JPH0995501A - Chain transfer agent for radical polymerization and production of polymer by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer having a narrow molecular weight distribution and being useful as a size, a dispersant, a hot melt adhesive or the like by polymerizing a radical-polymerizable monomer by using a specified chain transfer agent for radical polymerization. SOLUTION: A chain transfer agent for radical polymerization represented by the formula (wherein Q is a polyvalent organic group; X<1> is carbonyl or CONH; A<1> and A<2> are each a 1-8C alkylene; X<2> is O, S or NH; Z is a chain transfer group; (p), (q), (r) and (x) are each 0 or 1; (m) is 1-50; and (n) is 2-100) is prepared. Suitable examples of the chain transfer agents include a polyoxyethylene glycol di-2-mercaptoethyl ether, triethanolamine/ε-caprolactone adduct to tri-3-mercaptopropionic acid ester, etc. A polymer is produced by polymerizing a radical-polymerizable monomer (e.g. styrene) in the presence of this chain transfer agent and a radical polymerization initiator (e.g. dibenzoyl peroxide).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a chain transfer agent for radical polymerization and a method for producing a polymer using the chain transfer agent for radical polymerization. More specifically, it relates to a chain transfer agent which gives a polymer having a narrow molecular weight distribution, and a production method for using the chain transfer agent to obtain a polymer having a narrow molecular weight distribution.

[0002]

2. Description of the Related Art Conventionally, a polymer obtained by radical polymerization has a relatively wide molecular weight distribution. In order to obtain a polymer of acrylic acid and / or methacrylic acid having a narrow molecular weight distribution, a method of bulk polymerization in the presence of a sulfur compound (Japanese Patent Laid-Open No. 6-49131) is known.

[0003]

However, in the above method, the monomer and the polymerization method are limited, and further improvement in the molecular weight distribution is desired.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have earnestly studied a chain transfer agent which gives a polymer having a narrow molecular weight distribution, and a method for producing a polymer having a narrow molecular weight distribution by using the chain transfer agent. In the polymerization of the radical-polymerizable monomer, a chain transfer agent having a plurality of chain transfer groups and controlling the mutual positional relationship of the chain transfer groups to obtain a chain transfer agent giving a polymer having a narrow molecular weight distribution, and The present invention has been accomplished by finding a method for producing a polymer having a narrow molecular weight distribution using a chain transfer agent. That is, the present invention provides a radical polymerization chain transfer agent represented by the following general formula (1) and a method for producing a polymer in which a radical polymerizable monomer is polymerized by using a radical polymerization initiator. A method for producing a polymer characterized by using a chain transfer agent. General formula In the formula, Q is a polyvalent organic group, X ¹ is a carbonyl group or -C
ONH-, A ¹ and A ² are alkylene groups having 1 to 8 carbon atoms, X
² is an oxygen atom, a sulfur atom or an NH group, Z is a chain transfer group, p, q, r and x are 0 or 1 respectively, and m is 1 to 5
An integer of 0 and n are integers of 2 to 100, and may be the same or different in [] and in {} when m is 2 to 50.

In the general formula (1), Q is a residue obtained by removing OH from polyhydric alcohol or polyhydric phenol,
Examples thereof include a residue obtained by removing COOH from a polycarboxylic acid. As the polyhydric alcohol, alkylene glycol having 2 to 8 carbon atoms (ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6
-Hexanediol, neopentyl glycol, etc.),
Dioxy alcohols such as polyoxyalkylene glycol (diethylene glycol, triethylene glycol, polyethylene glycol, etc.) and diols having a cyclic group and having 5 to 10 carbon atoms; carbon number 3 such as glycerin, trimethylolpropane, trimethylolethane, hexanetriol, etc. ~ 12 trihydric alcohol; 4 to 4 carbon atoms such as pentaerythritol, methyl glycoside, diglycerin
20 tetrahydric alcohols; and alcohols having a higher number of functional groups, such as pentitol (such as adonitol, arabitol, xylitol), hexitol (such as sorbitol, mannitol, iditol, taritol, dulcitol), sugar [sucrose, monosaccharide ( Glucose, mannose, fructose, sorbose, etc.), oligosaccharides (crehalose, lactose, raffinose, etc.)]; glucosides (eg, glucosides of polyols (alkane polyols such as glycol, glycerin, trimethylolpropane, hexanetriol)); polyalkane polyols [Polyglycerin such as triglycerin and tetraglycerin]; polypentaerythritol (dipentaerythritol, tripentaerythritol, etc.) ; Cycloalkane polyol [tetrakis (hydroxymethyl) cyclohexanol, etc.] and the like. Further, polyvinyl alcohol having a degree of polymerization of up to 100 can be used.

Further, di- and triethanolamine; alkylamines having 2 to 20 carbon atoms, 2 to 6 carbon atoms
Alkylenediamines such as ethylenediamine, propylenediamine, hexamethylenediamine, polyalkylenepolyamines such as aliphatic amines such as diethylenetriamine, triethylenetetramine, aniline, phenylenediamine, diaminotoluene, xylylenediamine, methylenedianiline, diphenyletherdiamine, etc. Examples thereof include alicyclic amines such as group amines, isophoronediamine, cyclohexylenediamine, and dicyclohexylmethanediamine, and alkylene oxide adducts such as aminoethylpiperazine.

Examples of polyhydric phenols include monocyclic polyhydric phenols such as pyrogallol, hydroquinone and phloroglucin; bisphenols such as bisphenol A and bisphenol sulfone; condensates of phenol and formaldehyde (novolak) and polyphenols.

As the polyvalent carboxylic acid, divalent carboxylic acid [(1) aliphatic dicarboxylic acid having 2 to 20 carbon atoms (maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, malonic acid, azelaic acid, Mesaconic acid, citraconic acid, glutaconic acid, etc.); (2) Alicyclic dicarboxylic acid having 8 to 20 carbon atoms (cyclohexanedicarboxylic acid, methylmedic acid, etc.); (3) Aromatic dicarboxylic acid having 8 to 20 carbon atoms (phthalate) Acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, naphthalenedicarboxylic acid, etc.);
(4) Alkyl or alkenyl succinic acid having a hydrocarbon group having 4 to 35 carbon atoms in the side chain (isododecenyl succinic acid, n-dodecenyl succinic acid, etc.), trivalent or higher carboxylic acids [(1) carbon number 7 to 20 aliphatic polycarboxylic acids (1,2,4-butanetricarboxylic acid, 1,2,5
-Hexanetricarboxylic acid, 1,3-dicarboxylic acid-
2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, etc.); (2) carbon number 9-20
Alicyclic polycarboxylic acids (e.g., 1,2,4-cyclohexanetricarboxylic acid); (3) aromatic polycarboxylic acids having 9 to 20 carbon atoms (1,2,4-benzenetricarboxylic acid, 1,2,5 -Benzenetricarboxylic acid, 2,5,7
-Naphthalene tricarboxylic acid and 1,2,4-naphthalene tricarboxylic acid, pyromellitic acid, benzophenone tetracarboxylic acid, etc.)] and the like. Further, an unsaturated polycarboxylic acid polymer having a degree of polymerization of up to 100 can be mentioned.

In the general formula (1), Z is SH,
SR, SSR, CX ₃ (R is an alkyl, aryl, aralkyl, alkoxy, aryloxy or cycloalkyl group having 1 to 20 carbon atoms, which may be substituted with a halogen atom, an alkyl group, a cyano group or a nitro group. Is a chlorine atom, a bromine atom.) And the like. Of these, SH is preferred.

In the general formula (1), p is 0 when Q is a polyhydric alcohol or polyhydric phenol residue, and p is 1 when it is a polycarboxylic acid residue. If p is 0,
x and q are 0 or 1, and r is 0. When p is 1, x is 0 and q and r are 0 or 1, respectively.

In the general formula (1), n is preferably 2 to 8 and m is preferably 1 to 30. However, n is 100 or less when the polyhydric alcohol is polyvinyl alcohol.

The chain transfer agent represented by the general formula (1) is Z
When is SH, it can be manufactured by the following method, for example. Chain Transfer Agent 1 (when p is 0, x is 0, q is 0 and r is 0) After the cyclic ether is added to the ω-mercapto-alkyl alcohol, it is etherified with the polyhydric alcohol. Alternatively, a cyclic ether is added to a polyhydric alcohol, the terminal is chlorinated with thionyl chloride or the like, and then reacted with an alkali hydrosulfide. Specific examples of chain transfer agents include polyoxyethylene glycol-di-2-mercaptoethyl ether.

Chain transfer agent 2 (p is 1, x is 0, q is 0,
When r is 0) A cyclic ether (cyclic sulfide, cyclic imine) is added to ω-mercapto-alkyl alcohol, and then esterified with a polyvalent carboxylic acid.

Chain transfer agent 3 (p is 0, x is 1, q is 1,
When r is 0) A cyclic lactone (cyclic lactam) is added to the polyhydric alcohol, and then esterified (amidated) with ω-mercapto-carboxylic acid. Specific examples of chain transfer agents include triethanolamine-ε-caprolactone adduct-tri-3-mercaptopropionic acid ester.

Chain transfer agent 4 (p is 0, x is 1, q is 0,
When r is 0) After adding a cyclic lactone (cyclic lactam) to the polyhydric alcohol, etherification (amination) is carried out with ω-mercapto-halogenide. Specific chain transfer agents include triethanolamine-ε-caprolactone adduct-tri-2
-Mercaptoethyl ether and the like.

Chain transfer agent 5 (p is 0, x is 0, q is 1,
When r is 0) After adding a cyclic ether (cyclic sulfide, cyclic imine) to the polyhydric alcohol, esterification (thioesterification, amidation) is carried out with ω-mercapto-carboxylic acid. Specific examples of chain transfer agents that can be produced by this method include the following. (1) 1-10 alkylene oxides (ethylene glycol, propylene glycol, etc.) in alkylene glycols (ethylene glycol, propylene glycol, etc.)
A product obtained by adding 0 mol and forming a diester with 3-mercaptopropionic acid at the end. Polyoxyethylene glycol (number average molecular weight 630) di-3-mercaptopropionic acid ester, polyoxypropylene glycol (number average molecular weight 600) di-3-mercaptopropionic acid ester and the like. (2) A compound in which 1 to 150 mol of alkylene oxide is added to a trihydric or higher polyhydric alcohol (glycerin, pentaerythritol, sho, etc.), and the end is formed into a diester with 3-mercaptopropionic acid. Tetra-3-mercaptopropionic acid ester of pentaerythritol ethylene oxide 20 mol adduct and the like. (3) Polyvinyl acetate (weight average molecular weight 50,000,
Esterified with 2-mercaptoacetic acid (saponification degree 10%).

Chain transfer agent 6 (p is 1, x is 0, q is 1,
When r is 0) After adding a cyclic ether (cyclic sulfide, cyclic imine) to the polycarboxylic acid, esterification (thioesterification, amidation) is carried out with ω-mercapto-carboxylic acid. Specific examples of the chain transfer agent include propylene oxide adipate 4 mol adduct-di-2-mercaptoacetic acid ester.

Chain transfer agent 7 (p is 1, x is 0, q is 0,
When r is 1) A cyclic lactone (cyclic lactam) is added to the polycarboxylic acid, and then esterified with ω-mercapto-alcohol.

Of these chain transfer agents, preferred are chain transfer agents 1 to 4, more preferred are chain transfer agents 1 and 2, and particularly preferred is chain transfer agent 1.

In the production of the above compound, it is possible to co-add a cyclic ether and a cyclic lactone, for example.
When co-adding, either random co-adding or block co-adding may be used. Examples of cyclic ethers include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, and styrene oxide, examples of cyclic thioethers include episulfide, and examples of cyclic imines include ethyleneimine. These may be co-added, and when co-added, either random co-addition or block co-addition may be performed. Of these, preferred are cyclic ethers, and more preferred are ethylene oxide, propylene oxide and mixtures thereof. Examples of the cyclic lactone include ε-caprolactone and δ-valerolactone, and examples of the cyclic lactam include ε-caprolactam. These may be co-added, and when co-added, either random co-addition or block co-addition may be performed.

The object of the chain transfer agent of the present invention is that a plurality of chain transfer groups are mutually at least 4 functional groups (ether,
(Ester, amide, etc.) are present apart from each other, which makes it possible to produce a polymer having a narrow molecular weight distribution.

As long as the above conditions are satisfied, the structure can be arbitrarily selected depending on the properties of the polymer to be obtained. For example, the cyclic ether to be added in the case of the chain transfer agent 1 is preferably ethylene oxide for obtaining a (meth) acrylic acid (salt) polymer, and for obtaining a (meth) acrylic acid ester polymer or a styrene polymer. Preferred is propylene oxide.

The amount of the chain transfer agent used in the production method of the present invention is usually 0.001 with respect to the radical-polymerizable monomer.
-50% by weight, preferably 0.01-30% by weight, particularly preferably 0.1-15% by weight.

The following are examples of the monomers used in the method for producing the polymer of the present invention. (A) Aromatic ethylenically unsaturated monomer: styrene, α-
Styrenes such as methylstyrene, vinyltoluene and hydroxystyrene, halogen-substituted styrenes such as vinylnaphthalene and dichlorostyrene, etc. (b) Aliphatic ethylenically unsaturated monomers: ethylene, propylene, butene, isobutylene , Penten, heptene,
Diisobutylene, octene, dodecene, octadecene,
(C) alicyclic ethylenically unsaturated monomers such as butadiene and isoprene: cyclopentadiene, pinene, limonene, indene, bicyclopentadiene, ethylidene norbornene, etc. (d) alkyl having an alkyl group having 1 to 50 carbon atoms ( (Meth) acrylate: methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate, etc. ,

(E) Hydroxyl group-containing (meth) acrylate: hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc. (f) Amide-containing ethylenically unsaturated monomer: (meth) acrylamide, N-methylol (G) Ethylenically unsaturated monomer having a polyalkylene glycol chain such as (meth) acrylamide: polyethylene glycol (molecular weight 30
0) mono (meth) acrylate, polypropylene glycol (molecular weight 500) monoacrylate, methyl alcohol ethylene oxide 10 mol adduct (meth) acrylate, lauryl alcohol ethylene oxide 30 mol adduct (meth) acrylate, etc. Saturated carboxylic acid (salt) and its derivative (salt): (meth) acrylic acid (salt), (anhydrous) maleic acid (salt), maleic acid ester (salt) [maleic acid mono (methyl, ethyl, butyl, 2- Ethylhexyl,
(Lauryl, oleyl, stearyl, etc.) ester (salt)], fumaric acid (salt), fumaric acid ester (salt)
[Fumaric acid mono (methyl, ethyl, butyl, 2-ethylhexyl, lauryl, oleyl, stearyl, etc.) ester (salt)], citraconic acid, citraconic acid ester, etc.

(I) Sulfone group-containing monomer: vinyl sulfonic acid (salt), (meth) allyl sulfonic acid (salt), styrene sulfonic acid (salt), α-methylstyrene sulfonic acid (salt), sulfopropyl (salt) (Meth) acrylate, 2-hydroxy-3- (meth) acryloxypropyl sulfonic acid (salt), 2- (meth) acryloylamino-2,2-
Dimethylethanesulfonic acid (salt), 3- (meth) acryloyloxyethanesulfonic acid (salt), 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid (salt), 2- (meth) acrylamido-2-methyl Propanesulfonic acid (salt), 3- (meth) acrylamide-
2-hydroxypropanesulfonic acid (salt), alkyl (C3-18) allylsulfosuccinic acid (salt), poly (n = 2-30) oxyalkylene (ethylene, propylene, butylene: single, random, or block)
Sulfate ester of mono (meth) acrylate (salt)
[Poly (n = 5 to 15) oxypropylene monomethacrylate sulfate ester (salt) and the like], polyoxyethylene polycyclic phenyl ether sulfate (salt), and other compounds represented by the following general formula. (In the formula, R represents an alkyl group having 1 to 15 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and when n is plural, they may be the same or different, and when different, they may be random or blocks. , X represents an alkali metal, an alkaline earth metal, ammonium, or an amine cation, Ar represents a benzene ring, and n represents an integer of 1 to 50.)

[0027] (In the formula, R represents an alkyl group having 1 to 15 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and when n is plural, they may be the same or different, and when different, they may be random or blocks. , X represents an alkali metal, an alkaline earth metal, ammonium, or an amine cation, Ar represents a benzene ring, and n represents an integer of 1 to 50.)

[0028] (In the formula, R ′ represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a fluorine atom, and X represents an alkali metal, an alkaline earth metal, ammonium or an amine cation.)

The polymerization initiator used in the method for producing a polymer of the present invention is of a type that forms free radicals to initiate polymerization, such as 2,2'-azobisisobutyronitrile, 2,2. '-Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1)
-Arbonitrile), 2,2'-azobis (2,4,4
-Trimethylpentane), dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis [2- (hydroxymethyl) propionitrile], 1,
Azo compounds such as 1′-azobis (1-acetoxy-1-phenylethane); dibenzoyl peroxide,
Organic peroxides such as dicumyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, benzoyl peroxide, lauroyl peroxide, persuccinic acid; inorganic peroxides such as persulfates and perborates. Things can be used. Hydrogen peroxide, a redox type initiator or the like can be used. These may be used in combination of two or more. The amount of the polymerization initiator is usually 0.01 to 10% by weight, preferably 0.
0.5 to 5% by weight.

In the method for producing the polymer of the present invention, the polymerization method may be any of solution polymerization, emulsion polymerization, suspension and bulk polymerization, but solution polymerization is preferred in order to obtain a polymer having a narrow molecular weight distribution. Solvents for solution polymerization include water, alcohols (eg, methanol, ethanol, isopropanol), ketones (eg, acetone, methyl isobutyl ketone), ethers (eg, tetrahydrofuran), and aliphatic hydrocarbons (eg, hexane, heptane, etc.). ), Aromatic hydrocarbons (eg, toluene, xylene), halogenated solvents (eg, ethylene dichloride), and mixtures thereof.

The polymerization temperature is usually 50 to 300 ° C.,
It is preferably 60 to 250 ° C. Examples of the temperature include a temperature lower than the boiling point of the polymerization solution under normal pressure, a boiling point of the polymerization solution under normal pressure, and a temperature higher than the boiling point of the polymerization solution under pressure. In order to further narrow the molecular weight distribution, it is preferable to carry out the polymerization at a boiling point or higher of the polymerization solution under pressure. Further, when a dispersion medium, an emulsifier, a dispersant, etc. are used, there is no particular limitation and known ones can be used.

The weight average molecular weight of the polymer obtained by the production method of the present invention is usually 2,000 to 2,000,000.
It is 0, preferably 3,000 to 500,000. The molecular weight distribution is usually 1.05 to 4.50, preferably 1.0
5 to 3.00, particularly preferably 1.10 to 2.50. Although it depends on the polymerization system, it is often used 1
When compared with chain transfer agents having one chain transfer group, such as butanethiol, isopropanol, butyl iodide, t-butylbenzene, the molecular weight distribution is significantly narrowed when the chain transfer agent of the present invention is used. Here, the molecular weight distribution means (weight average molecular weight / number average molecular weight).

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In Examples and Comparative Examples,% and parts represent% by weight and parts by weight. The method for measuring the weight average molecular weight and the molecular weight distribution by GPC is as follows. <In the case of water-soluble (co) polymer> Machine type: Waters 510 (manufactured by Japan Waters Limited) Column: TSK gel G5000pwXL + TSK gel G3000pwXL (both manufactured by Tosoh Corporation) Column temperature: 40 ° C Detector: RI solvent: 0.5% sodium acetate / water / methanol (volume ratio 70/30) Flow rate: 1.0 ml / min Sample concentration: 0.25 wt% Injection volume: 200 μl Standard: Polyoxyethylene glycol (Tosoh Corporation; TSK STANDARD POLYETHYLENE OXIDE) <In the case of oil-soluble (co) polymer> (in the case of weight average molecular weight of 100,000 or less) Machine type: HLC-8120GPC (manufactured by Tosoh Corporation) Column: TSK gel Super H4000 + TSK gel Super H3000 + K gel Super H2000 (all manufactured by Tosoh Corporation) Column temperature: 40 ° C. Detector: RI solvent: Tetrahydrofuran Flow rate: 0.6 ml / min Sample concentration: 0.25 wt% Injection volume: 10 μl Standard: Polystyrene (Tosoh Co., Ltd .; TSK STANDARD POLYSTYRENE) (when weight average molecular weight is 100,000 or more) Machine type: HLC-802AGPC (manufactured by Tosoh Corporation) Column: TSK gel GMH XL + TSK gel GMH XL (both manufactured by Tosoh Corporation) Column temperature : 40 ° C. Detector: RI Solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Sample concentration: 0.25% by weight Injection volume: 200 μl Standard: Polystyrene (Tosoh Corporation; TSK STANDARD POLYSTYRENE)

[0034]

【Example】

(Production of Chain Transfer Agent) Production Example 1 of Chain Transfer Agent A pressure-resistant reactor was charged with 620 parts of ethylene glycol and 3 parts of potassium hydroxide, and the temperature was raised to 130 ° C. after purging with nitrogen.
5,740 parts of ethylene oxide was charged and reacted at 130 to 160 ° C. for 5 hours. After aging at the same temperature for 1 hour, the mixture was cooled to 50 to 70 ° C., 160 parts of water and 60 parts of synthetic magnesium silicate were added, and the mixture was stirred for 2 hours and then filtered. Then, it was dehydrated to obtain 6,000 parts of polyoxyethylene glycol having a number average molecular weight of 630. Then, 630 parts of this polyoxyethylene glycol was charged into a reaction vessel, and 260 parts of thionyl chloride was added dropwise at 80 ° C. over 2 hours while stirring. After maintaining the same temperature for 1 hour, 500 parts of a 30% sodium hydrosulfide aqueous solution was added dropwise over 3 hours. After being kept at the same temperature for 1 hour, the temperature was returned to room temperature, liquid separation was performed, and polyoxyethylene glycol-di-
600 parts of 2-mercaptoethyl ether were obtained. This is designated as chain transfer agent A.

Chain Transfer Agent Production Example 2 A pressure resistant reactor was charged with 760 parts of propylene glycol and 12 parts of potassium hydroxide, and the temperature was raised to 100 ° C. after purging with nitrogen. Propylene oxide 5,30 at 100-115 ° C
0 part was charged and reacted for 8 hours. After aging at the same temperature for 2 hours, the mixture was cooled to 50 to 70 ° C., 150 parts of water and 60 parts of synthetic magnesium silicate were added, and the mixture was stirred for 2 hours and filtered.
Then, it was dehydrated to obtain 5,900 parts of polyoxypropylene glycol having a number average molecular weight of 600. Next, 600 parts of this polyoxypropylene glycol was charged into a reaction vessel, and while stirring, 2 parts of 260 parts of thionyl chloride were added at 80 ° C.
It dripped over time. After keeping the same temperature for 1 hour, 30
% 500% aqueous sodium hydrosulfide solution was added dropwise over 3 hours. After maintaining at the same temperature for 1 hour, the temperature was returned to room temperature and liquid separation was performed to obtain 580 parts of polyoxypropylene glycol-di-2-mercaptopropyl ether which is the chain transfer agent of the present invention. This is designated as chain transfer agent B.

Chain Transfer Agent Production Example 3 A pressure resistant reactor was charged with 680 parts of pentaerythritol and 5 parts of potassium hydroxide, and the temperature was raised to 130 ° C. after purging with nitrogen. Ethylene oxide 4,450 at 130-160 ° C
The parts were charged and reacted for 5 hours. After aging at the same temperature for 1 hour, the mixture was cooled to 50 to 70 ° C., 160 parts of water and 60 parts of synthetic magnesium silicate were added, and the mixture was stirred for 2 hours and then filtered. Then, it was dehydrated to obtain 5,000 parts of an ethylene oxide 20 mol adduct of pentaerythritol. Then, 510 parts of this adduct was charged into a reaction vessel and stirred to 80
520 parts of thionyl chloride was added dropwise at 4 ° C. over 4 hours. After maintaining the same temperature for 1.5 hours, 1,000 parts of a 30% sodium hydrosulfide aqueous solution was added dropwise over 5 hours. After maintaining at the same temperature for 2 hours, the temperature was returned to room temperature, and liquid separation was performed to obtain a pentaerythritol ethylene oxide adduct tetra-2-mercaptoethyl ether which is the chain transfer agent of the present invention. This is designated as chain transfer agent C.

Chain Transfer Agent Production Example 4 A pressure resistant reactor was charged with 680 parts of pentaerythritol and 5 parts of potassium hydroxide, and the temperature was raised to 130 ° C. after purging with nitrogen. Propylene oxide 5,85 at 110 to 130 ° C
0 part was charged and reacted for 5 hours. After aging at the same temperature for 1 hour, the mixture was cooled to 50 to 70 ° C., 160 parts of water and 60 parts of synthetic magnesium silicate were added, and the mixture was stirred for 2 hours and then filtered.
Then, dehydration was performed to obtain 6,500 parts of a pentaerythritol propylene oxide 20 mol adduct. Then,
650 parts of this adduct was placed in a reaction vessel, and 520 parts of thionyl chloride was added dropwise at 80 ° C. over 4 hours while stirring. After maintaining the same temperature for 1.5 hours, 1,000 parts of a 30% sodium hydrosulfide aqueous solution was added dropwise over 5 hours. After holding at the same temperature for 2 hours, the temperature was returned to room temperature, and liquid separation was performed to obtain pentaerythritol propylene oxide adduct tetra-2-mercaptoethyl ether which is the chain transfer agent of the present invention. This is designated as chain transfer agent D.

(Production of Polymer) Example 1 260 parts of isopropyl alcohol and 5 parts of water were placed in a pressure resistant reactor.
50 parts were charged, the atmosphere was replaced with nitrogen, the vessel was sealed, and the temperature was raised to 100 ° C. With stirring, a uniform mixture of 170 parts of methacrylic acid, 120 parts of butyl methacrylate and 20 parts of chain transfer agent A, and 45 parts of a 4% sodium persulfate aqueous solution were simultaneously added dropwise from separate containers over 4 hours. After holding at the same temperature for 1 hour, it was neutralized with 15 parts of a 48% aqueous sodium hydroxide solution. Then, the isopropyl alcohol was distilled off and further neutralized with an aqueous 28% ammonia solution to obtain 1,000 parts of a 30% aqueous solution of a methacrylic acid salt copolymer. The weight average molecular weight was 100,000 and the molecular weight distribution was 1.8.

Comparative Example 1 A 30% aqueous solution of a methacrylic acid copolymer was prepared in the same manner as in Example 1 except that the chain transfer agent A was not used.
I got 0 copies. The weight average molecular weight was 110,000 and the molecular weight distribution was 4.2.

Example 2 A pressure resistant reactor was charged with 320 parts of ethylene dichloride, 95 parts of maleic anhydride and 20 parts of a chain transfer agent C, and the temperature was raised to 80 ° C. after purging with nitrogen. With stirring, a mixture of 27 parts of butyl acrylate and 90 parts of styrene and 20 parts of a 2,2′-azobisisobutyronitrile 10% ethylene dichloride solution were added dropwise from separate containers simultaneously over 3 hours for polymerization. . After holding at the same temperature for 1 hour, a mixture of 40 parts of 2-ethylhexyl alcohol and 30 parts of butyl cellosolve was added for esterification. After neutralizing with 6 parts of 48% aqueous sodium hydroxide solution, the ethylene dichloride was distilled off,
Further, 140 parts of 28% aqueous ammonia solution was added, and a 30% aqueous solution of maleic acid half-ester salt copolymer salt was added to 1,000.
Got a part. The weight average molecular weight was 30,000 and the molecular weight distribution was 1.5.

Comparative Example 2 1,000 parts of a 30% aqueous solution of a maleic acid half-ester salt copolymer was obtained in the same manner as in Example 2 except that the chain transfer agent C was not used. The weight average molecular weight is 40,000,
The molecular weight distribution was 3.2.

Comparative Example 3 A 30% aqueous solution of a maleic acid half-ester salt copolymer was obtained in the same manner as in Example 2 except that 10 parts of lauryl mercaptan was used as the chain transfer agent. The weight average molecular weight was 20,000 and the molecular weight distribution was 3.8.

(Evaluation) Examples 1 and 2 and Comparative Examples 1 to 3
Table 1 shows the results of evaluation of the size effect using the 30% aqueous solution of the copolymer obtained in (1). The evaluation conditions are as follows. (1) Base paper Pulp L-BKP 100% Filler Talc (12% ash in paper) pH 4.9 (hot water extraction method) Stekihit sizing degree 2 seconds (2) Surface sizing device Lab size press combined drug Oxidized starch (1) 0.8 g / m ² ,
Solid content) Drying rotary auto dryer, 105
℃, 60 seconds

[0044]

[Table 1] ----------------------------------------- Steckigt sizing degree (sec) Cobb sizing degree (g / m ²⁾ coating amount ^{(g / m 2) 0.01 0.03} 0.01 0.03 -------------------------- --------------- Example 1 27 39 14 13 Example 2 26 38 15 13 Comparative Example 1 22 22 20 20 19 Comparative Example 2 20 25 21 19 Comparative Example 3 18 22 22 25 22 -------- ----------------------------------------- The coating amount is based on the solid content (copolymer salt).

Example 3 A flask equipped with a stirrer, a reflux condenser, two dropping funnels, a thermometer and a gas blowing port was charged with 400 parts of xylene and 5 parts of a chain transfer agent D, and the atmosphere was replaced with nitrogen while stirring.
The temperature was raised to ° C. A mixture of 500 parts of styrene and 4.5 parts of chain transfer agent A was added dropwise from one dropping funnel at the same temperature over 5 hours, and at the same time, di-tert-butyl peroxide 12 was added from the other dropping funnel.
And 200 parts of xylene was added dropwise over 6 hours. After maintaining the same temperature for 3 hours, the solvent and unreacted monomers were distilled off to obtain 8800 parts of a styrene polymer. The number average molecular weight was 4,000 and the molecular weight distribution was 1.7.

Comparative Example 4 The same procedure as in Example 3 was repeated except that no chain transfer agent was used and 20 parts of di-tert-butyl peroxide was used.
A styrene polymer was obtained. The number average molecular weight was 4,000 and the molecular weight distribution was 3.1.

Table 2 shows the results of performance evaluation as the dispersant. The evaluation method is as follows. 1. Dispersibility 100 parts by weight of fine powder of each dispersant and 100 parts by weight of fine powder of phthalocyanine blue were mixed using a V-type blender (manufactured by Tsutsui Rikagaku Kikai Co., Ltd.) to prepare a dry blend. This dry blend composition was kneaded with a three-roll kneader at 130 ° C. The kneaded composition and polystyrene were mixed at a ratio such that the pigment concentration became 1.3% by weight.
Each was supplied to a Brabender kneader rotating at a speed of 50 rpm at 160 ° C. and kneaded for 5 minutes. This kneaded product is pressed under the condition of a pressing temperature of 170 ° C.,
A film having a thickness of 0.1 mm was obtained. The number of pigment particles in this film was read with an optical microscope, and LA- manufactured by Pierce was used.
The dispersibility was evaluated by the 555 image analyzer in the following 5 grades from 5 to 1. 5: The number of particles of 50 μm or more is 1 × 1000 or less / cubic centimeter 4: The same, 1 × 1000 to 7 × 1000 / cubic centimeter 3: The same, 7 × 1000 to 2.7 × 10000 / cubic centimeter 2: same, 2.7 × 10,000 to 7 × 10000 / cubic centimeter 1: same, 7 × 10000 or more / cubic centimeter

2. Transparency The haze of the above film was measured according to JIS-K7105. The smaller the value, the better the transparency. 3. Kneading Workability The dry blend composition comprising the dispersant and phthalocyanine blue was examined for workability in the three-roll kneading process. The workability was evaluated as good when the kneaded product was satisfactorily attached to the roll during kneading, and the amount of dust generated when scraping from the roll was small. 4. Bleed-out property The above-mentioned film surface was visually observed and examined for bleed-out.

[0049]

Table 2 ------------------ Polymer-Pigment dispersibility Film haze (%) Kneading workability Bleed-out property ------------------------------------------ Example 3 3 5 8 Good Good Good Comparison Example 4 4 15 Poor Good −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−

As shown in Table 2, the polymer of the present invention is extremely excellent in transparency (film haze) and kneading workability.

Example 4 150 parts of styrene, 50 parts of acrylonitrile, 50 parts of maleic anhydride, 800 parts of ethylene dichloride and a chain transfer agent were placed in a flask equipped with a stirrer, a reflux condenser, two dropping funnels, a thermometer and a gas inlet. Part D1 was charged, the atmosphere was replaced with nitrogen with stirring and the temperature was raised to 80 ° C. A mixture of 500 parts of styrene, 250 parts of acrylonitrile, 1.5 parts of a chain transfer agent C and 100 parts of tetrahydrofuran was added dropwise from one dropping funnel at the same temperature over 6 hours, and at the same time, azo was simultaneously discharged from the other dropping funnel. A mixture of 12 parts of bisisobutyronitrile and 200 parts of tetrahydrofuran was added dropwise over 7 hours. After maintaining the same temperature for 3 hours, the solvent and unreacted monomers were distilled off to obtain 920 parts of a styrene / acrylonitrile / maleic anhydride copolymer.
The number average molecular weight was 12,000 and the molecular weight distribution was 1.8.

Comparative Example 5 The procedure of Example 4 was repeated except that no chain transfer agent was used.
A styrene / acrylonitrile / maleic anhydride copolymer was obtained. The number average molecular weight was 13,000 and the molecular weight distribution was 2.9.

Evaluation of compatibilizer 6-nylon [trade name: UBE nylon 1013B, Ube Industries, Ltd.] 60 parts, ABS resin [trade name: Toyolac 500, Toray Co., Ltd.] 40 parts and Example 1 Alternatively, 5 parts of the copolymer of Comparative Example 1 was mixed using a twin-screw extruder at a cylinder temperature of 265 ° C. Cylinder temperature of 270 ° C., injection pressure of 600 Kg / c
A test piece was obtained by injection molding at m ² and a mold temperature of 80 ° C. Table 3 shows the fluidity, the characteristics of the test piece, and the dispersed particle size of the test piece (broken surface in liquid nitrogen and observed by electron microscope for fracture surface).

[0054]

[Table 3] ------------------ Co-polymer Fluidity Impact strength Heat distortion temperature Appearance Dispersed particle size (mm) (Kg · cm / cm) (° C) (μm) −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−− Example 4 90 50 90 No abnormality 2 or less Comparative Example 5 75 18 89 With layered peeling 5-10 −−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−

As shown in Table 3, the polymer of the present invention, when used as a compatibilizer, has a good appearance and a good dispersion (small dispersed particle size), so that the resin composition has an excellent impact strength. You can provide things.

Example 5 200 parts of xylene was placed in a pressure resistant reactor and heated to 165 ° C. 500 parts of styrene, 500 parts of 2-ethylhexyl acrylate, 2 parts of chain transfer agent B and di-t at the same temperature.
A mixture of 30 parts of ert-butyl peroxide was added dropwise over 3 hours to carry out polymerization. After maintaining the same temperature for 30 minutes, volatile matter was removed and styrene / acrylic copolymer 950
Got a part. The weight average molecular weight was 5,500, the number average molecular weight was 4,000, the molecular weight distribution was 1.4, and the melt viscosity at 180 ° C. was 46 cps.

Comparative Example 6 A styrene / acrylic copolymer was obtained in the same manner as in Example 5 except that the chain transfer agent B was not used. The weight average molecular weight was 5,500, the number average molecular weight was 3,100, the molecular weight distribution was 1.8, and the melt viscosity at 180 ° C. was 50.5 cps.

Evaluation of Hot Melt Adhesive 30 parts of SEBS resin (trade name: Kraton G1657, manufactured by Shell Kagaku), paraffin oil (trade name: PW-9)
0, Idemitsu Kosan) 10 parts, hydrogenated petroleum resin (trade name: Alcon M-100, Arakawa Chemical Co., Ltd.) 30 parts and the styrene / acrylic copolymer of Example 3 or Comparative Example 3 30 parts,
A hot kneader was uniformly mixed at 190 ° C. to obtain a hot melt adhesive. Table 4 shows the melt viscosity (180 ° C., unit is cps), heat resistance and peel strength of each. In addition, the heat resistance is the same as that of a 25 mm × 25 mm PET film laminated sheet coated with 200 μm of hot melt adhesive,
A time of applying a load of 1.5 kg at 40 ° C. and peeling the film and dropping it was measured. The unit is minutes. The peel strength was measured with a PET film based on JISK6854. The unit is g / 25 mm.

[0059]

[Table 4] ------------- Co-polymer Melt viscosity Heat resistance Peel strength ---------- --------------- Example 5 9,000 120 2,500 Comparative Example 6 9,500 85 2,300 --------------------. −−

As shown in Table 4, the hot melt adhesive of the present invention is superior in heat resistance, peel strength and melt viscosity as compared with Comparative Examples.

[0061]

The (co) polymer obtained by using the chain transfer agent of the present invention can be obtained by using a chain transfer agent having only one chain transfer group which has been often used conventionally. Since the molecular weight distribution is narrower than that of the polymer, it exerts an unprecedented function, and when used as a sizing agent, a dispersant, a compatibilizing agent and a hot melt adhesive, it exhibits excellent performance with a small amount of additives. It can also be used as a polymer drug such as a polymer plasticizer or a surface modifier (a lubricant, a release agent, etc.).

Claims (8)

[Claims] 1. A chain transfer agent for radical polymerization of a radically polymerizable monomer represented by the following general formula (1). General formula In the formula, Q is a polyvalent organic group, X ¹ is a carbonyl group or -C
ONH-, A ¹ and A ² are alkylene groups having 1 to 8 carbon atoms, X
² is an oxygen atom, a sulfur atom or an NH group, Z is a chain transfer group, p, q, r and x are 0 or 1 respectively, and m is 1 to 5
An integer of 0 and n are integers of 2 to 100, and may be the same or different in [] and in {} when m is 2 to 50. 2. The chain transfer agent according to claim 1, wherein Z is SH in the general formula (1). 3. The chain transfer agent according to claim 1, wherein in the general formula (1), n is an integer of 2-8. 4. In the general formula (1), p, q, r, x
Are 0 and X ² is an oxygen atom, respectively, The chain transfer agent according to claim 1. 5. The chain transfer agent according to claim 1, wherein in the general formula (1), m is 1 to 30. 6. In the general formula (1), A ² has 1 carbon atom.
6. The chain transfer agent according to claim 1, which is an alkylene group of 4 to 4. 7. A method for producing a polymer in which a radical polymerizable monomer is polymerized using a radical polymerization initiator, wherein the chain transfer agent for radical polymerization according to any one of claims 1 to 6 is used. A method for producing a polymer. 8. The method according to claim 7, wherein the amount of the chain transfer agent is 0.001 to 50% by weight based on the radical-polymerizable monomer.