereof is incorporated in this application.

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

Reversible addition-fragmentation chain transfer (RAFT) polymerization can precisely control the polymerization reaction of monomers, so it has been tried to apply to various applications such as resist technology, dispersant, and adhesive. The terminal bond of the polymer produced by RAFT polymerization is derived from the thiocarbonylthio group of the RAFT agent. Therefore, when radicals are generated by irradiating the polymer with ultraviolet rays, there is a concern that coloration or the like occurs. In order to avoid such disadvantages, various methods have been previously proposed to remove or convert a thiocarbonylthio group bonded to a terminal of a polymer obtained by RAFT polymerization (for example, refer to Patent Documents 1 to 3). , Non-patent literature 1, non-patent literature 2).

Patent Document 1 discloses a method in which a metal phosphite and a radical generator are brought into contact with a polymer having a thiocarbonylthio group at a terminal. Non-Patent Document 1 discloses a method of using a tin compound as a metal catalyst and removing a thiocarbonylthio group at a polymer terminal. In addition, Patent Document 2 discloses that a free radical source (radical generator) is added to a polymer having a thiocarbonylthio group at its terminal, thereby replacing the thiocarbonylthio group with a free radical source. Partially structured approach. Patent Document 3 discloses a method of 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 a terminal. Non-Patent Document 2 discloses that a thiol compound and azobisisobutyronitrile (AIBN) are reacted with a polymer having a thiocarbonylthio group at the terminal.
[Prior Art Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2007-537341
[Patent Document 2] Japanese Patent Laid-Open No. 2005-226051
[Patent Document 3] Japanese Patent Laid-Open No. 2006-2096
[Non-patent literature]

[Non-Patent Document 1] A. Postma et.al, American Chemical Society, 2006, 5293-5306.
[Non-Patent Document 2] S. Harrisson et.al, Macromolecules, 2009, 42, 897-898.

[Problems to be Solved by the Invention]
In the previous method, the structure derived from the compound used when the polymer terminal was inertized was introduced into the polymer terminal, and the efficiency of replacing the thiocarbonylthio group at the polymer terminal with a hydrogen atom (hydrogenation) was not sufficiently high. . In addition, as in Patent Literature 1 or Non-Patent Literature 1, as a radical generator or using a metal in combination with a radical generator to remove or convert a thiocarbonylthio group at the terminal of a polymer to make it inert, there is a concern. Its use in electrical applications is limited. A polymer obtained by substituting a terminal of a polymer obtained by RAFT polymerization with a hydrogen atom is expected to be used in various applications in addition to electrical materials.

This disclosure is made in view of the said subject, and one of the objects is to provide the manufacturing method of the polymer which can replace the thiocarbonylthio group which is bonded to the polymer terminal with a hydrogen atom easily and highly selectively.
[Means for solving problems]

According to the present disclosure, the following means are provided.
[1] A method for producing a polymer, comprising: step A, polymerizing a monomer in the presence of a thiocarbonylthio compound to obtain a group having "-SC (= S) R ¹ " at the end (where R ¹ is Polymer T of a monovalent organic group); and step B, contacting the polymer T with a thiol group-containing compound without adding a radical generator, and bringing the group "-SC" of the polymer T (= S) R ¹ ″ is replaced with a hydrogen atom.
[2] A method in which a polymer T having a group "-SC (= S) R ¹ " (where R ¹ is a monovalent organic group) and a thiol group are added without adding a radical generator. contacting the compound, the polymer has a group T "-SC (= S) R ^1" is a hydrogen atom substituent.
[3] A polymer obtained by the production method of [1].
[4] A polymer composition containing the polymer of [3].
[Effect of the invention]

According to the manufacturing method of the present disclosure, a polymer having a group "-SC (= S) R ¹ " at the end can be brought into contact with a thiol group-containing compound by a simple operation without the addition of a radical generator. The group "-SC (= S) R ¹ " at the end of the polymer is substituted with a hydrogen atom. In addition, it is not necessary to use a metal when the polymer terminal is inertized, and it is preferable from the viewpoint that the use in an electrical material application is not easily restricted.

[Manufacturing method of polymer]
Hereinafter, the manufacturing method of the polymer of this indication is demonstrated. This manufacturing method includes the following steps A and B.
Step A: thiocarbonylthio compound in the presence of the monomer is polymerized to obtain a group having a terminal "-SC (= S) R ^1" polymer (hereinafter, also referred to as "polymer T") step.
Step B: A step in which the polymer T is brought into contact with a thiol group-containing compound without adding a radical generator, and the group "-SC (= S) R ¹ " in the polymer T is replaced with a hydrogen atom.

＜〈 Step A 〉＞
＜ monomer ＞
The monomer used for polymerization is not particularly limited as long as it can be polymerized, and a compound having a radical polymerizable unsaturated bond (hereinafter, also referred to as a "polymerizable unsaturated compound") can be preferably used. Among these, it is more preferable to include at least one selected from the group consisting of a (meth) acrylic compound and an aromatic vinyl compound, and it is further preferable to include at least a (meth) acrylic compound. In addition, in this specification, a (meth) acrylic compound means the meaning containing an acrylic compound and a methacrylic compound.

Specific examples of the (meth) acrylic compound include (meth) acrylic acid, (meth) acrylic ω-carboxy polycaprolactone, crotonic acid, α-ethylacrylic acid, α-n-propylacrylic acid, Unsaturated carboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, vinyl benzoic acid;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, allyl (meth) acrylate, n-butyl (meth) acrylate Ester, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, cyclohexyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, (meth) acrylic acid- 2-methyl-2-adamantyl ester, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, (methyl ) Acrylic acid-α-hydroxy-γ-butyrolactone, norbornane (meth) acrylate carbolactyl, α- (meth) acryloxy-γ-butyrolactone, β- (formyl) Propyl) propenyloxy-γ-butyrolactone, 3- (2,2-bis (trifluoromethyl) -2-hydroxyethyl) -endo-2- (2-methylpropenyl) -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, trimethoxysilylpropyl (meth) acrylate, methyl (meth) acrylate Ethyl ester, (N) N-dimethylaminoethyl (meth) acrylate, -N, N-diethylaminoethyl (meth) acrylate, methoxypolyethyl (meth) acrylate Glycol ester, octyloxyethylene glycol (meth) acrylate, α-methoxymethyl acrylate, α-ethoxy methyl acrylate, 3-methoxy acrylate, methyl crotonate, croton Α, β-unsaturated carboxylic acid ester compounds such as ethyl acetate and dialkyl fumarate;
N-isopropyl (meth) acrylamide, N-third butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl ( (Meth) acrylamide and other α, β-unsaturated carboxylic acid amidine compounds;
Α, β-unsaturated carbonyl compounds such as methyl vinyl ketone, ethyl vinyl ketone, methyl isopropenone, ethyl isopropenone; carboxylates such as vinyl acetate, vinyl butyrate, vinyl benzoate, etc. Acid vinyl ester compounds; maleic anhydride, itaconic anhydride, N-butylmaleimide, N-phenylmaleimide and other cyclic vinyl compounds; N-vinylpyrrolidone, vinyl N-vinyl compounds such as azole and vinylimidazole; compounds having two or more carbon-carbon double bonds such as ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate; ( (Meth) acrylonitrile and the like. Moreover, a single quantity (B) may be used individually by 1 type, and may use 2 or more types together. (Meth) acrylic acid in the present specification refers to acrylic acid and methacrylic acid.

As the aromatic vinyl compound, a styrene-based compound can be preferably used. Specific examples include styrene, hydroxystyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, m-ethylstyrene, p-ethylstyrene, tertiary butoxystyrene, vinylbenzyldimethylamine, N , N-dimethylaminomethylstyrene, 4-vinylbenzyl glycidyl ether, p-ethoxylated styrene and the like. Furthermore, as the aromatic vinyl compound, one kind may be used alone, or two or more kinds may be used in combination.

At the time of polymerization, the use ratio of the (meth) acrylic compound is preferably 20% by mass or more, more preferably 50% by mass or more, and even more preferably the total amount of monomers used in the polymerization. It is 60% by mass or more. The use ratio of the aromatic vinyl compound is preferably less than 50% by mass, more preferably 40% by mass, and even more preferably 20% by mass with respect to the total amount of monomers used in the polymerization.

In the polymerization, other monomers other than the (meth) acrylic compound and the aromatic vinyl compound may be used. Examples of other monomers include ethylene, propylene, 1,3-butadiene, isoprene, and 1,3-pentadiene. The use ratio of other monomers with respect to the total amount of monomers used in the polymerization is preferably 10% by mass or less, and more preferably 5% by mass or less.

<Thiocarbonylthio compounds>
In this step, in the presence of a thiocarbonylthio compound under polymerizing the monomers, whereby the polymer introduced to the end from thiocarbonylthio compounds monovalent group "-SC (= S) R ^1."
Examples of the monovalent organic group of R ¹ include an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, an alkylthio group, an aralkylthio group, a heterocyclic group, and -NR ¹¹ R ¹² , NR ¹¹ -NR ¹² R ¹³ , -COOR ¹¹ , -OCOR ¹¹ , -CONR ¹¹ R ¹² , -P (= O) (OR ¹¹ ) ₂ or -OP (= O) R ¹¹ R ¹² (wherein, R ¹¹ , R ^12, and R ¹³ are each independently an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. The same applies hereinafter). In addition, R ¹ may be a monovalent group in which one or more hydrogen atoms bonded to a carbon atom in each group is substituted with a cyano group, a carboxyl group, or the like.

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

(In 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 formulae (s-1) to (s-3) include an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group, an aryl group, Aralkyl, alkylthio, aralkylthio, heterocyclyl, -NR ¹¹ R ¹² , -NR ¹¹ -NR ¹² R ¹³ , -COOR ¹¹ , -OCOR ¹¹ , -CONR ¹¹ R ¹² , -P ( = O) (OR ¹¹ ) ₂ or -OP (= O) R ¹¹ R ¹² and so on. In addition, R ¹ may be a monovalent group in which one or more hydrogen atoms bonded to a carbon atom in each group is substituted with a cyano group, a carboxyl group, or the like.
Z ⁴ in the formula (s-2) is preferably an aromatic group such as phenyl, and Z ⁶ in the formula (s-3) is preferably an alkyl group.

Specific examples of the thiocarbonylthio compound include bis (thiocarbonyl) disulfide compounds. Examples include tetraethylthiuram disulfide, tetramethylthiuram disulfide, and bis (n-octyl mercapto). -Thiocarbonyl) disulfide, bis (n-dodecylmercapto-thiocarbonyl) disulfide, bis (benzylmercapto-thiocarbonyl) disulfide, bis (n-butylmercapto-thiocarbonyl) ) Disulfide, bis (third butylmercapto-thiocarbonyl) disulfide, bis (n-heptylmercapto-thiocarbonyl) disulfide, bis (n-hexylmercapto-thiocarbonyl) disulfide, Bis (n-pentylmercapto-thiocarbonyl) disulfide, bis (n-nonylmercapto-thiocarbonyl) disulfide, bis (n-decylmercapto-thiocarbonyl) disulfide, bis (third- Dodecylmercapto-thiocarbonyl) disulfide, bis (n-tetradecylmercapto-thiocarbonyl) disulfide, bis (n-hexadecylmercapto-thiocarbonyl) disulfide, bis ( N-octadecyl mercapto-thiocarbonyl) disulfide, etc .;
Examples of the dithioester compound include 2-phenyl-2-propylbenzothio, 4-cyano-4- (phenylthiocarbonylthio) valeric acid, and 2-cyano-2-propylbenzene And disulfide, etc .;
Examples of the trithiocarbonate compound include S- (2-cyano-2-propyl) -S-dodecyl trithiocarbonate and 4-cyano-4-[(dodecylmercapto -Thiocarbonyl) mercapto] valeric acid, cyanomethyldodecyltrithio-carbonate, 2- (dodecylthiocarbonylthiolthio) -2-methylpropanoic acid, and the like.

The use ratio of the thiocarbonylthio compound in the polymerization is preferably 0.05 parts by mass or more, and more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the total of the monomers. In addition, the use ratio of the thiocarbonyl sulfur compound is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less with respect to 100 parts by mass of the total of the monomers. The thiocarbonylthio compounds may be used alone or in combination of two or more.

<Free Radical Generator>
From the viewpoint of productivity, the polymerization is preferably performed in the presence of a radical generator. The radical generator can be appropriately selected from radical polymerization initiators generally used in conventionally known radical polymerization. Specifically, compounds that generate radicals by heat or light include, for example, compounds that generate radicals by heating, such as peroxides, azo compounds, and redox initiators, or compounds that generate radicals by radiation. Compounds that generate free radicals upon irradiation.

Specific examples of the compound that generates a radical upon heating include, for example, a third butyl hydroperoxide, cumene hydroperoxide, a third butyl peroxide, and a benzoic acid peroxide. Tertiary butyl ester, Tertiary butyl peroxylate, Tertiary butyl peroxydecanoate, Tertiary butyl peroxyisobutyrate, Laurel peroxide, Tertiary pentyl trimethylacetate, Peroxide Tributyl trimethylacetate, dicumyl peroxide, benzamidine peroxide, potassium persulfate, ammonium persulfate, etc .;
Examples of the azo compound include azobisisobutyronitrile (AIBN), 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-butyronitrile), 4,4 ' -Azobis (4-valeric acid), 1,1'-Azobis (cyclohexanecarbonitrile), 2- (Third-butylazo) -2-cyanopropane, 2,2'-Co Azobis [2-methyl-N- (1,1) -bis (hydroxymethyl) -2-hydroxyethyl] propanamide, 2,2'-azobis (2-methyl-N-hydroxyl Ethyl) propanamide, 2,2'-azobis (N, N'-dimethylene isobutylphosphonium) dichloride, 2,2'-azobis (2-fluorenylpropane) di Chloride, 2,2'-Azobis (N, N-dimethylmethyleneisobutylamidine), 2,2'-Azobis (2-methyl-N- [1,1-bis (hydroxyl (Methyl) -2-hydroxyethyl] propanamide), 2,2'-azobis (2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propanamine), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propanamide], 2,2'-azobis (isobutylamidamine) dihydrate, etc .;

Examples of the redox-based initiator include a combination of sulfate and acidic sodium sulfite and ferrous sulfate, a composition of third butyl hydroperoxide, acidic sodium sulfite and ferrous sulfate, and mentane hydrogen peroxide and A composition of ferrous sulfate, sodium ethylenediamine tetraacetate, and sodium formaldehyde sulfoxylate. As a compound which generates a radical by heating, an azo compound is preferable, and an azobisisobutyronitrile is more preferable from the point that a side-reactant formed by oxygen or the like is not easily generated.

Specific examples of the compound that generates radicals upon irradiation of radiation include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexylphenyl ketone, and 2,2-dimethoxy- 1,2-diphenylethane-1-one, xanthone, benzaldehyde, pyrene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, benzoin propyl ether, benzoin dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1 -Ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, diethylthiaxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholinyl-propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1,4- (2-hydroxyethoxy ) Phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, bis- (2,6-dimethoxybenzylidene) ) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) acetone) and the like.

In the case where the polymerization is performed in the presence of a radical generator, the use ratio of the radical generator is preferably 1 part by mass or more, more preferably 10 with respect to 100 parts by mass of the thiocarbonyl sulfur compound used in the polymerization. More than mass parts. In addition, the use ratio of the radical generator is preferably 1,000 parts by mass or less, and more preferably 100 parts by mass or less, based on 100 parts by mass of the thiocarbonylthio compound used in the polymerization. The radical generator may be used singly or in combination of two or more kinds.

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

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

The polymerization temperature is not particularly limited as long as it is a temperature at which polymerization can be performed, but from the viewpoint of productivity, it is preferably set to 0 ° C, more preferably set to a range of 0 ° C to 140 ° C, and further preferably set to The range of 20 ° C to 100 ° C is particularly preferably a range of 50 ° C to 90 ° C. The polymerization temperature is preferably set in consideration of the fact 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 or heating from the outside of the reactor. The polymerization reaction is preferably performed under a pressure sufficient to keep the monomers in a substantially liquid phase. The polymerization reaction time is preferably 30 minutes to 20 hours, and more preferably 1 minute to 10 hours. By the above-mentioned polymerization reaction, a polymer solution containing a polymer T having a group "-SC (= S) R ¹ " derived from a thiocarbonylthio compound at the terminal is obtained.

The polymer T may be separated from the polymer solution after the polymerization is completed. When the polymer T is separated, a conventionally known method can be used. Specifically, for example, a method of separating the polymer by steam stripping, filtering the polymer, and then dehydrating and drying the polymer to obtain the polymer can be applied; and concentrated in a flushing tank Then, a method of devolatilization using a vent extruder or the like; a method of direct devolatilization using a drum dryer or the like is used.

<< Step B>
In the subsequent step B, after the polymerization in the step A, the polymer T obtained in the step A is brought into contact with the thiol group-containing compound without adding a radical generator. By this operation, the terminal group “-SC (= S) R ¹ ” in the polymer T is substituted with a hydrogen atom. In addition, in the present manufacturing method, a 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 radical generation. However, in step B, a non-decomposed radical generating agent among the radical generating agents used in step A may exist within a range that does not impair the effect of the present invention.

<Mercapto group-containing compound>
The thiol group-containing compound used is not particularly limited as long as it has the 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 formula (1), R ² is at least one of a monovalent hydrocarbon group having 1 to 30 carbon atoms or a group having -C (= O) O- between carbon-carbon bonds of a hydrocarbon group having 2 to 30 carbon atoms. The hydrogen atom can also be substituted with hydroxyl, carboxyl or -SO ₃ Na)

Examples of the monovalent hydrocarbon group of R ² in the formula (1) include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and the like. Among these, R ^{2 is} preferably a monovalent hydrocarbon group, more preferably an alkyl group having 1 to 30 carbon atoms, and even 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, thioglycolic acid, methyl thioglycolate, ethyl thioglycolate, and 2-ethylhexyl thioglycolate. Ester, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, hexyl 3-mercaptopropionate, cyclohexyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, octyl 3-mercaptopropionate Esters, dodecyl 3-mercaptopropionate, tridecyl 3-mercaptopropionate, octadecyl 3-mercaptopropionate, mercaptosuccinic acid, sodium 2-mercaptoethanesulfonate, 1- Ethylmercaptan, 1-propanethiol, 1-butanethiol, 2-butanethiol, 1-pentanethiol, 1-hexanethiol, 1-heptanethiol, 1-octylthiol, 1-decanethiol Alcohol, 1-dodecanethiol, 1-hexadecanethiol, 1-octadecanethiol, 2-methyl-1-propanethiol, tertiary-dodecylthiol, cyclohexylthiol Alcohol (cyclohexanethiol), thiophenol (thiophenol), etc.

In step B, the use ratio of the thiol group-containing compound is preferably 0.1% by mass or more with respect to the total amount of the polymer T used when the thiol group-containing compound is brought into contact with the polymer T. It is 0.3 mass% or more. The use ratio of the thiol group-containing compound to the total amount of the polymer T used is preferably 20% by mass or less, and more preferably 15% by mass or less. The thiol group-containing compound may be used singly or in combination of two or more kinds.

The contact between the polymer T obtained in the step A and the thiol group-containing compound is preferably performed in an organic solvent. Examples of the organic solvent used include organic solvents exemplified as solvents that can be used in polymerization. From the viewpoint of productivity, it is preferable to directly use the polymer solution obtained in the step A and add a thiol group-containing compound to the polymer solution. In this case, it is desirable to set the use ratio of the thiol group-containing compound to 100 parts by mass of the polymer, preferably 0.1 to 20 parts by mass, and more preferably 0.3 to 15 parts by mass. The use ratio of the monomer in the step A and the use ratio of the thiol group-containing compound in the step are set.

Can more selectively the group "-SC (= S) R ¹ 'is substituted with a hydrogen atom in terms of reactivity of the polymer containing a thiol group and a temperature T (hereinafter, when contacted with a compound, It is also referred to as "modification temperature") preferably at 40 ° C or higher. The modification temperature is more preferably 50 ° C or higher, even more preferably 60 ° C or higher, and even more preferably 70 ° C or higher. In addition, in terms of a high effect of suppressing a decrease in reactivity due to heat, the modification temperature is preferably 130 ° C or lower, more preferably 120 ° C or lower, and even more preferably 110 ° C or lower. The reaction time is preferably 15 minutes to 15 hours, and more preferably 30 minutes to 8 hours.

In step B, after the polymerization in step A is completed, the polymer T and the thiol group-containing compound are preferably contacted in an organic solvent without adding a radical generator to the system. When the polymer solution obtained in the step A is directly used and a thiol group-containing compound is brought into contact with the polymer T in the polymer solution, the use of the thiol group-containing compound is not hindered. The reaction mechanism of the terminal hydrogenation of the polymer T that is carried out allows a small amount of a radical generator added as a polymerization initiator in step A in the system containing the polymer T and the thiol group-containing compound in step B. Undecomposed ingredients in. In this case, the content ratio of the undecomposed radical generator in the system is preferably 1 mass based on the total amount of the thiol group-containing compound used when the polymer T is brought into contact with the thiol group-containing compound. % Or less, more preferably 0.5% by mass or less.

When the polymer T and the thiol group-containing compound are brought into contact with each other in a solution, in order to separate a solution containing the polymer (hereinafter, also referred to as "polymer P") obtained by the reaction, for example, This is performed by a known desolvent method such as steam 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 preferable in that it is not easily restricted in use in electrical applications.

The conversion efficiency of the group "-SC (= S) R ¹ " to a hydrogen atom at the end of the polymer T (hereinafter, also referred to as "terminal conversion efficiency") is preferably 40% or more, more preferably 50% The above is more preferably 60% or more. The terminal conversion efficiency (%) is a value calculated using measurement data of ¹ H-nuclear magnetic resonance (NMR), and is expressed by the following formula (3).

End conversion efficiency = 100-[{(A1 / R1) / (A2 / R2)} × 100]… (3)

(In formula (3), A1 is an integrated value derived from the peak of the terminal group after the polymer T is brought into contact with the thiol group-containing compound, and A2 is derived from the terminal before the polymer T is brought into contact with the thiol group-containing compound. The integrated value of the peak of the polymer group, R1 is the integrated value of the peak of the polymer except the terminal group after the polymer T and the thiol group-containing compound are in contact, and R2 is the value Peak integral value of the entire polymer other than the terminal group.)

The polystyrene-equivalent weight average molecular weight (Mw) of the obtained polymer P that is obtained by gel permeation chromatography (GPC) may be appropriately selected depending on the use of the polymer and the like, and is preferably 1.0 × 10 ³ to 2.0 × 10 ⁶ , more preferably 1.0 × 10 ³ to 1.0 × 10 ⁵ . 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, and more preferably 2.5 or less.

[Polymer composition]
The polymer composition of the present disclosure includes, as a polymer component, a polymer obtained by substituting a group “-SC (= S) R ¹ ” with a hydrogen atom by a production method of the present disclosure. The polymer and polymer composition obtained by the production method of the present disclosure are used in various applications. Specifically, it can be applied to various resin compositions such as a photoresist composition or a liquid immersion composition, an upper film forming composition, an adhesive, a dispersant, a compatibilizer, a surfactant, and a shoe. Various applications such as raw materials, various automotive parts, industrial supplies, asphalt compositions, coatings, and biomaterials.
[Example]

Hereinafter, specific description will be made based on the examples, but the content of the present disclosure is not limited to these examples. In addition, "part" and "%" in an Example and a comparative example are a quality basis unless there is particular notice. The measurement method of each physical property value of a polymer is as follows.
[Mass average molecular weight Mw and number average molecular weight Mn]
Under the following conditions, according to a retention time corresponding to the apex of the largest peak of the GPC curve obtained by gel permeation chromatography (trade name "HLC-8120GPC", manufactured by Tosoh Corporation), polystyrene was used. It is calculated by conversion.
Tubular string: 2 tubular columns under the trade name "GMHXL" (manufactured by Tosoh). Temperature: 40 ° C
Mobile phase: Tetrahydrofuran Flow rate: 1.0 ml / min
Sample concentration: 10 mg / 20 ml
[End conversion efficiency]
The terminal conversion efficiency (%) is calculated based on the formula (3) using measurement data obtained by ¹ H-NMR.
[Quality Analysis of Thermal Decomposition Gas Chromatograph]
Under the following conditions, the polymer end groups were analyzed using a thermal decomposition gas chromatograph mass spectrometer. About the sample, it measured by wrapping in a hot foil (pyrofoil).
(Measurement conditions)
[Table 1]

[Example 1]
In a 50 ml flask under a nitrogen atmosphere, 2.9 g of 2-cyano-2-propyldodecyl trithiocarbonate, 16 g of p-ethoxyloxystyrene, and 1-methoxyl as a polymerization solvent were charged. 0.080 g of 2-propanol and stirred. Next, after adding 7.7 g of a 1-methoxy-2-propanol solution (0.1 mol / L) of azobisisobutyronitrile, the temperature of the flask was raised to 80 ° C, and polymerization was started. After the polymerization reaction was performed for 3 hours, the polymer powder A was obtained by reprecipitating in a hexane solvent.
Then, in a 30 ml flask under a nitrogen atmosphere, 3.2 g of polymer powder A was dissolved in 2.1 g of 1-methoxy-2-propanol, and 1.7 g of tertiary-dodecyl mercaptan was added. The reaction was carried out at a temperature of 80 ° C for 1 hour. The obtained polymer Ap was reprecipitated and purified, and polymer analysis was performed by ¹ H-NMR. As a result, it was confirmed that a decrease in a peak derived from the terminating end of the polymer was obtained (the end conversion efficiency was 78%).

[Example 2]
In a 50 ml flask under a nitrogen atmosphere, 2.9 g of 2-cyano-2-propyldodecyltrithiocarbonate, 17 g of 1-methylcyclopentyl methacrylate, and 1- 0.37 g of methoxy-2-propanol was stirred. Next, after adding 7.7 g of a 1-methoxy-2-propanol solution (0.1 mol / L) of azobisisobutyronitrile, the temperature of the flask was raised to 80 ° C, and polymerization was started. After reacting for 3 hours, it was reprecipitated in a hexane solvent to obtain a polymer powder B.
Then, in a 30 ml flask under a nitrogen atmosphere, 3.4 g of polymer powder B was dissolved in 2.2 g of 1-methoxy-2-propanol, and 1.7 g of tertiary-dodecyl mercaptan was added. , And allowed to react for 1 hour at a reforming temperature of 80 ° C. The obtained polymer Bp was reprecipitated and purified, and polymer analysis was performed by ¹ H-NMR. As a result, it was confirmed that a decrease in a peak originating from the terminating end of the polymer was obtained (the end conversion efficiency was 86%).

[Example 3]
In a 50 ml flask under a nitrogen atmosphere, 0.86 g of 2-cyano-2-propyldodecyltrithiocarbonate, 8.4 g of methyl methacrylate, and 1-methoxy-2 as a polymerization solvent were added. -1.7 g of propanol and stir. Then, 2.5 g of a 1-methoxy-2-propanol solution (0.1 mol / L) of azobisisobutyronitrile was added, and then the temperature was raised to a temperature of 80 ° C. to start polymerization. The 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 tertiary-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, it was confirmed that a peak derived from the terminating end of the polymer was reduced (the end 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, and 1-methylcyclopentyl methacrylate were added. 20 g of the ester and 9.8 g of 1-methoxy-2-propanol as a polymerization solvent were stirred. Next, after adding 5.9 g of a 1-methoxy-2-propanol solution (0.1 mol / L) of azobisisobutyronitrile, the temperature of the flask was raised to 80 ° C., and polymerization was started. Halfway through, 5.3 g of a 1-methoxy-2-propanol solution (0.1 mol / L) of azobisisobutyronitrile was added and reacted for 6 hours to obtain a polymer solution. In addition, polymer powder D was obtained by reprecipitating the obtained polymer solution in a hexane solvent.
Next, in a 30 ml flask under a nitrogen atmosphere, 4.4 g of polymer powder D was dissolved in 2.6 g of 1-methoxy-2-propanol, and 0.80 g of tertiary-dodecyl mercaptan was added. It was made to react at 80 degreeC for 1 hour. The obtained polymer Dp was reprecipitated and purified, and polymer analysis was performed by ¹ H-NMR. As a result, it was confirmed that a peak derived from the terminating end of the polymer was reduced (the end conversion efficiency was 63%).

[Example 5]
A polymer powder D was obtained by performing the same operation as in Example 4. Next, in a 30 ml flask under a nitrogen atmosphere, 4.4 g of the polymer powder D obtained in Example 4 was dissolved in 2.6 g of 1-methoxy-2-propanol, and 0.80 g of a third- Dodecyl mercaptan was 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, it was confirmed that a decrease in a peak originating from the terminating end of the polymer was obtained (the end conversion efficiency was 80%).

[Comparative Example 1]
A polymer powder B was obtained by performing the same operation as in Example 2. Then, in a 30 ml flask under a 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), and allowed to react at a temperature of 80 ° C for 1 hour. The obtained polymer B1 was reprecipitated and purified.
[Comparative Example 2]
A polymer powder B was obtained by performing the same operation as in Example 2. Then, 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 1.6 g of 2,2'-azobis (2 , 4-dimethylvaleronitrile), and 1.6 g of tertiary-dodecyl mercaptan, and reacted at a temperature of 80 ° C for 1 hour. The obtained polymer B2 was reprecipitated and purified.

(Identification of polymer end groups)
1. Thermal decomposition gas chromatograph mass analysis For the terminal hydrogen-modified polymer Bp obtained in Example 2, a pyrolysis-gas chromatograph-mass spectrometer (pyGCMS) The end structure was analyzed. The measurement results are shown in FIG. 1. In addition, in FIG. 1, the inverted triangle mark in the upper graph is derived from the peak near the hydrogen terminal structure obtained by the modification reaction.
2. Matrix-assisted laser desorption ionization time-of-flight mass analysis For the polymers Bp, B1, and B2 obtained in Example 2, Comparative Example 1, and Comparative Example 2, respectively, matrix-assisted laser desorption A matrix-assisted laser desorption ionization-time of flight-mass spectrometry (MALDI-TOF-MS) was attached to determine the molecular weight of the polymer and the end structure was analyzed. The measurement results are shown in FIG. 2. In addition, in FIG. 2, inverted triangle marks are peaks of polymers having terminal structures derived from azo compounds (structures represented by the following formula (2)), and circular marks are derived from terminals converted to hydrogen ( Peak of the polymer structure of the structure represented by the following formula (3).
[Chemical 2]

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

From the above results, it is understood that the polymer having a functional group derived from the RAFT agent at the end is brought into contact with the thiol group-containing compound without adding a radical generator after the polymerization is completed, whereby the functional group derived from the RAFT agent is substituted Is a hydrogen atom. In addition, the end conversion efficiency is also high. From these, it is clear that the method of contacting a polymer having a functional group derived from a RAFT agent at a terminal with a thiol group-containing compound without adding a radical generator after the completion of polymerization can be easily performed without using a metal. The functional group derived from the RAFT agent is highly selectively removed and substituted with a hydrogen atom.

no

FIG. 1 is a view showing a result of analyzing a polymer terminal structure by thermal analysis gas chromatography mass spectrometry.

FIG. 2 is a diagram showing a result of analyzing a polymer terminal structure by matrix-assisted laser desorption ionization time-of-flight mass spectrometry.

Claims (8)

A method for producing a polymer, comprising: Step A: polymerizing a monomer in the presence of a thiocarbonylthio compound to obtain a terminal having a group "-SC (= S) R ¹ " (wherein R ¹ is a monovalent organic Polymer T); and step B, the polymer T is brought into contact with a thiol group-containing compound without adding a radical generator, and the group "-SC (= S" ) R ¹ ″ is replaced by a hydrogen atom. The method for producing a polymer according to item 1 of the scope of application, wherein in the step B, the polymer T and the thiol group-containing compound are brought into contact with each other at a temperature of 40 ° C or higher and 130 ° C or lower. The method for producing a polymer according to item 1 or 2 of the scope of patent application, wherein the monomer includes at least one selected from the group consisting of a (meth) acrylic compound and an aromatic vinyl compound. . 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. 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 formula (1), R ² is a monovalent hydrocarbon group having 1 to 30 carbon atoms or a group having -C (= O) O- between carbon-carbon bonds of a hydrocarbon group having 2 to 30 carbon atoms. At least one hydrogen atom may be substituted by a hydroxyl group, a carboxyl group, or -SO ₃ Na. A method in which a polymer T having a group "-SC (= S) R ¹ " (where R ¹ is a monovalent organic group) is contacted with a compound containing a thiol group without adding a radical generator. , the polymer has a group T "-SC (= S) R ^1" is a hydrogen atom substituent. A polymer obtained by the manufacturing method according to any one of claims 1 to 5 in the scope of patent application. A polymer composition containing the polymer according to item 7 of the scope of patent application.