JPH04183701A - Polymerization initiator and polymerization - Google Patents

Abstract

PURPOSE:To provide the subject initiator having a specific structure having a (substituted) aromatic hydrocarbon group, an ability to initiate living radical polymerizations, and capable of giving polymers having a narrow mol.wt. distribution and at whose molecular ends various functional groups have been introduced. CONSTITUTION:For example, a compound of formula R<1>SH [R<1> is (substituted) aliphatic hydrocarbon, (substituted) alicyclic hydrocarbon, (substituted) aromatic hydrocarbon group] and a compound of formula I [R<2>, R<3>, R<4> are (substituted) aromatic hydrocarbon] are subjected to a dehalogenation reaction, etc., to provide the objective polymerization initiator. It is preferable that R<2>, R<3>, R<4> are (substituted) phenyl or (substituted) naphthyl and that the R<1> is aliphatic hydrocarbon substituted with a carboxyl group, etc.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a living radical polymerization initiator, a method for living radical polymerization of vinyl monomers using the same, and a block and/or graft type polymer obtained by the polymerization. The present invention relates to a polymer composition.

[Prior art] As a polymerization initiator having the ability to initiate living radical polymerization, there is a research report on phenylazotriphenylmethane [Otsu et al.
erBulletin) Volume 11, pp. 277-284 (
198B), and research report on tetraethylthiuram disulfide, etc. [Otsu et al., Poly+aer Bulletin 7
Vol., pp. 45-50 (1982)]. In Gagaho, it is reported that a block copolymer of alkyl methacrylate and styrene was synthesized using each initiator.

Problems to be solved by the invention C] In the case of living radical polymerization using each of the above initiators,
■If you are aiming for a polymer with a large molecular weight, the molecular weight distribution will be wide.■The only functional groups that can be introduced at the end of the polymer are phenyl, triphenylmethyl, and diethyldithiocarbamyl groups, making the functional polymer There were problems such as: (1) the polymerization rate was not very high; (2) a graft product could not be obtained; and (2) a block product other than vinyl monomers could not be obtained.

[Means for Solving the Problems] In order to solve the above problems, the present inventors have conducted extensive studies on a polymerization initiator capable of initiating living radical polymerization and a method for living radical polymerization of vinyl monomers using the same, and as a result, the present invention has been developed. reached. That is, the present invention provides the following [1
] ~ [It is composed of 7 pieces.

[1 Collagen polymerization initiator General formula % Formula % (1) [In the formula, R1 is a (substituted) aliphatic hydrocarbon group, (substituted) alicyclic aliphatic hydrocarbon group, or (substituted) aromatic hydrocarbon group] group, R2+ R''l R4 each represents a (substituted) aromatic hydrocarbon group] A radical polymerization initiator represented by the following.

[2] Method for polymerizing vinyl monomers: [Method for polymerizing vinyl monomers using one radical polymerization initiator.

[3-polymer type radical polymerization initiator general formula % formula % (2) [[R2, R3, R4 are each R21R in general formula (1)]
A polymeric radical polymerization initiator characterized by comprising a polymer having one or more groups represented by z and C representing a group similar to R4 at the terminal and/or side chain.

[4-polymer type radical polymerization initiator general formula % formula % (3) [R2, R3, R4 are each R2rR in general formula (1)
1. A polymeric radical polymerization initiator characterized by comprising a polymer having one or more groups represented by C representing a group similar to R' and R' at the terminal and/or side chain.

[Method for producing 5 polymeric radical polymerization initiators: [4 polymeric radical polymerization initiators, characterized by reacting 1 radical polymerization initiator or 3 polymeric radical polymerization initiators with a vinyl monomer, A method for producing a polymeric radical polymerization initiator.

[6 Method for producing a block and/or graft polymer composition: From a block and/or graft type polymer characterized by reacting the polymeric radical polymerization initiator of [4 or [5] with a vinyl monomer] A method for producing a polymer composition.

[7 Coblock and/or graft polymer composition general formula % formula % (3) [R2, R3, R4 are each R2+R in general formula (1)
3. A polymer composition comprising a block and/or graft type polymer, characterized in that it has one or more groups represented by C representing a group similar to R4 at the end of the main chain and/or side chain.

In the present invention, examples of the group represented by RI in general formula (1) include those exemplified in the following (1) to (2).

■ Saturated or unsaturated aliphatic hydrocarbon groups having 1 to 30 carbon atoms (methyl group, ethyl group, isopropyl group, delene group,
2-ethylphenyl group, stearyl group, impropenyl group, 1-isobutenyl Ll-)'decenyl group, 2-ethylhexyl-2-yl group, etc.).

(2) A saturated or unsaturated alicyclic hydrocarbon group having 3 to 30 carbon atoms (cycloprobyl group, cyclohexyl group, norbornyl group, ethylide 7-norbornyl group, 2-chlorohexynolethyl L 3-7 chlorohexenyl group, etc.).

■Saturated or unsaturated aromatic hydrocarbon M with 6 to 30 carbon atoms
[Phenyl group, 4-ethylphenyl group, 2,4-dimethylphenyl group, naphthyl group, benzyl group, 4-methylbenzyl group, naphthylmethyl group, benzyl group, 3-phenylpropyl group, diphenylmethyl group, 2,2 -diphenylpropyl group, triphenylmethyl group, tophenylmethylethyl group, tri(4-methylphenyl)methyl group, diphenyl(4-methylphenyl)methyl group, tri(
4-methylphenyl)methylpropyl group].

■Substituted aliphatic hydrocarbon group, [carboxine methyl group, 1.
2-carboxy/ethyl group, sodium carboxyfurmethyl group, 1,2-di(sodium carboxyl)ethyl group, 2-baroxy/carboxyl-2-methylethyl group, thiocarboxylethyl group, 1-thiocarboxylene-2 -carboxinmethyl group, 2-sulfonylethyl group, 2-sodium sulfonium ethyl group, m water 1°2-
Dicarboquinlethyl group, metquincarbonylethyl group, 1-ethoxycarbonyl-2-carboxyl group, formylethyl group, chloroformylmethyl group, carbamoylmethyl group, N, N-dimethylcarbamoylmethyl L
N,N-diethylthiocarbamoyl group, cyanethyl group, 1. 2-dicyanoethyl group, 6-iso/anohequinyl group, cyanatomethyl group, 6-ineanatohequinyl group, thiocyanatoethyl group, thioisonanatoethyl group, formylpropyl group, 2-thioformylethyl group, ethylcarbonyl Ethyl group, ethylthiocarbonylethyl group, 2-hydroquinolethyl group, 2,3-dihydroquinolepropyl group, mercaptomethyl group, hydroberoquinolbutyl group, amineethyl group, dimethylamineethyl group, maleiminoethyl group, 3-(2-propenyl group) propyl group, nitropropyl group, metquinethyl group,
Glyenyl group, 2,3-:,5 glinonorprobyl group,
acetylacetoxyl group, ethylmercaptoethyl group,
Bromopropyl group, inpropyldiazopropyl group, propylhydrazinoethyl group, fenoquinethyl group, phenylmercaptomethyl group, carpoquinruphenylpropyl group, diphenylmethochinomethyl group, fenoquinemethyl group, 3-(1-ly phenylmethquine)propyl group, triphenylaminopropyl group, diphenylmethylmercaptoethyl group, triphenylmethylmercaptoethyl group, 2-phenoquinecarbonylethyl group, tri(4-
nitrophenyl) methylmercaptoethyl group, tri(4
-sulfonylphenyl)methylmercaptoethyl group,
Tri(4-sodium sulfoniumphenyl)methylmercaptoethyl group, diphenylnaphthylmethylmercaptoethyl group, 2.3-bis(triphenylmethylmercapto)propyl L 2-nitro-3-(triphenylmethylmercapto)propyl group, 3. 6. 9-
tris(triphenylmethylmercapto)decyl 2&,
5-triphenylmethylmercapto-3-triphenylmethylmercaptomethylpentyl L 2. 3. 4
- Tris [tri(4'-nitrophenyl)methylmercaptocobutyl group, etc.].

■Substituted alicyclic hydrocarbon group [carpoquinecyclohexyl group, isocyanocyclohexylmethyl group, 2,5-diisocyanatocyclohexyl group, methquinecyclohexylpropyl group, 4-triphenylmethylcyclohexyl group,
2,5-oxaneclohexyl group, 2-methoxynorbornyl group, tri(4-nitrophenyl)methylmercaptoneclohexyl group, etc.

■Substituted aromatic hydrocarbon group [4-)U phenylmethylmercaptophenyl group, diphenylnaphthylmethylmercaptoethylbenzyl group, 4-carphoki/phenyl group, tri(4-carboquinophenyl)methyl group, tri(4-sodium carboxy) nylamphenyl)methyl group, 4-
peroxycarboquinlepenzyl group, dithiocarboxylphenyl group, 4-sulfonylbenzyl group, tri(4-
sulfonylphenyl)methyl group, 4-sodium sulfoniumphenyl group, tri(4-sodiumsulfoniumphenyl)methyl group, methoxycarbonylphenyl group, 2-phenyloxycarbonylmethylphenyl group,
4-formylphenyl group, chloroformylbenzyl group,
Carbamoylphenyl group, 4-cyanophenyl group, 2.
4-dicyanophenyl group, diphenyl(4-cyanophenyl)methyl group, tri(4-cyanophenyl)methyl group, 4-incyanobenzyl group, cyanatophenyl group,
4-isocyanato-3-methylphenyl group, thiocyanatophenyl group, thioisocyanatophenyl group, 4-formyl-2-ethylbenzyl group, 2-thioformylethylphenyl group, ethylcarbonylphenyl group, ethylthiocarbonylbenzyl group , 4-glycidylphenylethyl group, 2-hydroxylphenyl group, 3-hydroxynaphthyl group, mercaptophenyl group, hydroberoxylbenyl group, aminophenyl group, dimethylaminoethylbenzyl group, 4-nitrophenyl group, 3-methoxy Phenyl group, 4-di(4-nitrophenyl)phenylmethylmercaptoethylphenyl group, tri(4-nitrophenyl)methyl group, 3,5-dimethoxyphenyl group, phenoxyphenyl group, phenoxymethyl group, ethylmercaptophenyl group, Phenylmercaptobenzyl group, bromophenyl group, triphenylmethylmercaptoethylbenzyl group, 2,4-dichlorobenzyl group, tri(4-bromophenyl)methyl group, tri(4-chlorophenyl)
Methylmercaptohexynyl group, inpropyldiazomethylphenyl group, triphenylmethylmercaptophenyl group, bis(triphenylmethylmercapto)phenyl group, etc.

Among the groups exemplified in (1) to (2) as the groups represented by R1, preferred are the following (a) to (c).

(a) Among those exemplified in ■ to ■, carboxyl groups,
Sulfonyl group, sulfonium group, anhydride carboxyl group,
One or more substituents selected from a dithiocarbamoyl group, a cyano group, an incyanato group, a hydroxyl group, an amino group, a nitro group, a halogen, a glycidyl group, a phenyl group, a naphthyl group, a triphenylmethoxy group, and a triphenylmethylmercapto group. - Those with more than one.

(b) Among those exemplified in ■ to ■, general formula % formula % (2) [R'', R'', R' each represents the same group as R2゜R2, R4 in general formula (1) Particularly preferred are those substituted with one or more of the substituents represented by R21R"IR4, each of which is a phenyl group, a naphthyl group, a nitro group, a sulfonyl group, a sulfonium group, a cyano group, When it is either a phenyl group or a naphthyl group substituted with one or more substituents selected from a carboxyl group, a carboxinium group, and a halogen atom.

(c) Among those exemplified in ■ or ■, general formula % formula % (3) [R", R", R' represent the same groups as R2+R", R' in general formula (1), respectively A (substituted) aromatic hydrocarbon represented by R, particularly preferably R
2, R3, R- each represents a phenyl group, a naphthyl group,
and a phenyl group or a naphthyl group substituted with one or more substituents selected from a nitro group, a sulfonyl group, a sulfonium group, a cyan group, a carboxyl group, a carboxinium group, and a halogen atom. If so.

In the present invention, general formulas (1), (2), (3)
Among them, the (substituted) aromatic hydrocarbon groups represented by R21Rs and R4 may be different by only one or all of them may be different.

Examples of (substituted) aromatic hydrocarbon groups represented by R2, R3, and R- include the following (a) to (d).

(a) Unsubstituted aromatic hydrocarbon group (phenyl group, naphthyl group, anthranyl group, benzyl group, 1-phenylethyl group, 4-phenylbutyl group, etc.).

(b) Substituted phenyl group (4-methylphenyl group, 3-isopropylphenyl group, 4-phenylphenyl group, 4-
Calhoki/phenyl group, dithiocarphoki/phenyl group,
4-sulfonylphenyl L 4-sodium sulfonium phenyl group, methylokinecarponylphenyl group,
2-phenyloxycarbonylmethylphenyl group, carbamoylphenyl L 4-noanophenyl group, 1.
4-dineanophenyl group, cyanatophenyl group, 4-isocyanato-3-methylphenyl group, thiocyanatophenyl group, thioisonanatophenyl group, 2-+oformylethylphenyl group, ethylcarbonylphenyl group, 2
-Hydroxy/ruphenyl group, mercaptophenyl group, aminophenyl group, 4-nitrophenyl group, 3-methquinophenyl group, 3. 5-dineanophenyl group, phenoquinophenyl group, ethylmercaptophenyl group, bromophenyl group, isopropyldiazomethylphenyl group, etc.).

(C) Substituted naphthyl group (3-methyl-1-naphthyl group,
6-carboxy-2-naphthyl group, 5,8-disulfonyl-1-naphthyl group, 6-nitro-1-naphthyl group, etc.)
.

(a) Other aromatic hydrocarbon groups (carpoquinrubenzyl group, dithiocarboxylphenylethyl group, 4-sulfonylbenzyl 21.4-sodiumsulfoniumbenzyl group, 2-phenyloxycarbonylethyl group, chloroformylbenzyl M, 4 -cyanobenzyl group, 4-formyl-2-ethylbenzyl group, ethylcarbonylbenzyl group, ethylthiocarbonylbenzyl group, hydroberoquinolbenzyl group, trimethylaminoethylbenzyl group, 4-nitrobenzyl group, phenokhinebenzyl group , phenoxymethyl group, phenylmercaptomethyl group, phenylmercaptobenzyl group, 2.4-dichlorobenzyl group, etc.).

Among these, preferred are (a) phenyl group, naphthyl group, substituted phenyl M (b) and substituted naphthyl group (C), and particularly preferred are phenyl group, naphthyl group, and substituent group. That is, it is a phenyl group or a naphthyl group substituted with one or more substituents selected from a nitro group, a sulfonyl group, a sulfonium group, an /ano group, a carboxyl group, a carboxinium group, and a halogen atom.

Typical methods for synthesizing radical polymerization initiators include the following reaction formula (a) or (b). In addition, in each formula, R' to R4 are R in general formula (1)
It is the same as 1-R', and X represents a halogen atom.

R2R2 I R'SH+XCR3-=R'5CR3+HX(a)R'
R' R2R2 In method (a), dehydrogenation reaction between (4) and (5) is performed, and in reaction (b), dehydrogenation reaction is performed between (6) and (7), respectively. By carrying out this process, one initiator of the present invention represented by general formula (1) is obtained. Each hydrogen halide reaction is usually carried out in a basic solvent or in a suitable organic solvent in the presence of a basic catalyst. Specific examples of basic solvents include pyridine, methylpyridine, triethylamine, and trimethylformamide. Specific examples of the basic catalyst include dimethylpyridine, trimethylaminopyridine, DBUl DBNl sodium hydroxide, potassium hydroxide, sodium metkind, and the like. Specific examples of suitable organic solvents include benzene, toluene, xylene, ethanol, nomethylsulfoquine, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, cyclohexanone, heptane, kerosene, dimethylformamide, and the like.

The reaction conditions in the above methods (a) and (b) are not particularly limited, and vary depending on the type of raw material, the type of solvent used, the concentration, etc. For example, the polymerization temperature is usually
-80 to 250″C1 Preferably, 0 to 120°C, and the reaction pressure is usually 1 to 3 atm, preferably 1
It is atmospheric pressure. The reaction time is usually 0.5 to 36 hours, preferably 1 to 24 hours. The reaction concentration is usually 1
-90%, preferably 10-60%.

The three polymeric radical polymerization initiators are derived from various polymers. Examples of polymers include ■polyolefin polymers, ■polyvinyl polymers, ■O-L/fin-hinyl copolymers, ■polyalkylene oxide polymers, ■polyester polymers, ■polyamide polymers, and ■polyimide polymers. Examples include: (1) polyurethane polymer, (2) polyurea polymer.

(2) Examples of polyolefin polymers include single, binary, or multi-component polymers of olefin monomers and modified products thereof. Specific examples of olefinic monomers include ethylene, olefins having 1 to 30 carbon atoms (propylene, butene, 4-methylpentene-1, heptene, nonene, isodecene, eicosene, etc.), alicyclic olefins (cyclohentene, cyclohexene, cyclohexene, etc.). - Methylchloroheptene, cyclooctene, norbornene, 2-ethylnorbornene, etc.), dienes (butadiene, isoprene,
cyclopentadiene, ethylidenenorbornene), etc.

(2) Examples of polyvinyl polymers include single, binary, or multi-component polymers of vinyl monomers and modified products thereof. Specific examples of vinyl monomers include styrene, substituted styrene (sodium p-styrene sulfonate, α-methylstyrene, p-ethylstyrene, etc.), (meth)acryloyl group-containing monomers [(meth)acrylonitrile, (meth)acrylamide, etc. , (meth)acrylic acid, sodium (meth)acrylate, ester of (meth)acrylic acid with alcohol having 1 to 30 carbon atoms,
Amides of (meth)acrylic acid and amines having 1 to 30 carbon atoms, hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, N.

N-dimethylaminoethyl (meth)acrylate, 1 to 100 mole adduct of alkylene oxide (ethylene oxide and/or propylene oxide and/or styrene oxide, etc.) of (meth)acrylic acid and hydroxyethyl (meth)acrylate, N-vinylpyrrolidone , maleic acid monomers (maleic anhydride, half and diesters of maleic anhydride with alcohols having 1 to 30 carbon atoms, monoamides, diamides and imides of maleic anhydride with amines having 1 to 30 carbon atoms, vinyl chloride, vinyl acetate, Examples include allyl alcohol, an alkylene oxide adduct of 1 to 100 moles of allyl alcohol, divinylbenzene, vinyl (meth)acrylate, and the like.

(2) Examples of the olefin-vinyl copolymer include copolymers of the olefin monomers exemplified in (1) and the vinyl monomers exemplified in (2).

(2) Examples of polyalkylene oxide polymers include single, binary, or multi-component alkylene oxide polymers and modified products thereof. Specific examples of alkylene oxides include ethylene oxide, propylene oxide, styrene oxide, glycidyl (meth)acrylate, epichlorohydrin, glycidol, glycidyl ethers (butyl glycidyl ether, phenyl glycidyl ether, mono- or diglycidyl ether of polyethylene glycol), Examples include polytetramethylene oxide.

(2) Examples of polyester polymers include polyesters made from polybasic acids and polyhydric alcohols, polyesters made from caprolactone, and modified products thereof. Specific examples of polybasic acids include divalent acids (oxalic acid, succinic acid, adipic acid, himelic acid, sebacic acid,
-propyl-2-pentenoic acid, malonic acid, maleic acid,
= Maleic acid hydroxide, fumaric acid, phthalic acid, phthalic anhydride,
terephthalic acid, naphthalene dicarboxylic acid, quinoline diacetic acid, etc.) and/or trivalent or higher acid (glycerin, 1
．． 2. 3-butanetricarboxylic acid, butane-1,2
, 3,4-tetrecarbic acid, etc.). Specific examples of polyhydric alcohols include dihydric alcohols (ethylene glycol, 1.4-butanediol, 3-methyl-1,5-pentanol, 1,8-octanediol, hydroquinone, bisphenol A, etc.), and These alkylene oxide adducts, polybutadiene diol, hydrogenated polybutadiene diol, polyisoprene diol, polystyrene diol, etc.) and/or trihydric or higher alcohols (glycerin, polyglycitol, pentaerythritol, and these alkylene oxides) additives, etc.). Specific examples of caprolactone include γ-caprolactone and ε-caprolactone.

(2) Examples of polyamide polymers include polyamides made of polybasic acids and polyvalent amines as exemplified in (2), polyamides made of caprolactam, and modified products thereof. Specific examples of polyvalent amines include ethylenediamine, triethylenetetramine, 1,4-diaminocyclohexane, 1°4-diaminobenzene, and 1,4-diaminomethylbenzene. Specific examples of caprolactam include γ-caprolactam, ε-caprolactam, and the like.

■ Polyimide polymers include polyvalent amines exemplified in ■ and compounds having two or more acid anhydride groups in one molecule (
pyromellitic anhydride, etc.) and modified products thereof.

■Polyurethane polymers include polym alcohols and/or ■polyalkylene oxide polymers and/or ■polyester polymers as exemplified in (■), polyurethanes made from polyvalent isocyanates, and modified products thereof. can give. Specific examples of polyvalent isocyanates include 2.8-tolylene diisocyanate), 4. 4'-
diphenylmethane diisocyanate, 1. 4-chlorohexane diisocyanate, 6-hexane diisocyanate, 1. 3. Examples include 5-benzene triisocyanate.

(2) Examples of polyurea-based polymers include polyureas made of polyvalent amines exemplified by (2) and polyvalent incyanates exemplified by (2).

These polymers can be modified with various functional groups or
It is possible to be modified. Preferred among these polymers are (1) polyolefin polymers, (2) polyalkylene oxide polymers, (2) polyester polymers, (2) polyamide polymers, and (3) polyurethane polymers among the above-mentioned (1) to (2) above. .

The weight average molecular weight of these polymers varies depending on the type of polymer, but is usually 5 million to 1 million.

Typical synthesis methods for the three polymeric radical polymerization initiators include the following methods (a) to (c).

(a) Adding a hydroxyl group to the terminal and/or side chain After converting the hydroxyl group of the polymer to -5H using a known method, the general formula % formula % (7) [: R2, R3, R4 are each of the general formula (1) R2+ in
A method of reacting with a compound in which the method is the same as R3 and R4, and X is a halogen atom: As a polymer having a hydroxyl group at the terminal and/or side chain, for example, among the above polymers, ■ polyalkylene oxide type Copolymers of hydroxyl group-containing vinyl monomers (allyl alcohol, hydroquine ethyl (meth)acrylate, etc.) among polymers, ■polyester polymers, ■polyurethane polymers, and ■polyvinyl polymers, living anionic polymerization. Possible vinyl monomers [styrene, methyl (meth)acrylate, butyl (meth)acrylate,
Examples include polymers in which hydroxyl groups are introduced at the terminals by polymerizing acrylonitrile, butadiene, isoprene, etc. by living anionic polymerization and then reacting with oxygen or ethylene oxide, and polymers in which hydroxyl groups are introduced through various modifications. Methods for introducing hydroxyl groups into polymers by modification include: (1) hydrolyzing copolymers such as glycidyl (meth)acrylate or vinyl acetate in polyvinyl polymers; (2) hydrolyzing copolymers such as glycidyl (meth)acrylate or vinyl acetate in polyvinyl polymers; A method of adding alkylene oxide, etc. to a copolymer of containing monomers [(meth)acrylic acid, maleic acid, etc.; ■ A method of graft-adding a hydroxyl group-containing monomer among vinyl monomers to a polyolefin polymer; ■ A method of graft-adding a hydroxyl group-containing monomer among vinyl monomers to a polyolefin polymer; Examples include a method of graft-adding a carboxylic acid group-containing monomer among vinyl monomers to a vinyl monomer.

A method of converting a hydroxyl group to -SH by a known method, and Shiteha,
Examples include a method of reacting with diphenylurea, a method of reacting with sodium sulfide, and the like.

(b) In the double bond of the double bond-containing polymer, the general formula % formula % [R2, R'', R4 are each R2 in the general formula (1)
1R', R', and Rs is an aliphatic hydrocarbon group or an aromatic hydrocarbon group] A method of thermally adding a compound represented by: As a specific example of a double bond-containing polymer, the above polymer Among them, ■polybutadiene, polyisoprene, copolymers of olefin monomers and dienes among polyolefin polymers, ■thermally degraded products of polyolefin polymers, ■polyester polymers, and ■polyamide polymers and ■Among polyurethane polymers, polybasic acids with unsaturated double bonds (4
-7''ropyru-2-pentenoic acid, maleic acid, fumaric acid, etc.).

(c) Any of the polymers of ■ to ■ has the general formula [R2, R4, and R' are each R2 in the general formula (1)]
1R", R', and R6 is an aliphatic hydrocarbon group or an aromatic hydrocarbon group] A method of radically adding a compound represented by the following in the presence of a peroxide catalyst: As a peroxide catalyst, benzoyl peroxide, Examples include dicumyl peroxide, ditertiary butyl peroxide, etc. The amount of peroxide used is usually 0.01 to 5%, preferably 0.1 to 3%, based on the compound represented by general formula (8). It is.

The reaction conditions when synthesizing these three initiators by the methods exemplified in (a) to (c) above are not particularly limited and may vary depending on the type of raw materials, the type of solvent used, the concentration, etc. . For example, the polymerization temperature is usually -80 to 250°C,
Preferably the temperature is 0 to 180°C, and the reaction pressure is usually 1
~3 atm, preferably 1 atm. The reaction time is usually 0.5 to 36 hours, preferably 1 to 12 hours.

The reaction concentration is usually 1 to 90%, preferably 10 to 90%.
It is 60%.

Methods for producing polymeric radical polymerization initiators [Representative examples of the five methods include methods (d) and (e) below.

(d) Method of synthesizing initiator [4] by radically polymerizing one or more vinyl monomers using initiator [1] As the vinyl monomer, all vinyl monomers that are radically polymerizable can be used. , for example, [vinyl monomers exemplified in section ① of polymers constituting 3] and
Examples include butadiene and isoprene.

(e) A method of synthesizing the initiator [4] by radical polymerizing one or more vinyl heptanomers using three initiators: Examples of vinyl monomers include the same vinyl monomers as in (d) above. Lalel.

The reaction conditions when synthesizing these initiators [4] by the method exemplified in (d) or (e) above are not particularly limited, and include the type and amount of the initiator [1] or [3], the vinyl monomer It varies depending on the type, amount used, type of solvent used if necessary, etc. Polymerization temperature is usually -80 to 2
50°C, preferably 50 to 180°C. The reaction pressure is usually -0, 1 to 3000 atm, preferably 0.
The pressure is 5 to 50 atmospheres. The reaction time is usually 0.5 to 36 hours, preferably 1 to 12 hours.

A solvent can be used if necessary. It may be carried out in bulk using the vinyl monomer as a solvent. When using solvents,
The concentration of the vinyl monomer varies depending on the type of monomer used, the molecular weight of the desired polymer, the reaction temperature, etc. This concentration is usually 3-99%, preferably 30-99%
It is.

There are no particular limitations on the type of solvent used if necessary.

Specific examples include commonly used aqueous solvents (water, water/methanol or water/isopropyl alcohol mixed systems, etc.), hydrocarbon solvents (heftane, nclohexane,
isoparaffin, mineral oil, benzene, toluene, xylene, tetralin, etc.), chlorinated solvents (ethylene chloride, carbon tetrachloride, chlorobenzene, chlorinated paraffin, etc.)
etc. In addition to these, alcohol solvents (ethanol, impropatol, benzyl alcohol, ethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.), ether solvents (diethyl ether, dioxane, tetrahydrofuran, diphenyl ether, etc.), ketone solvents ( acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ester solvents (ethyl acetate, dibutyl phthalate, etc.), amide solvents (acetamide, dimethylacetamide, dimethylformamide, etc.), sulfoxide solvents (dimethylformhokind, etc.), acidic solvents ( Acetic acid, trifluoroacetic acid, phenol, benzoic acid, etc.), basic solvents (triethylamine, pyridine, etc.), etc. can also be used.

There are no particular limitations on the polymerization method, and homogeneous polymerization, precipitation polymerization, emulsion polymerization, suspension polymerization, and dimensional polymerization are also possible. Obtaining a homopolymer of one kind of vinyl monomer, a random copolymer of two or more kinds of vinyl monomers, and a block copolymer by polymerizing one kind of vinyl monomer and then polymerizing another vinyl monomer. You can also get

The amount of initiator [1] or [3 used is also the desired initiator [
Although it varies depending on the molecular weight of the four components, it is usually 0.0001 to 2000 molar per mole of vinyl monomer.
mol, preferably 0.01 to 100 mmol.

The weight average molecular weight of the initiator [4] varies depending on the purpose, but is usually 5 million to 1 million.

The vinyl monomer in the methods [2 and 6] of the present invention is not particularly limited as long as it is a radically polymerizable vinyl monomer. Specific examples include vinyl monomers and the like exemplified in the method (d) for producing the above-mentioned initiator [4]. These vinyl monomers may be used alone or in combination of two or more.

In the methods [2 and 6] of the present invention, the polymerization conditions are not particularly limited, and include the type and amount of initiator [1], type 3 and type 4, the type and amount of vinyl monomer used, and the type and amount of vinyl monomer used, as necessary. It varies depending on the type of solvent used. Specific examples of polymerization conditions such as polymerization temperature, reaction pressure, reaction time, type and amount of reaction solvent, and polymerization method include the same conditions as those exemplified in the conditions for producing the initiator [4] above. It will be done.

The amount of initiator [1, [3, or [4] used varies depending on the desired molecular weight of the polymer, etc., but is usually 0.0001 to 2000 mmol, preferably 0.0001 to 2000 mmol per mole of vinyl monomer. .01 to 100 mmol.

The composition [7] of the present invention is produced by the method [6] of the present invention using the initiator [3] or [4] of the present invention.

Initiator [Among the 3 initiators, an initiator having a group represented by general formula (2) only at the end of the main chain of the polymer [3 initiators yield a polymer composition containing a block polymer; An initiator having one or more groups represented by (2) in the side chain of the polymer [3
] A graft copolymer can be obtained. Initiator [Among the 4 initiators, an initiator having a group represented by general formula (3) only at the end of the main chain of the polymer [4 initiators] yields a polymer composition containing a graft polymer; A graft copolymer can be obtained from the initiator [4] having one or more groups represented by formula (3) in the side chain of the polymer.

The present composition [7] consists of, as a polymer component, a mixture of a block and/or graft body and a homopolymer that did not participate in the block and/or grafting reaction. However, this homopolymer can also be purified and removed. Therefore, the content of blocks and/or grafts in the polymer component in the composition [7] of the present invention is usually 40 to 100%, preferably 70 to 100%.
%. The molecular weight of the block and/or graft body is not particularly limited, but is usually 5 to 2 million, preferably 1 to 500,000.

There are no particular limitations on the purification method used to extract pure block and/or graft polymers from this composition. ) ■Methods that utilize differences in molecular weight (preparative gel vermini-silon, membrane dialysis, etc.).

The present composition may contain various solvents in addition to the polymer component. Examples of the solvent include the reaction solvents exemplified in the method [2 or 6] of the present invention. The content of the solvent is usually 3 to 99%, preferably 30 to 99%.
It is.

In addition, in this composition, those having a group represented by general formula (3) have radical polymerization ability and can also be used as the initiator [4] of the present invention.

A method for polymerizing vinyl monomers using the initiator [1] of the present invention [2] It is possible to obtain a polymer with a narrow molecular weight distribution that could not be obtained by conventional methods, and to obtain a polymer with a main chain or side chain of the polymer. It is possible to obtain polymers having various functional groups at their terminals in high yields. Furthermore, among the initiators [1], when an initiator having three or more groups represented by the general formula (2) is used, it is possible to obtain a high molecular weight polymer in a short time and to synthesize a star polymer. It is possible.

A block and/or graft polymer composition [7] is obtained by the method [6] of polymerizing a vinyl monomer using the initiator [3] of the present invention. In this case, a block and/or graft polymer can be obtained in high yield, and a block and/or graft polymer of incompatible segments can be obtained. In this case, a block copolymer is obtained from an initiator having a group represented by general formula (2) only at the end of the main chain of the polymer; A graft copolymer can be obtained from the initiator [3] having one or more initiators in the side chain. In particular, among the initiators [3], when initiators based on polymers other than polyvinyl polymers are used, non-vinyl-vinyl block and/or graft copolymers, which cannot be obtained by conventional methods, can be produced in high yields. You can get it at a high rate.

The initiator of the present invention [4 t?] is the initiator of the present invention [1 t? −
is produced by the method [5] of reacting [:3] with a vinyl monomer, and the method [6] of the present invention gives a block and/or graft polymer composition [7].

When the initiator [4] is used as the initiator [1], a block and/or graft polymer of polyvinyl segments with controlled molecular weight and molecular weight distribution can be obtained in high yield. In this case, −
An initiator produced from an initiator having one or two groups represented by the general formula (2) [If 4 initiators are used, a block polymer is obtained; A graft polymer can be obtained by using an initiator produced from an initiator having [4].

In addition, when an initiator obtained from initiator [3] is used as initiator [4], block and/or graft polymers having three or more types of polymer segments having two or more types of polyvinyl polymer segments can be produced with high yield. You can get it at a high rate. In this case, if an initiator [4] manufactured from an initiator having a group represented by the general formula (2) only at the end of the main chain of the polymer is used, a block polymer is obtained, and the group represented by the general formula (2) is used. A graft copolymer can be obtained by using a polymer prepared from a polymer having one or more groups represented by the above in its side chain.

[Examples] Hereinafter, the present invention will be further explained with reference to production examples and examples, but the present invention is not limited thereto. In the following, parts represent parts by weight, and % represents weight %.

Production Example 1 40 parts of pyridine and 5 parts of triphenylmethyl chloride were placed in a glass reactor. After 6 parts of the mixture were uniformly stirred and mixed, 4.0 parts of dodecyl mercaptan was added dropwise at 40°C over 5 minutes. After the addition was completed, scuttling occurred.

After stirring at 80°C for 1 hour, scuttling was removed by filtration.
By distilling off pyridine, reaction raw materials, and byproducts from the filtrate under reduced pressure, the initiator of the present invention [1, dodecyltriphenylmethyl sulfide (DTPMS) Ei, 8
I got the department.

Production Example 2 The procedure was repeated in the same manner as Production Example 1 except that 3.6 parts of thioglycolic acid was added instead of 4.0 parts of dodecyl mercaptan. 6.0 parts of CMTPMS) were obtained.

Production example 3 Dodecyl mercaptan 4. The procedure was repeated in the same manner as in Production Example 1, except that 2.5 parts of thiophenol was added instead of 0 parts, to obtain 5.5 parts of phenyltriphenylmethyl sulfide (FTPMS), which is the initiator of the present invention. .

Production Example 4 The same procedure as Production Example 1 was carried out except that 7.5 parts of tri(4-chlorophenyl)methyl chloride was added instead of 5.6 parts of triphenylmethyl chloride. 8.0 parts of dodecyltri(4-chlorophenyl)methyl sulfide (DTCPMS) was obtained.

Production Example 5 The same procedure as Production Example 3 was carried out except that 8.5 parts of tri(4-nitrophenyl)methyl chloride was added instead of 5.6 parts of triphenylmethyl chloride. 7.2 parts of certain phenyltri(4-nitrophenyl)methyl sulfide (PTNPMS) were obtained.

Production Example 6 Production Example 4 except that 5.5 parts of triphenylmethylmercaptan was added instead of 4.0 parts of dodenylmercaptan.
In the same manner as above, 12.0 parts of triphenylmethyltri(4-chlorophenyl)methylsulfide (PMCPMS), which is the initiator [1] of the present invention, was obtained.

Production Example 7 Instead of 4.0 parts of dodecylmercabutane, 0.0 parts of ethylene disulfide was used. The procedure was carried out in the same manner as in Production Example 5 except that 9 parts of the initiator of the present invention [1 part, bis[tri(4
-nitrophenyl) methylcoethylene disulfide (B
NPMDS)7. I got 1 copy.

Production Example 8 The same procedure as Production Example 1 was carried out except that 0.9 parts of propylene trisulfide was added instead of 4.0 parts of dodenlumel butane. ) Propane (TTPMMP)
7.0 parts were obtained.

Production Example 9 Polypropylene glycol (molecular weight 1
000) and 50 parts of toluene were added and dissolved, 1.5 parts of thiourea was added, and the mixture was reacted for 5 hours under reflux. After filtration, water washing, and dehydration, triphenylmethane chloride 5
．． Add 5 parts and 1.6 parts of pyridine under reflux,
The reaction was allowed to proceed for 5 hours. The initiator of the present invention [polypropylene glycol (TPPPG) having a terminal triphenylmethyl mercapto group (TPPPG) 14] was obtained by removing scuttling by filtration and distilling off pyridine, reaction raw materials, and byproducts from the filtrate under reduced pressure. I got the department.

Production Example 10 20 parts of polyester (molecule j12000) made of adipic acid and 1,4-butanediol was used instead of 10 parts of polypropylene glycol, and tri(4-chlorophenyl)methane chloride was used instead of 5.5 parts of triphenylmethane chloride. The procedure was carried out in the same manner as in Example 9 except that 7.6 parts of the initiator of the present invention [tri(4-chlorophenyl)methylmercapto group-containing polyester (TCPPES) 2
6.8 parts were obtained.

Production Example 11 Instead of 10 parts of polypropylene glycol, 40 parts of polyester (molecular weight 1000) made of adipic acid and 1,4-butanediol and polyurethane (molecular j 14000) made of tolylene diisocyanate were used, and 5.5 parts of triphenylmethane chloride was used. The same procedure as in Example 9 was carried out except that 8.2 parts of tri(4-nitrophenyl)methane chloride was used instead. (TN
47.8 parts of PPU) were obtained.

Production Example 12 Instead of polypropylene glycol 1ON, hydrogenated polyisoprene having -OH at the terminal and pendant (molecular weight 2500. Average -oH number per molecule: 2.5)
The same procedure as in Example 9 was carried out except that 20 parts of the initiator was used to obtain 23.4 parts of tri-taphenylmethyl group-containing overnight hydrogenated polyisoprene (TPHPIP), which is the initiator of the present invention.

Production Example 13 After replacing the glass reactor with nitrogen, ethylene-propylene random copolymer (ethylene content 45%, molecular weight 150,000)
20 parts and 100 parts of toluene were added and dissolved by heating. Under a nitrogen blanket, a solution of 0.54 parts of tri(4-nitrophenyl)methylmercaptoethylmaleimide and 0.01 parts of benzoyl peroxide dissolved in 10 parts of toluene,
The mixture was added dropwise at 110°C over 1 hour. Furthermore, it was stirred for 3 hours under reflux, and the reaction solution was poured into methanol.
After washing with methanol and drying under reduced pressure, 23.5 parts of an ethylene-propylene copolymer (TNPEPM) having three tri(4-nitrophenyl)methylmercapto groups pendant as the initiator of the present invention was obtained. Ta.

Examples 1 to 11 As shown in each Example shown in Table 1, each sulfide produced in Production Examples 1 to 8 was used as a radical polymerization initiator of the present invention. In addition, styrene (St) or methyl methacrylate (MMA) was used as the monomer or hinyl monomer in each of the Examples shown in Table 1. In each example, 0.5 mmol of sulfide was added to 1 mol of vinyl monomer in a glass reactor purged with nitrogen. Next, after degassing the inside of the reactor,
Under a nitrogen seal at 80°C for 6 hours (Examples 13 to 1
In No. 1, the polymerization reaction was carried out for 4 hours.

After this polymerization reaction, the polymers were isolated by pouring each reaction solution into methanol.

Table 1 shows the yield, weight molecular weight (My) and molecular weight distribution (My/Mn) determined by GPC of each polymer obtained. In addition, NMR confirmed a sulfide bond at the terminal of each polymer and residues of each polymerization initiator.

Table 1 Examples 17 to 29 As shown in each example shown in Table 2, the polymers containing radically polymerizable functional groups produced in Production Examples 9 to 13 and Example 7
．． 10. The polymer obtained in step 14 (in order, DTC-5
t, PTN-MMA, and BNP-MMA) were used as the polymer type radical polymerization initiator 4] of the present invention.

In addition, as shown in each example shown in Table 2, styrene (St) or methyl methacrylate (
MMA) was used. In each example, in 50% toluene,
A polymer having a radically polymerizable functional group per mole of vinyl monomer is added in an amount equivalent to 5 mmol of the functional group to a glass reactor purged with nitrogen, degassed, and heated at 80°C under a nitrogen blanket. The polymerization reaction was carried out for 3 hours. After this polymerization reaction, the polymers were isolated by pouring each reaction solution into methanol.

The resulting block and/or graft copolymers (A-B-A block in Examples 17-22 and 29, block/graft in Examples 23.24, Example 25)
．． The weight average molecule Ji (grafted body in Example 26, A-B block body in Example 27.28) determined by GPC
My), and molecular weight distribution (My/Kn), determined by solvent fractionation.

Percentage of grafting and/or grafting (blocking rate)
are shown in Table 2.

Table 2 [Effects of the Invention] The radical polymerization initiator [1] and the polymeric radical polymerization initiators [3 and 4] of the present invention have the ability to initiate living radical polymerization. When the method of the present invention using one initiator [two initiators] results in a larger molecular weight of the resulting polymer than when using a conventional living radical polymerization initiator such as phenylazotriphenylmethane; However, it is possible to obtain polymers with a narrow molecular weight distribution, (1) to obtain polymers with various functional groups introduced at the terminals, and (2) to synthesize star polymers.

By the method of the present invention [6] using initiators [3] and [4], (1) block and/or graft polymers can be obtained in high yield, and (2) block and/or graft polymers between incompatible segments can be obtained. It is also possible to obtain a body.

In particular, if an initiator [out of the three initiators] is based on a non-vinyl polymer, It can be obtained in high yield.

Claims (1)

[Claims] 1. General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, R^1 is a (substituted) aliphatic hydrocarbon group, a (substituted) alicyclic aliphatic hydrocarbon group or (substituted) aromatic hydrocarbon group, R^2, R^3, and R^4 each represent a (substituted) aromatic hydrocarbon group] A radical polymerization initiator represented by the following. 2. The initiator according to claim 1, wherein each of R^2, R^3, and R^4 is a (substituted) phenyl group or a (substituted) naphthyl group. 3, R^1 is a carboxyl group, sulfonyl group, sulfonium group, anhydrous carboxyl group, formyl group, cyano group,
an aliphatic hydrocarbon group substituted with one or more groups selected from an isocyanato group, a hydroxyl group, an amino group, a ketimine group, a nitro group, a halogen atom, a glycidyl group, a triphenylmethyloxy group, and a triphenylmethylmercapto group; The initiator according to claim 1 or 2, which is an alicyclic aliphatic hydrocarbon group or an aromatic hydrocarbon group. 4. R^1 is a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) [R^2, R^3, R^4 are each R^ described in claim 1
2, represents a group similar to R^3, R^4] Claims that the group is an aliphatic hydrocarbon group, an alicyclic aliphatic hydrocarbon group, or an aromatic hydrocarbon group substituted with one or more groups represented by Item 4. The initiator according to any one of items 1 to 3. 5. R^1 is a general formula ▲ There is a mathematical formula, a chemical formula, a table, etc. ▼ (3) [R^1, R^3, R^4 are each the R^ described in claim 1
2, R^3, and R^4] The initiator according to any one of claims 1 to 3, which is a group represented by the following. 6, R^2, R^3, R^4 each represents a nitro group, a sulfonyl group, a sulfonium group, a cyano group, a carboxyl group,
The initiator according to any one of claims 1 to 5, which is a phenyl group or a naphthyl group substituted with one or more groups selected from a carboxinium group and a halogen atom. 7. A method for polymerizing vinyl monomers, which comprises polymerizing using the initiator according to any one of claims 1 to 6. 8. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) [R^2, R^3, R^4 are each R^ described in claim 1
2. A polymer-type radical polymerization initiator characterized by comprising a polymer having one or more groups represented by [, which represent groups similar to R^3 and R^4, at the terminal and/or side chain. 9. The initiator according to claim 8, wherein the polymer is one or more polymers selected from polyolefin polymers, polyalkylene oxide polymers, polyester polymers, polyamide polymers, and polyurethane polymers. . 10. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) [R^2, R^3, and R^4 are each R^ described in claim 1
2, represents a group similar to R^3, R^4] A polymeric radical polymerization initiator comprising a polymer having one or more groups represented by the following at the terminal and/or side chain. 11. The initiator according to any one of claims 8 to 10, wherein each of R^2, R^3, and R^4 is a (substituted) phenyl group or a (substituted) naphthyl group. 12. Phenyl in which each of R^2, R^3, and R^4 is substituted with one or more groups selected from a nitro group, a sulfonyl group, a sulfonium group, a cyano group, a carboxyl group, a carboxinium group, and a halogen. The initiator according to any one of claims 8 to 11, which is a group or a naphthyl group. 13. A method for producing a polymeric radical polymerization initiator, which comprises reacting the initiator according to any one of claims 1 to 6 with a vinyl monomer. 14. A method for producing a polymeric radical polymerization initiator, which comprises reacting the initiator according to claim 8 or 9 with a vinyl monomer. 15. A block and/or block characterized by reacting the initiator according to any one of claims 8 to 12 with a vinyl monomer.
Or a method for producing a polymer composition comprising a graft type polymer. 11. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) [R^2, R^3, R^4 are each R^ described in claim 1
2, represents a group similar to R^3, R^4] A polymer consisting of a block and/or graft type polymer characterized by having one or more groups represented by the following at the end of the main chain and/or side chain. Coalescing composition.