JP2012158696A - Method for producing vinyl polymer, and vinyl polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing vinyl polymer where the residue of secondary aggregate and vinyl monomer is small, the molecular weight is small, and the terminal double bond amount is large.SOLUTION: In this method for producing vinyl polymer, vinyl monomer is suspended and polymerized in a condition satisfying formula (2) using, as a polymerization initiator, organic peroxide where a carboxy group-containing compound generated by thermal decomposition is 0.07 moles or less per 1 mole of organic peroxide. Formula (2) shows 0.0002<cobalt complex amount (mol)/organic peroxide amount (mol)<0.01.

Description

  The present invention relates to a method for producing a vinyl polymer and a vinyl polymer.

  Suspension polymerization is one of the polymerization methods for vinyl polymers, and is well known as a method for producing a vinyl polymer having a particle size of about 10 to 1000 μm in solid form.

  Conventionally, when producing a vinyl polymer having a weight average molecular weight of 20000 or less by suspension polymerization, a large amount of an initiator or a mercaptan chain transfer agent is used, and the polymerization temperature is heated to the boiling point of the medium or higher. The method of polymerizing under pressure was common.

  However, in this method, it was difficult to control the heat generation, and because a large amount of initiator and chain transfer agent were used, an initiator decomposition product, residual chain transfer agent, or odor derived from residual vinyl monomer was obtained. There was a problem that the performance of the coating film deteriorated when the vinyl polymer was converted into a paint.

  For this reason, as a method for producing a vinyl polymer having a weight average molecular weight of 20000 or less, a method using a specific cobalt complex as a chain transfer agent is known. Moreover, since the polymer obtained by this method has an unsaturated double bond at the terminal, it can be used as a macromonomer. As the use of the macromonomer, a polymer obtained by copolymerization with other vinyl monomers can be used for paints, inks, adhesives and the like.

  As such a method, for example, Patent Document 1 describes a method of producing a vinyl polymer having a weight average molecular weight of 20000 or less using a cobalt complex and an azo initiator.

  Patent Document 2 describes that a peroxide is used as an initiator when a cobalt complex is used as a chain transfer agent.

JP-A-61-241302 Japanese National Patent Publication No. 10-508333

  However, in the method described in Patent Document 1, since an azo-based initiator is used as a polymerization initiator, a large amount of vinyl polymer or secondary aggregate having a low specific gravity is generated due to nitrogen derived from the initiator. However, there is a problem that the yield is remarkably lowered. Furthermore, secondary agglomerates and vinyl monomers remain in the vinyl polymer, and when used for odor and paint applications, the appearance of the coating film was insufficient.

  In addition, in the method described in Patent Document 2, a cobalt complex is decomposed and deactivated by a carboxyl group-containing compound generated from an initiator, and a polymer having a weight average molecular weight of 20000 or less and a large amount of terminal double bonds cannot be obtained. There was a problem.

  The present invention aims to solve these problems.

  The gist of the present invention is an organic peroxide in which the amount of a carboxyl group-containing compound generated by thermal decomposition is 0.07 mol or less per mol of organic peroxide in the presence of the cobalt complex represented by the following general formula (1). It exists in the manufacturing method of the vinyl polymer which uses as a polymerization initiator and suspension-polymerizes a vinyl monomer on the conditions which satisfy | fill following formula (2).

〔式（１）中、Ｒ１〜Ｒ４は、それぞれ独立して、アルキル基、シクロアルキル基及びアリール基；Ｘは、それぞれ独立して、Ｆ原子、Ｃｌ原子、Ｂｒ原子、ＯＨ基、アルコキシ基、アリールオキシ基、アルキル基及びアリール基〕
０．０００２＜コバルト錯体量（ｍｏｌ）／有機過酸化物量（ｍｏｌ）＜０．０１・・・（２）

[In Formula (1), R1-R4 are each independently an alkyl group, a cycloalkyl group, and an aryl group; X is each independently F atom, Cl atom, Br atom, OH group, alkoxy group, Aryloxy group, alkyl group and aryl group]
0.0002 <Cobalt complex amount (mol) / Organic peroxide amount (mol) <0.01 (2)

  According to the production method of the present invention, a vinyl polymer having a small amount of residual secondary aggregates and vinyl monomers, a weight average molecular weight of 20000 or less, and a large amount of terminal double bonds can be obtained. In addition, when a polymer obtained by copolymerizing with another vinyl monomer as a macromonomer is used as a coating resin, it has excellent adhesion, coating appearance, coating coloring, coating hardness, and workability. A coating film is obtained.

  As the cobalt complex used in the present invention, a cobalt complex represented by the formula (1) can be used. Those described in Japanese Laid-Open Patent Publication No. 4694054, US Pat. No. 4,837,326, US Pat. No. 4,886,861, US Pat.

〔式（１）中、Ｒ１〜Ｒ４は、それぞれ独立して、アルキル基、シクロアルキル基及びアリール基；Ｘは、それぞれ独立して、Ｆ原子、Ｃｌ原子、Ｂｒ原子、ＯＨ基、アルコキシ基、アリールオキシ基、アルキル基及びアリール基〕
具体的には、ビス（ボロンジフルオロジメチルジオキシイミノシクロヘキサン）コバルト（ＩＩ）、ビス（ボロンジフルオロジメチルグリオキシメイト）コバルト（ＩＩ）、ビス（ボロンジフルオロジフェニルグリオキシメイト）コバルト（ＩＩ）、ビシナルイミノヒドロキシイミノ化合物のコバルト（ＩＩ）錯体、テトラアザテトラアルキルシクロテトラデカテトラエンのコバルト（ＩＩ）錯体、Ｎ，Ｎ’−ビス（サリチリデン）エチレンジアミノコバルト（ＩＩ）錯体、ジアルキルジアザジオキソジアルキルドデカジエンのコバルト（ＩＩ）錯体、コバルト（ＩＩ）ポルフィリン錯体などがあげられる。

[In Formula (1), R1-R4 are each independently an alkyl group, a cycloalkyl group, and an aryl group; X is each independently F atom, Cl atom, Br atom, OH group, alkoxy group, Aryloxy group, alkyl group and aryl group]
Specifically, bis (borondifluorodimethyldioxyiminocyclohexane) cobalt (II), bis (borondifluorodimethylglyoxymate) cobalt (II), bis (borondifluorodiphenylglyoxymate) cobalt (II), vicinal Cobalt (II) complex of iminohydroxyimino compound, cobalt (II) complex of tetraazatetraalkylcyclotetradecatetraene, N, N′-bis (salicylidene) ethylenediaminocobalt (II) complex, dialkyldiazadioxodialkyldodeca Examples thereof include cobalt (II) complexes of diene and cobalt (II) porphyrin complexes.

  One or more of these can be appropriately selected and used. Among these, bis (borondifluorodiphenylglyoxymate) cobalt (II) (R1 to R4: phenyl group, X: F atom) that is stably present in an aqueous medium and has a high chain transfer effect is preferable.

  The amount of the cobalt complex used is preferably 20 to 350 ppm with respect to 100 g of the vinyl monomer. If the amount of cobalt complex used is less than 20 ppm, the molecular weight tends to be insufficiently reduced, and if it exceeds 350, the resulting vinyl polymer tends to be colored.

  As the polymerization initiator used in the present invention, an organic peroxide having a carboxyl group-containing compound amount generated by thermal decomposition of 0.07 mol or less per 1 mol of organic peroxide is used.

  If the amount of the carboxyl group-containing compound generated by thermal decomposition is 0.07 mol or less per 1 mol of the organic peroxide, the cobalt complex may be decomposed and deactivated by the carboxyl group-containing compound generated by the thermal decomposition of the organic peroxide. In addition, a polymer having a weight average molecular weight of 20000 or less and a large amount of terminal double bonds can be obtained.

  The amount of the carboxyl group-containing compound generated by thermal decomposition from the polymerization initiator is measured by the following method.

  In an apparatus equipped with a stirrer, a condenser, and a thermometer, 95 parts of xylene and 5 parts of an organic peroxide were added and stirred, and the temperature was raised to 100 ° C. while replacing the inside of the apparatus with nitrogen. After reaching 100 ° C., the solution was held at 100 ° C. for 3 hours and then cooled to room temperature to obtain a solution.

  Using 1 μl of the obtained solution, while increasing the temperature from 50 ° C. to 240 ° C. at 10 ° C./min, measurement is performed at a flow rate of 20 ml / min, and the amount of the generated carboxyl group-containing compound is measured. The amount of the carboxyl group-containing compound generated from 1 mol of the product was determined.

  “Agilent 6890N” (trade name, manufactured by Agilent Technologies, Inc.) was used for gas chromatography (GC), and J & W DB-FFAP (trade name, manufactured by Agilent Technologies, Inc.) was used for the column. The calibration curve was prepared using TSK standard polystyrene F288 / F80 / F40 / F10 / F4 / F1 / A5000 / A1000 / A500 (trade name, manufactured by Tosoh Corporation) and styrene.

As the organic peroxide of the present invention,
1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-amylperoxy 2-ethylhexanoate, t-butylperoxy 2 -Ethylhexanoate, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate Ate, t-butylperoxyneoheptanoate, t-hexylperoxypivalate, t-butylperoxypivalate, di-t-butylperoxyhexahydrophthalate, 2,5-dimethyl-2,5-di (2-Ethylhexanoylperoxy) hexane, 2,5-dimethyl-2,5-di (2-benzoylperoxy) he Sun, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-hexylperoxybenzoate, di (4-t-butylcyclohexyl) peroxycarbonate, di ( 2-ethylhexyl) peroxycarbonate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylper Examples thereof include oxyisopropyl monocarbonate and t-butyl peroxyisopropyl monocarbonate.

  In addition, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexano is high in that the chain transfer constant is high and the polymerization temperature can be easily controlled during suspension polymerization at a 10-hour half-life temperature. Acid, t-hexylperoxy 2-ethylhexanoate, and t-butylperoxy 2-ethylhexanoate are preferred.

In the present invention, it is necessary that the amount of cobalt complex and the amount of organic peroxide satisfy the formula (2).
0.0002 <Cobalt complex amount (mol) / Organic peroxide amount (mol) <0.01 (2)
When the amount of cobalt complex (mol) / the amount of organic peroxide (mol) was more than 0.0002, the amount of terminal double bonds of the vinyl polymer increased, and the vinyl polymer of the present invention was obtained as a macromonomer. The adhesion of the paint film is improved.

  Moreover, when the amount of cobalt complex (mol) / the amount of organic peroxide (mol) is less than 0.01, the vinyl polymer is not colored, the polymerization yield is high, and the residual vinyl monomer is also reduced.

  The amount of cobalt complex (mol) / the amount of organic peroxide (mol) is preferably 0.0004 or more, and preferably 0.009 or less.

In order to further reduce the molecular weight with the same initiator amount, it is preferable that the chain transfer effect is high. The chain transfer effect can be quantitatively expressed by determining the chain transfer constant Cs when each initiator is used.
That is,
1 / DPn = 1 / DPn, 0 + Cs [Co (II)] / [M] (3)
Dpn: degree of polymerization of vinyl polymer produced by polymerization in the presence of chain transfer agent Dpn, 0: degree of polymerization of vinyl polymer produced by polymerization in the absence of chain transfer agent Cs: chain transfer constant [Co (II)] / [M]: mol ratio of charged cobalt complex and vinyl monomer (reference: radical polymerization handbook, supervised by Mikiharu Tsunoike, 1999, TNS Inc., p38-48)
The larger the chain transfer constant Cs determined by the formula (3), the lower the molecular weight even with the same initiator amount. Preferably, Cs is 2000 or more, more preferably 3000 or more.

  Examples of the vinyl monomer of the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl. (Meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 2-methoxyethyl ( (Meth) acrylates such as (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydride Hydroxyl-containing (meth) acrylic acid esters such as xylbutyl (meth) acrylate and glycerol (meth) acrylate; (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexa Hydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- Carboxyl group-containing vinyl monomers such as (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monomethyl itaconate; Anhydrous male Acid anhydride group-containing vinyl monomers such as acid and itaconic anhydride; epoxy group-containing vinyl such as glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, and 3,4-epoxybutyl (meth) acrylate Monomers; amino group-containing (meth) acrylic ester vinyl monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; (meth) acrylamide, Nt-butyl (meta ) Vinyl monomers containing amide groups such as acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide, maleic acid amide, maleimide Styrene, α-methylstyrene, vinyltoluene, (meth) a Vinyl monomers such as rilonitrile, vinyl chloride, vinyl acetate, vinyl propionate, divinylbenzene, ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) ) Acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, N, N'- And polyfunctional vinyl monomers such as methylene bis (meth) acrylamide. One or more of these can be appropriately selected and used.

  “(Meth) acrylate” means “acrylate and / or methacrylate”, “(meth) acrylic acid” means “acrylic acid and / or methacrylic acid”, and “(meth) acryloyl” means “acryloyl”. And / or methacryloyl ”,“ (meth) acrylonitrile ”means“ acrylonitrile and / or methacrylonitrile ”, and“ (meth) acrylamide ”means“ acrylamide and / or methacrylamide ”.

  In the present invention, suspension polymerization may be carried out by a known method. A vinyl monomer, a chain transfer agent, and a polymerization initiator are added to water containing a dispersant to suspend the aqueous suspension. The polymerization reaction is allowed to proceed by heating, and the aqueous suspension after polymerization is filtered, washed, dehydrated and dried.

  Examples of the dispersant include poly (meth) acrylic acid alkali metal salts, alkali metal salts of copolymers of (meth) acrylic acid and methyl (meth) acrylate, polyvinyl alcohol having a saponification degree of 70 to 100%, and methylcellulose. Etc. can be used.

  The amount of the dispersant is preferably 0.005 to 5% by mass in the aqueous suspension, and more preferably in the range of 0.01 to 1% by mass. When the amount of the dispersant used is 0.005% by mass or more, the dispersion stability of the suspension polymerization liquid is good, and the resulting vinyl polymer has good cleaning properties, dehydration properties, drying properties, and fluidity. There is a tendency. On the other hand, when the content is 5% by mass or less, there is little foaming during polymerization and the polymerization stability tends to be good. For the purpose of improving the dispersion stability of the aqueous suspension, an electrolyte such as sodium carbonate, sodium sulfate or manganese sulfate may be used.

  Moreover, it is preferable that superposition | polymerization temperature is T-10 degreeC or more and 130 degrees C or less as 10-hour half life temperature T degreeC of a polymerization initiator. When the polymerization temperature is T-10 ° C. or higher, the amount of peroxide as a polymerization initiator is reduced, the amount of acid compound generated is reduced, and the amount of terminal double bonds of the vinyl polymer tends to be increased. In addition, the polymerization can be completed in a relatively short time, and the dispersion stability tends to be good during suspension polymerization. Further, when the temperature is 130 ° C. or lower, the polymerization exotherm is alleviated and the polymerization temperature tends to be easily controlled.

  Since the vinyl polymer obtained by the production method of the present invention has a low molecular weight, it retains a low viscosity even when dissolved in a high concentration in an organic solvent or a vinyl monomer, and has excellent paintability. As a resin, it can be applied to environmentally friendly paints with low VOC.

  The resin composition for coatings containing the vinyl polymer of the present invention can be produced by a known method, and if necessary, a colorant, a filler, a pigment dispersant, an antigelling agent, an antioxidant, a radical scavenger, a light Various additives such as a stabilizer, an ultraviolet absorber, a leveling agent, a repellency inhibitor, a dripping agent, a surface conditioner, a wax, and a curing catalyst can be added. Furthermore, other resin components, photoreactive monomers, oligomers, and the like can be added.

Further, since the vinyl polymer of the present invention has a terminal double bond, it can be copolymerized with a vinyl monomer as a macromonomer to obtain a graft copolymer. The copolymerization may be performed by a known method such as suspension polymerization, solution polymerization, bulk polymerization, emulsion polymerization, or fine suspension polymerization.
For example, in the case of suspension polymerization, a vinyl polymer can be dissolved in a vinyl monomer, and suspension polymerization can be performed by a known method. Moreover, when performing solution polymerization, a vinyl polymer can be dissolved in a vinyl monomer and a solvent, and solution polymerization can be performed by a known method. It does not specifically limit as a solvent to be used, The solvent generally used in radical polymerization can be used.

  As the vinyl monomer to be copolymerized, those mentioned as the vinyl polymer monomer of the present invention can be used.

  When used as a macromonomer, the content of the terminal double bond of the vinyl polymer produced according to the present invention is preferably 0.7 or more, more preferably 0.8 or more per polymer chain. . When the content of terminal double bonds is 0.7 or more, the amount of copolymerization with the vinyl monomer is high, and when the polymer obtained by copolymerization is used as a coating resin, adhesion, coating film A coating film excellent in appearance, coating film hardness, and workability can be obtained.

  The content of the terminal double bond was measured using a nuclear magnetic resonance apparatus (NMR) “EXcalibur 270 superconducting FT-NMR” (trade name, manufactured by JEOL Ltd.). The obtained vinyl polymer was dissolved in deuterated chloroform and measured at 25 ° C., and the amount of terminal double bonds per polymer chain was calculated.

  The weight average molecule (Mw) of the vinyl polymer produced according to the present invention is preferably in the range of 1000 to 20000, and more preferably in the range of 1000 to 10,000. When the Mw of the vinyl polymer is 1000 or more, when used as a macromonomer, the polymerization stability is improved and the polymerization yield is improved. When the Mw of the vinyl polymer is 20000 or less, the reactivity of the terminal double bond is improved.

  Further, the Mw / Mn (weight average molecular weight / number average molecular weight) of the vinyl polymer produced according to the present invention is such that the Mw / Mn of the vinyl polymer is 4 or less when used as a resin for organic solvent-type paints. Preferably, it is more preferably 3 or less. When the Mw / Mn of the vinyl polymer is 4 or less, the solubility in various solvents tends to be improved.

Hereinafter, the present invention will be specifically described by way of examples. In the following, “part” represents “part by mass”. Moreover, the measurement and evaluation of each physical property in the present examples and comparative examples were performed by the following methods.

(1) Yield The mass of the obtained normal vinyl polymer was measured, and the yield (%) was calculated from the following formula (4). The normal vinyl polymer means a net mass, and excludes aggregates adhering to the polymerization apparatus during polymerization, secondary aggregates containing air, and the like.
Yield (%) = mass of normal vinyl polymer (g) / mass of charged vinyl monomer (g) × 100 (4)
(2) Gardner color number 10 g of the obtained vinyl polymer was taken in a Gardner test tube and measured by colorimetry with a Gardner color number standard solution in accordance with JIS K 5600.

(3) Molecular weight (Mw, Mn and Mw / Mn)
The gel permeation chromatography (GPC) “HLC-8120” (trade name, manufactured by Tosoh Corporation) was used for measurement. The column used was TSKgel G5000HXL * GMHXL-L (trade name, manufactured by Tosoh Corporation). The calibration curve was prepared using TSK standard polystyrene F288 / F80 / F40 / F10 / F4 / F1 / A5000 / A1000 / A500 (trade name, manufactured by Tosoh Corporation) and styrene.
Measurement was carried out at 40 ° C. using 100 μl of a solution obtained by dissolving the obtained vinyl polymer in tetrahydrofuran (THF) so as to be 0.4% by mass. The weight average molecular weight (Mw), the number average molecular weight (Mn), and the weight average molecular weight / number average molecular weight (Mw / Mn) were calculated in terms of standard polystyrene.

(4) Based on the molecular weight measurement result obtained by the chain transfer constant (3), the chain transfer constant Cs when each initiator was used was determined from (Equation 4).
1 / DPn = 1 / DPn, 0 + Cs [Co (II)] / [M] (Formula 4)
Dpn: degree of polymerization of vinyl polymer produced by polymerization in the presence of chain transfer agent Dpn, 0: degree of polymerization of vinyl polymer produced by polymerization in the absence of chain transfer agent Cs: chain transfer constant [Co (II)] / [M]: molar ratio of charged Co complex to vinyl monomer In this application, for each initiator, the values of 1 / DPn and [Co (II)] / [M] are plotted, and the slope thereof. From this, Cs was obtained.

(5) Amount of carboxyl group-containing compound generated In a device equipped with a stirrer, a condenser, and a thermometer, 95 parts of xylene and 5 parts of an organic peroxide were added and stirred. The temperature was raised to ° C. After reaching 100 ° C., the solution was held at 100 ° C. for 3 hours and then cooled to room temperature to obtain a solution.

  Using 1 μl of the obtained solution, while increasing the temperature from 50 ° C. to 240 ° C. at 10 ° C./min, measurement is performed at a flow rate of 20 ml / min, and the amount of the generated carboxyl group-containing compound is measured. The amount of the carboxyl group-containing compound generated from 1 mol of the product was determined.

  “Agilent 6890N” (trade name, manufactured by Agilent Technologies, Inc.) was used for gas chromatography (GC), and J & W DB-FFAP (trade name, manufactured by Agilent Technologies, Inc.) was used for the column. The calibration curve was prepared using TSK standard polystyrene F288 / F80 / F40 / F10 / F4 / F1 / A5000 / A1000 / A500 (trade name, manufactured by Tosoh Corporation) and styrene.

(6) Quantity of terminal double bond Measured using a nuclear magnetic resonance apparatus (NMR) “EXcalibur 270 superconducting FT-NMR” (trade name, manufactured by JEOL Ltd.). The obtained vinyl polymer was dissolved in deuterated chloroform and measured at 25 ° C., and the amount of terminal double bonds per polymer chain was calculated.

(7) Residual vinyl monomer content High-performance liquid chromatography (HPLC) "Agilent 1200SL HPLC" (trade name, manufactured by Agilent Technologies, Inc.) was used for measurement. Developil ODS-5 (trade name, manufactured by Nomura Chemical Co., Ltd.) was used as the column.
Measurement was carried out at 40 ° C. using 5 μl of a solution obtained by dissolving the obtained vinyl polymer in THF.

<Evaluation of physical properties of coating film>
The film properties of the obtained vinyl polymer were measured by the following method.

  In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate and 0.25 part of dispersant 1 (solid content 10% by mass) were stirred and stirred uniformly. Solution. Next, 50 parts of the obtained vinyl polymer, 100 parts of n-butyl acrylate, and 0.5 part of lauroyl peroxide were added to obtain an aqueous suspension.

  Next, the inside of the polymerization apparatus was purged with nitrogen, heated to 80 ° C., reacted for about 1 hour, and further heated to 90 ° C. as a post-treatment temperature and held for 1 hour in order to increase the polymerization rate. Thereafter, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension. This aqueous suspension was filtered through a nylon filter cloth having an opening of 45 μm, and the filtrate was washed with deionized water, dehydrated, and dried at 40 ° C. for 16 hours to obtain a copolymer.

  50 parts of the resulting copolymer was dissolved in 50 parts of toluene, coated on an ABS plate with a bar coater No. 20, held at room temperature for 0.5 hours, and then heated at 80 ° C. for 1 hour to form a coating film. Got. The coating film adhesion, coating film appearance, and coating film hardness were evaluated. Furthermore, after apply | coating to the film made from PET with the bar coater No. 14 and hold | maintaining at room temperature for 0.5 hour, after heating at 60 degreeC for 1 hour and obtaining the coating film, workability was evaluated. Each evaluation method was performed by the method shown below.

(8) Adhesiveness The adhesiveness of the coating film was measured by a cross-cut method according to JIS K 5600-5-6: 1999, and judged according to the following criteria.
“◯”: The peeled area is less than 5% of the whole.
“Δ”: The peeled area is 5% or more and less than 30% of the whole.
“×”: The peeled area is 30% or more of the whole.

(9) The coating film surface of the coating film appearance test plate was visually observed and judged according to the following criteria.
“O”: No glossiness or irregularities.
“X”: An abnormality in either gloss or irregularity.

(10) The coating film surface of the coating color test plate was visually observed and judged according to the following criteria.
“◯”: Nearly colorless.
“△”: yellowish.
"X": There is quite yellowishness.

(11) Coating film hardness The pencil hardness of the coating film was measured by a hand-drawing method according to JIS K 5600-5-4: 1999. As for the pencil hardness, B or higher was accepted and 2B or lower was rejected.

(12) After applying to a processable PET film with a bar coater No. 14 and holding at room temperature for 0.5 hour, after heating at 60 ° C. for 1 hour to obtain a coating film, a test piece (10 mm × 10 mm) The crack of the coating film was observed when it was bent at 180 ° C.
“◯”: Unbreakable “×”: Cracking <Manufacture of Dispersant 1>
In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 900 parts of deionized water, 60 parts of sodium 2-sulfoethyl methacrylate, 10 parts of potassium methacrylate and 12 parts of methyl methacrylate were stirred and polymerized. While the inside was replaced with nitrogen, the temperature was raised to 50 ° C. Into this, 0.08 part of 2,2′-azobis (2-methylpropionamidine) dihydrochloride was added as a polymerization initiator, and the temperature was further raised to 60 ° C. After the temperature increase, methyl methacrylate was continuously added dropwise at a rate of 0.24 part / minute for 75 minutes using a dropping pump. The reaction solution was held at 60 ° C. for 6 hours and then cooled to room temperature to obtain Dispersant 1 having a solid content of 10% by mass as a transparent aqueous solution.
<Production of chain transfer agent 1>
In a synthesizer equipped with a stirrer, 1.00 g of cobalt (II) acetate tetrahydrate and 1.93 g of diphenylglyoxime, 80 ml of diethyl ether previously deoxygenated by nitrogen bubbling were added at room temperature. Stir for 30 minutes. Subsequently, 10 ml of boron trifluoride diethyl ether complex was added, and the mixture was further stirred for 6 hours. The mixture was filtered, and the solid was washed with diethyl ether and dried in vacuo for 15 hours to obtain 2.12 g of chain transfer agent 1 as a reddish brown solid.

Example 1
In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 145 g of deionized water, 0.1 g of sodium sulfate and 0.25 g of dispersant 1 (solid content 10% by mass) were added and stirred to obtain a uniform aqueous solution. did. Next, 100 g of methyl methacrylate, 0.008 g of chain transfer agent 1 (80 ppm with respect to 100 g of vinyl monomer) and 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (carboxyl group) (Generation amount of contained compound: 0.031 mol) 0.004 mol was added to obtain an aqueous suspension.

  Next, the inside of the polymerization apparatus was purged with nitrogen, heated to 80 ° C., reacted for about 1 hour, and further heated to 90 ° C. as a post-treatment temperature and held for 1 hour in order to increase the polymerization rate. Thereafter, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension containing the polymer. This aqueous suspension was filtered through a nylon filter cloth having an opening of 45 μm, and the filtrate was washed with deionized water, dehydrated, and dried at 40 ° C. for 16 hours to obtain a vinyl polymer. This vinyl polymer was Mw4700, Mn = 2000, Mw / Mn2.4. The evaluation results are shown in Table 1.

(Examples 2-11, Comparative Examples 1-7)
A vinyl polymer was obtained in the same manner as in Example 1 except that the type, addition amount, and monomer composition of the polymerization initiator were as shown in Table 1. The evaluation results are shown in Table 1.

(Example 12)
In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 145 g of deionized water, 0.1 g of sodium sulfate and 0.25 g of dispersant 1 (solid content 10% by mass) were added and stirred to obtain a uniform aqueous solution. did. Next, 100 g of methyl methacrylate, 0.01 g of chain transfer agent 1 and 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (the amount of carboxyl group-containing compound generated: 0.031 mol) 0 0.005 mol was added to make an aqueous suspension.

Next, the inside of the polymerization apparatus was purged with nitrogen, heated to 80 ° C., reacted for about 1 hour, and further heated to 90 ° C. as a post-treatment temperature and held for 1 hour in order to increase the polymerization rate. Thereafter, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension containing the polymer. This aqueous suspension was filtered through a nylon filter cloth having an opening of 45 μm, and the filtrate was washed with deionized water, dehydrated, and dried at 40 ° C. for 16 hours to obtain a vinyl polymer. In this vinyl polymer, the amount of terminal double bonds was 1, Mw 3200, Mn = 1600, and Mw / Mn 2.0.
Next, copolymerization of the obtained vinyl polymer and n-butyl acrylate was performed. In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate and 0.25 part of dispersant 1 (solid content 10% by mass) were stirred and stirred uniformly. Solution. Next, 50 parts of the obtained vinyl polymer, 50 parts of n-butyl acrylate, and 0.5 part of lauroyl peroxide were added to obtain an aqueous suspension. Next, the inside of the polymerization apparatus was purged with nitrogen, heated to 80 ° C., reacted for about 1 hour, and further heated to 90 ° C. as a post-treatment temperature and held for 1 hour in order to increase the polymerization rate. Thereafter, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension containing the polymer. This aqueous suspension was filtered through a nylon filter cloth having an opening of 45 μm, and the filtrate was washed with deionized water, dehydrated, and dried at 40 ° C. for 16 hours to obtain a copolymer.
50 parts of the obtained copolymer was dissolved in 50 parts of toluene, coated on an ABS plate with a bar coater No. 20, held at room temperature for 0.5 hours, and then heated at 80 ° C. for 1 hour to form a coating film. Got. The coating film adhesion, coating film appearance, and coating film hardness were evaluated. Furthermore, after apply | coating to the film made from PET with the bar coater No. 14 and hold | maintaining at room temperature for 0.5 hour, after heating at 60 degreeC for 1 hour and obtaining the coating film, workability was evaluated. The evaluation results are shown in Table 2.

(Examples 13 and 14)
Polymerization was carried out in the same manner as in Example 12 except that the type of monomer copolymerized with the vinyl polymer was changed as shown in Table 2. The evaluation results are shown in Table 2.

なお、表中の記号は以下の通りである。
ＭＭＡ：メチルメタアクリレート
ｉ−ＢＭＡ：ｉ−ブチルメタアクリレート
ｎ−ＢＡ：ｎ−ブチルアクリレート
ＥＨＡ：エチルヘキシルアクリレート
パーオクタＯ：１,１,３,３−テトラメチルブチルパーオキシ２−エチルヘキサノエート（日本油脂株式会社製、１０時間半減期温度６５．３℃）（カルボキシル基含有化合物の発生量：０．０３１ｍｏｌ）
パーヘキシルＯ：ｔ−ヘキシルパーオキシ２−エチルヘキサノエート（日本油脂株式会社製、１０時間半減期温度６９．９℃）（カルボキシル基含有化合物の発生量：０．０２２ｍｏｌ）
パーブチルＯ：ｔ−ブチルパーオキシ２−エチルヘキサノエート（日本油脂株式会社製、１０時間半減期温度７２．１℃）（カルボキシル基含有化合物の発生量：０．００３ｍｏｌ）
ＬＰＯ：ラウロイルパーオキサイド（１０時間半減期温度６１．６℃）（カルボキシル基含有化合物の発生量：０．１ｍｏｌ）
ＢＰＯ：ベンゾイルパーオキサイド（１０時間半減期温度７３．６℃）（カルボキシル基含有化合物の発生量：０．４５ｍｏｌ）
ＡＩＢＮ：２,２'−アゾビスイソブチロニトリル（１０時間半減期温度６５℃）
比較例１では、コバルト錯体と重合開始剤のモル比が高いため、ビニル系ポリマーの収率が低く、着色に課題があり、残存ビニル系単量体量が高く、更に共重合体による塗膜の塗膜外観、塗膜着色が悪く、塗膜硬度が低くなった。

The symbols in the table are as follows.
MMA: methyl methacrylate i-BMA: i-butyl methacrylate n-BA: n-butyl acrylate EHA: ethylhexyl acrylate perocta O: 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate ( Nippon Oil & Fats Co., Ltd., 10 hour half-life temperature 65.3 ° C.)
Perhexyl O: t-hexyl peroxy 2-ethylhexanoate (manufactured by NOF Corporation, 10 hour half-life temperature 69.9 ° C.) (Generation amount of carboxyl group-containing compound: 0.022 mol)
Perbutyl O: t-butyl peroxy 2-ethylhexanoate (manufactured by NOF Corporation, 10 hour half-life temperature 72.1 ° C.) (Generation amount of carboxyl group-containing compound: 0.003 mol)
LPO: Lauroyl peroxide (10-hour half-life temperature 61.6 ° C.) (Generation amount of carboxyl group-containing compound: 0.1 mol)
BPO: Benzoyl peroxide (10 hour half-life temperature 73.6 ° C.) (Generation amount of carboxyl group-containing compound: 0.45 mol)
AIBN: 2,2′-azobisisobutyronitrile (10 hour half-life temperature 65 ° C.)
In Comparative Example 1, since the molar ratio of the cobalt complex and the polymerization initiator is high, the yield of the vinyl polymer is low, there is a problem in coloring, the amount of the residual vinyl monomer is high, and the coating film by the copolymer The coating film appearance and coating color were poor, and the coating film hardness was low.

  In Comparative Example 2, since the molar ratio of the cobalt complex and the polymerization initiator was low, the amount of terminal double bonds of the vinyl polymer was low, and there was a problem in the processability of the coating film using the copolymer.

  In Comparative Example 3, since the molar ratio of the cobalt complex and the polymerization initiator is high, the yield of the vinyl polymer is low, there is a problem in coloring, the amount of residual vinyl monomer is high, and the obtained vinyl polymer The coating film appearance and coloration of the coating film with the copolymer using as a macromonomer were poor, and the coating film hardness was low.

  In Comparative Example 4, since the molar ratio of the cobalt complex to the polymerization initiator is low, the amount of terminal double bonds of the vinyl polymer is low. Further, the coating film made of a copolymer using the obtained vinyl polymer as a macromonomer is used. There was a problem in workability.

  In Comparative Example 5, since an initiator having a high generation amount of a carboxyl group-containing compound is used, the molecular weight of the vinyl polymer is high, the amount of terminal double bonds is low, there is a problem in coloring, and the obtained vinyl The adhesion and coating color of the coating film with a copolymer using a polymer as a macromonomer were poor, the coating film hardness was low, and there was a problem in processability.

  In Comparative Example 6, an initiator that generates a high amount of carboxyl group-containing compound is used, so the amount of terminal double bonds of the vinyl polymer is low, there is a problem with coloring, and the obtained vinyl polymer is macro- Coloring of the coating film by the copolymer used as the monomer was poor, and there was a problem in processability.

  In Comparative Example 7, since an azo polymerization initiator is used, the vinyl polymer yield is low, the residual vinyl monomer amount is high, and the obtained vinyl polymer is used as a macromonomer. The appearance of the coating film made of the polymer was poor.

Claims (4)

In the presence of the cobalt complex described in the following general formula (1),
Using an organic peroxide having a carboxyl group-containing compound amount generated by thermal decomposition of 0.07 mol or less per mol of the organic peroxide as a polymerization initiator,
A method for producing a vinyl polymer, in which a vinyl monomer is subjected to suspension polymerization under a condition satisfying the following formula (2).

[In Formula (1), R1-R4 are each independently an alkyl group, a cycloalkyl group, and an aryl group; X is each independently F atom, Cl atom, Br atom, OH group, alkoxy group, Aryloxy group, alkyl group and aryl group]
0.0002 <Cobalt complex amount (mol) / Organic peroxide amount (mol) <0.01 (2)   A vinyl polymer having a terminal double bond obtained by the production method according to claim 1.   A method for producing a vinyl polymer comprising copolymerizing a vinyl polymer having a terminal double bond and a vinyl monomer according to claim 2.   A vinyl polymer obtained by the production method according to claim 3.