JPH06256426A - Production of polymer having vinyl ether group - Google Patents

Abstract

PURPOSE:To produce the subject polymer having a specified chemical structure in a high yield in a short time at a high monomer concn. by polymerizing a monomer component under specified conditions. CONSTITUTION:A monomer component is polymerized in the presence of a radical polymn. initiator and a radical chain transfer agent to produce this polymer which has a number-average mol.wt. of 500-1,000,000 and is represented by formula I (wherein R<1> is H or CH3; R<2> is 1-10C alkylene; (m) is 1-10,000; (n) is 0-10,000; R<3> is CX2-CR4Y or a group of formula II or III; X is H or halogen; Y is phenyl, cyano, halogen, CO2R<2> [wherein R<5> is 1-10C alkyl, perfluoroalkyl, glycidyl, 3-10C hydroxyalkyl, (CH2CH2O)pH (wherein (p) is 0-5), or a group of formula IV (wherein (q) is 0-2)], OCOR<6> (wherein R<6> is H or 1-5C alkyl), or CON(R<6>)2; R<4> is H, CH3, or CH2CO2R<6>; R<7> to R<10> are each H or 1-10C alkyl; and Z is O or NR<11> [wherein R<11> is H, phenyl, or 1-10C (cyclo) alkyl]}.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a vinyl ether group-containing polymer, and more particularly to a method for industrially easily producing a vinyl ether group-containing polymer.

[0002]

2. Description of the Related Art Polymer compounds having a branched reactive functional group have been attracting attention since they can be industrially applied to thermosetting resins. Among them, a polymer compound in which a vinyl ether group is pendantly branched from the main chain has been attracting attention in recent years as a cationic curable resin. On the other hand, the physical properties of acrylic resins can be easily adjusted by combining them with a wide variety of monomers to form copolymers.Therefore, polymer compounds in which the main chain is an acrylic resin and the vinyl ether group is branched from it are industrially widely used. Highly effective and useful. However, since the monomer necessary to obtain such a polymer compound has two vinyl groups in one molecule, ordinary radical polymerization does not produce a linear polymer compound, but a high-molecular compound having a cross-linked three-dimensional structure. It has been reported to become a molecular compound.
Conventionally, as a method for selectively homopolymerizing a vinyl group on the (meth) acrylate side, anionic polymerization with potassium amide has been proposed [German Patent Nos. 1027401 and 1034363 (1958)]. However, anionic polymerization is an extremely sensitive polymerization method for water, carbon dioxide, etc., and is not industrially suitable,
At present, there is a strong demand for the development of various polymers having a vinyl ether group, especially the production method thereof.

[0003]

Under the circumstances, the present invention provides a vinyl ether group-containing polymer in which a main chain is an acrylic resin and a vinyl ether group which is a reactive functional group is branched from the acrylic resin. The object of the present invention is to provide a method for industrially easy production.

[0004]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that when a monomer is polymerized, a radical chain transfer agent is added in the presence of a radical polymerization initiator. It was found that the objective can be achieved by making them coexist, and the present invention has been completed based on this finding. That is, the present invention has the general formula

[0005]

[Chemical 5]

[Wherein R ¹ is a hydrogen atom or a methyl group, and R ^{2 is}
Is an alkylene group having 1 to 10 carbon atoms, and m is 1 to 10000.
, N is 0 or an integer of 1 to 10000, R ³ is CX ₂
-CR ⁴ Y,

[0007]

[Chemical 6]

Or

[0009]

[Chemical 7]

A group represented by, X is a hydrogen atom or a halogen atom, Y is a phenyl group, a cyano group, a halogen atom, CO
₂ R ⁵ , OCOR ⁶ or CON (R ⁶ ) ₂ , R ⁴ is a hydrogen atom, a methyl group or CH ₂ CO ₂ R ⁶ , R ⁵ is an alkyl group or a perfluoroalkyl group having 1 to 10 carbon atoms, a glycidyl group, carbon A hydroxyalkyl group of the number 3 to 10, (CH ₂ C
H ₂ O) _P- H or

[0011]

[Chemical 8]

A group represented by, p is 0 or an integer of 1 to 5,
q is 0, 1 or 2, R ⁶ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Z is Oxygen atom or NR ¹¹ , R ¹¹ is a hydrogen atom, a phenyl group, or a carbon number of 1 to 1.
An alkyl group of 0 or a cycloalkyl group of 1 to 10 carbon atoms] 500 to 100,000
In producing a vinyl ether group-containing polymer of 0,
The present invention provides a method for producing a vinyl ether group-containing polymer, which comprises allowing a radical chain transfer agent to coexist in the presence of a radical polymerization initiator. Hereinafter, the present invention will be described in detail. The polymer obtained by the method of the present invention,
General formula

[0013]

[Chemical 9]

(Wherein R ¹ , R ² , R ³ , m and n have the same meanings as defined above), and m or n in the formula exceeds 10,000. The viscosity of the resulting polymer becomes high and the workability deteriorates, which is not preferable. Further, when the carbon number of R ² is 1, the resulting polymer has an acetal structure, and therefore tends to be extremely susceptible to hydrolysis. On the other hand, the carbon number of R ² is 10
When it exceeds, the ratio of vinyl ether groups contained in the obtained polymer decreases, and therefore it is generally not preferable in efficiently exhibiting the effect of vinyl ether groups. Further, if an attempt is made to produce a polymer having a number average molecular weight of more than 1,000,000, gelation tends to occur and the desired polymer cannot be obtained with good reproducibility. Examples of the vinyl ether group-containing monomer constituting the vinyl ether group-containing polymer represented by the general formula [1] include 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, and 2-vinyloxypropyl ( (Meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 5-vinyloxypentyl (meth) acrylate, 6
-Vinyloxyhexyl (meth) acrylate, 7-vinyloxyheptyl (meth) acrylate, 8-vinyloxyoctyl (meth) acrylate, 9-vinyloxynonyl (meth) acrylate, 10-vinyloxydecanyl (meth) acrylate and the like are preferable. Can be mentioned.

Examples of the comonomer which gives the polymer represented by the general formula [1] include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and isobutyl ( (Meth) acrylate, sec-butyl (meth)
Alkyl (s) such as acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate. (Meth) acrylate, trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate,
Heptylfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluoroisobutyl (meth) acrylate, perfluoro-sec
-Butyl (meth) acrylate, perfluoropentyl (meth) acrylate, perfluorohexyl (meth)
Acrylate, perfluoroheptyl (meth) acrylate, perfluorooctyl (meth) acrylate, perfluoro-2-ethylhexyl (meth) acrylate, perfluorononyl (meth) acrylate, perfluoroalkyl (meth) acrylate such as perfluorodecyl (meth) acrylate, acetic acid Vinyl, methyl itaconate, ethyl itaconate, propyl itaconate,
Isopropyl itaconic acid, butyl itaconic acid, isobutyl itaconic acid, sec-butyl itaconic acid, t-butyl itaconic acid, pentyl itaconic acid, glycidyl (meth)
Acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, epoxy group-containing (meth) acrylate such as 5- (3,4-epoxycyclohexylmethyloxacarbonyl) pentyl (meth) acrylate, 2-hydroxyethyl (meth) Acrylate, 2-
Hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate,
Hydroxyhexyl (meth) acrylate, hydroxyheptyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxynonyl (meth) acrylate, hydroxydecyl (meth) acrylate, polyethylene glycol monomethacrylate [CH ₂ ═C
_{(CH 3) CO 2 (CH} 2 CH 2 O) n -H, n = 2~5], polyethylene glycol monoacrylate [CH ₂ = CHC
O ₂ (CH ₂ CH ₂ O) _n —H, n = 2 to 5], a hydroxy group-containing (meth) acrylate, (meth) acrylic acid, styrene, α-methylstyrene, (meth) acrolein, (meth) ) Acrylonitrile, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N
-Diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-dibutyl (meth) acrylamide, N, N-dipentyl (meth) acrylamide ( (Meth) acrylamide derivative, fumaric acid, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, diisopropyl fumarate, dibutyl fumarate, diisobutyl fumarate, disec-butyl fumarate, di-t-butyl fumarate, dipentyl fumarate, Dihexyl fumarate, diheptyl fumarate, dioctyl fumarate, dinonyl fumarate, didecyl fumarate, or monoesters of the aforementioned fumarate derivatives, asymmetric esters, maleic acid, dimethyl maleate, diethyl maleate, dipropyl maleate, maleate. Diisopropyl maleate, dibutyl maleate, diisobutyl maleate, disec-butyl maleate, di-t-butyl maleate,
Dipentyl maleate, dihexyl maleate, diheptyl maleate, dioctyl maleate, dinonyl maleate, didecyl maleate, maleic anhydride, maleimide, N-methylmaleimide, N-ethylmaleimide,
N-propyl maleimide, N-isopropyl maleimide, N-butyl maleimide, N-isobutyl maleimide, N-sec-butyl maleimide, Nt-butyl maleimide, N-pentyl maleimide, N-hexyl maleimide, N-heptyl maleimide, N -Octyl maleimide, N-nonyl maleimide, N-decyl maleimide,
Preferable examples include N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, and N-phenylmaleimide. In the method of the present invention, it is necessary to coexist a radical chain transfer agent in the presence of a radical polymerization initiator when polymerizing the monomer. Examples of the radical chain transfer agent include mercaptans such as octyl mercaptan, lauryl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, and n-tetradecyl mercaptan, and xanthogens such as dimethylxanthogen disulfide, diethylxanthogen disulfide, and diisopropylxanthogen disulfide. Disulfides, tetramethyl thiolam disulfide, tetraethyl thiolam disulfide, tetrabutyl thiolam disulfide and other thiolam disulfides, carbon tetrachloride, halogenated hydrocarbons such as ethylene bromide, terpinolene,
Unsaturated cyclic hydrocarbon compounds such as α-terpinene, γ-terpinene and dipentene, and further α-methylstyrene dimer, m-thiocresol, thiophenol, thioglycol, 2-ethylhexyl thioglycolate,
Examples include β-naphthalenethiol.

On the other hand, as the radical polymerization initiator, for example, m-diisopropylbenzene monohydroperoxide, p-diisopropylbenzene monohydroperoxide, t-butyl hydroperoxide, diisopropylcyclohexyl hydroperoxide, isopropylcyclohexyl hydroperoxide, p-menthane hydroperoxide, 1,3,5-trimethylcyclohexyl hydroperoxide, 1,3,4-trimethylcyclohexyl hydroperoxide, diisopropylbenzene hydroperoxide, 2,4,4-trimethylpentane-2-hydroper Oxide, 2,5-dimethylhexane-2,5-dihydroperoxide, cumene hydroperoxide, 2,5-dimethyl-2,5-di (t-
Hexylperoxy) hexane, dicumyl peroxide, t-hexyl-α-cumyl peroxide, t-amyl-α-cumyl peroxide, 2,5-dimethyl-2,5
-Di (t-butylperoxy) hexane, 1,1'-di-
t-peroxy-1,1′-dicyclohexylacetylene, t-butyl-α-cumyl peroxide, 2,5-dimethyl-2,5-di (t-hexylperoxy) hexyne-3, di-t-butylper Oxide, 3,6-dimethyl-3,6-di (t-butylperoxy) octyne-
4,2,5-Dimethyl-2,5-di (t-butylperoxy) hexyne-3,2-ethylhexanoyl peroxide, α-chloropropinoyl peroxide, 2-ethylbutyryl peroxide, 2-methyl Pentanoyl peroxide, isobutyryl-2-ethylhexanoyl peroxide, α-bromopropionyl peroxide, isobutyryl peroxide, n-butyryl-2-ethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, o- Chlorobenzoyl peroxide 3,5,
5-trimethylhexanoyl peroxide, o-methylbenzoyl peroxide, 2-butenoyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, n-butyryl peroxide, stearoyl peroxide, propionyl peroxide, Propionyl-n-butyryl peroxide, 3,
3-dimethyl butyryl peroxide, succinic acid peroxide, n-butyryl acetyl peroxide, propionyl benzoyl peroxide, acetyl cyclohexyl sulfonyl peroxide, t-butyl peroxy neodecanoate, t-butyl peroxy neoheptanoate, t
-Hexylperoxypivalate, t-butylperoxypivalate, 2,5-dimethyl-2,5-di (2-ethylhexylperoxy) hexane, 2,5-dimethyl-
2,5-Di (2-ethylbutyrylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (isobutyrylperoxy) hexane, t-butyl Peroxy-2-ethylhexanoate, t-butylperoxydiethyl acetate, t-hexylperoxyisobutyrate, t-butylperoxy-2-methylpentanoate, t-butylperoxy-2-methylbutyrate Rate, t-butylperoxyisobutyrate, t-hexylperoxy-o-methylbenzoate, t-hexylperoxy-3,5,5
-Trimethylhexanoate, t-hexylperoxylaurate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxycrotonate, t-
Butyl peroxy-n-octoate, t-butyl peroxy laurate, di-t-butyl peroxyazelate, t-butyl peroxy n-decanoate, 2,5-
Dimethylhexane-2,5-diperoxybenzoate, t-hexylperoxybenzoate, t-butylperoxyisovalerate, t-hexylperoxy-p-chlorobenzoate, t-butylperoxyacetate, t-butylper Oxy-pt-butylbenzoate, t-butylperoxy-p-methylbenzoate, t-butylperoxybenzoate, di (t-butyl) peroxyphthalate, t-butylperoxy-3
-Hydroxypropionate, t-butylperoxy-
2,4-dichlorobenzoate, mono-t-butylperoxyphthalic acid, mono-t-butylperoxysuccinic acid, t-hexylperoxy-n-butylcarbonate, t-hexylperoxy-2-ethylhexylcarbonate, t -Hexyl peroxy isopropyl carbonate, t-butyl peroxy isopropyl carbonate, t-butyl peroxy-sec-butyl carbonate, t-butyl peroxy cyclohexyl carbonate, t-butyl peroxy-n-propyl carbonate, t-butyl peroxy Isobutyl carbonate, t
-Butyl peroxyisoamyl carbonate, t-butyl peroxy-n-hexyl carbonate, t-butyl peroxy-n-dodecyl carbonate, t-butyl peroxy-2-ethylhexyl carbonate, t-butyl peroxy-n-butyl carbonate , T-butyl peroxyethyl carbonate, diethylene bis (t-butyl peroxy carbonate), t-butyl peroxymethyl carbonate, ethylene bis (t-butyl peroxy carbonate), diethyl peroxy dicarbonate, di-n-butyl Peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, dibenzyl peroxydicarbonate, di-n-propyl peroxydicarbonate, didodecyl Peroxydicarbonate, diisopropyl peroxydicarbonate, di-4-t-butylcyclohexyl peroxydicarbonate, diisobutyl peroxydicarbonate, diethyl carbitol peroxydicarbonate, dimethyl peroxydicarbonate, dimethyl carbitol peroxydicarbonate Carbonate, dibutyl carbitol peroxydicarbonate, diethoxyethyl peroxydicarbonate, dibutoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, dimethoxyethyl peroxydicarbonate, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethyl Cyclohexane, 1,1-bis (t-butylperoxy) -3,3,
5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-
Hexylperoxy) heptane, 2,2-bis- (t-
Hexylperoxy) butane, 2,2-bis (t-butylperoxy) -5-methylhexane, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-
Hexylperoxy) propane, n-butyl-4,4-
Bis (t-butylperoxy) valerate, cyclohexyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) propane, α, α-bis (t- Butylperoxy) toluene,
Organic peroxides such as isoamyl-3,3-bis (t-butylperoxy) butyrate, benzyl-3,3-bis (t-butylperoxy) butyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, or 2,2 '-Azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile) (AIBN) 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide, 2- Phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-azobis (2-methyl-N-phenylpropionamidine) dihydrochloric acid , 2,2'-azobis [N
-(4-Chlorophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [N- (4-hydroxyphenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [ 2-Methyl-N- (phenylmethyl) -propionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2′-azobis ( 2-Methylpropionamidine) dihydrochloride, 2,2′-azobis [N
-(2-Hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2 ' -Azobis [2- (2-imidazoline-2-
Il) propane] dihydrochloride, 2,2′-azobis [2-
(4,5,6,7-Tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (3,4,5,6-tetrahydropyrimidine- 2-
Il) propane] dihydrochloride, 2,2′-azobis [2-
(5-Hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- [1- (2-hydroxyethyl) -2-imidazoline-2 -Yl] propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane]
Dihydrochloride, 2,2'-azobis [2-methyl-N- [1,
1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide], 2,2'-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) ethyl]
Propionamide] 2,2'-azobis [2-methyl-
N- (2-hydroxyethyl) propionamide],
2,2'-azobis (2-methylpropionamide) dihydrate, 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), dimethyl 2 , 2'-azobis (2-methylpropionic acid),
Azo initiators such as 4,4′-azobis (4-cyanovaleric acid) and 2,2′-azobis [2- (hydroxymethyl) propionitrile] can be preferably mentioned.

In the present invention, the concentration of the monomer in the system during the polymerization is preferably in the range of 1 to 80% by weight, particularly 10
A range of ˜50% by weight is preferred. If this concentration exceeds 80% by weight, a polymerization reaction takes place in the vinyl ether group, and the gelation of the produced polymer is extremely likely to occur, making it difficult to obtain the desired polymer represented by the general formula [1]. On the contrary, when it is lower than 1% by weight, the polymerization efficiency is poor and it is not industrial. The amount of the radical polymerization initiator added to the monomer is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight. If this amount is less than 0.01% by weight, the yield of the produced polymer is low, and if it exceeds 10% by weight, a radical terminating reaction is likely to occur and the molecular weight of the target polymer tends to be low. Further, the polymerization temperature is preferably 0 to 160 ° C, particularly preferably 20 to 140 ° C. If this temperature is less than 0 ° C, the polymerization reaction tends to be difficult to proceed smoothly.
If it exceeds 60 ° C, the vinyl ether group tends to react during the polymerization reaction, which is not preferable. The reaction time at this time is preferably 1 to 20 hours, particularly preferably 3 to 10 hours. If the reaction time is less than 1 hour, the polymerization reaction does not proceed sufficiently, and if it exceeds 20 hours, the conversion rate of the monomer in the polymerization reaction tends not to increase. The amount of the radical chain transfer agent used in the method of the present invention is preferably in the range of 1 to 30% by weight based on the total amount of the monomers used. If the amount used exceeds the above range, it tends to be difficult to produce the desired polymer. In particular, when the radical chain transfer agent is not used, it becomes difficult to produce the target polymer in a state where the monomer concentration in the system is high (for example, 10% by weight or more). The target vinyl ether group-containing polymer can be produced by any of the solution method, the emulsification method and the suspension method as the polymerization method in the invention.

[0018]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Example 1 In a reaction vessel equipped with a stirrer, a reflux tube, a thermometer, and a nitrogen inlet, 12.8 g of benzene and methyl methacrylate (MM
A) 2.5 g, 2-vinyloxyethyl methacrylate (2-VEM) 3.9 g, Nofmer M as a chain transfer agent
SD [trade name: manufactured by NOF CORPORATION, α-methylstyrene dimers] 1.35 g, perbutyl N as a polymerization initiator
274 mg of D [trade name: t-butylperoxyneodecanate manufactured by NOF CORPORATION] was charged and heated to 55 ° C., and the temperature was maintained for 6 hours to carry out a polymerization reaction. After the reaction was completed, the solvent benzene was distilled off under reduced pressure, and the residue was reprecipitated in 500 ml of n-hexane to obtain a white precipitate. By drying this white precipitate under reduced pressure, 5.6 g of a polymer of methyl methacrylate-2-vinyloxyethyl methacrylate was obtained as a colorless solid (yield 7
2%) was obtained. Table 1 shows the average molecular weight of the polymer obtained by reprecipitation, the dispersion ratio, the peak position of ¹ H-NMR, the copolymerization ratio obtained from the integrated value of the peak, and the main absorption of IR.

[0019]

[Chemical 10]

(Copolymerization ratio x: y = 51: 49) Examples 2 to 5 Instead of Nofmer MSD, which is the chain transfer agent of Example 1, lauryl mercaptan is used in Example 2, and dimethylxanthogen disulfide is used in Example 3. Was carried out in the same manner as in Example 1 using carbon tetrachloride in Example 4 and Nofmer TP [trade name: manufactured by NOF CORPORATION, unsaturated cyclic hydrocarbon compounds] in Example 5. . Table 1 shows the average molecular weight of the polymer obtained by reprecipitation, the dispersion ratio, the peak position of ¹ H-NMR, the copolymerization ratio obtained from the integrated value of the peak, and the main absorption of IR. The basic structure of each polymer is shown in Example 1.
And the copolymerization ratio x: y was 52: 4 in Example 2.
8 was 50:50 in Example 3, 52:48 in Example 4, and 51:49 in Example 5.

[0021]

[Table 1]

Comparative Example 1 123 g of benzene, 40.7 g of methyl methacrylate, 59.4 g of 2-vinyloxyethyl methacrylate, 59.4 g of perbutyl were placed in a 500 ml four-necked flask equipped with a stirrer, a reflux tube, a thermometer, and a nitrogen inlet. 1.5 g of ND [trade name: manufactured by Nippon Oil & Fats Co., Ltd.] was charged and heated to 55 ° C, and the polymerization reaction was carried out while maintaining the temperature. Gelation was observed 2 hours after the start of the reaction. Comparative Example 2 123 g of benzene, 72 g of methyl methacrylate, 28 g of 2-vinyloxyethyl methacrylate, 28 g of perbutyl ND [trade name: NOF Corporation] in a 500 ml four-necked flask equipped with a stirrer, a reflux tube, a thermometer, and a nitrogen inlet. (stock)
[Preparation] 1.5 g was charged and heated to 55 ° C., and the polymerization reaction was carried out while maintaining the temperature. Gelation was observed 3 hours after the start of the reaction.

[0023]

EFFECTS OF THE INVENTION According to the present invention, when a monomer is polymerized, a radical chain transfer agent is allowed to coexist in the presence of a radical polymerization initiator so that the charged concentration of the monomer can be increased to about 80% by weight. The vinyl ether group-containing polymer can be produced at high yield in a short time with good yield, easily, and efficiently without using a special apparatus. Since the vinyl ether group-containing polymer obtained by the method of the present invention has a highly reactive cross-linking site branched from the polymer main chain, it may be used as it is or may be cross-linked to obtain various derivatives or raw materials thereof, intermediate raw materials, and resins. And its raw materials, biomaterials, electronic materials, optical materials, surfactant materials, sliding materials, heat-resistant materials, reactive diluents, paints and ink materials, adhesives and the like It is preferably used as a raw material and a molded product.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08F 222/12 MLY 7242-4J 222/40 MNE 7242-4J

Claims (1)

[Claims] 1. A general formula: [In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is a carbon atom having 1 to 1 carbon atoms.
10 alkylene groups, m is an integer from 1 to 10000, n is 0 or an integer from 1 to 10000, R ³ is CX ₂ —CR ⁴ Y, Or A group represented by, X is a hydrogen atom or a halogen atom, Y is a phenyl group, a cyano group, a halogen atom, CO ₂ R ⁵ , or OCO.
R ⁶ or CON (R ⁶ ) ₂ and R ⁴ are hydrogen atom, methyl group or C
H ₂ CO ₂ R ⁶ and R ⁵ are each an alkyl group having 1 to 10 carbon atoms, a perfluoroalkyl group, a glycidyl group, or a carbon number of 3 to
A hydroxyalkyl group of 10, (CH ₂ CH ₂ O) _P- H or A group represented by, p is 0 or an integer of 1 to 5, q is 0, 1 or 2, R ⁶ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Z is an oxygen atom or N—R ¹¹ , R
¹¹ is a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 1 to 10 carbon atoms] in producing a vinyl ether group-containing polymer having a number average molecular weight of 500 to 1,000,000, A method for producing a vinyl ether group-containing polymer, which comprises allowing a radical chain transfer agent to coexist in the presence of a radical polymerization initiator.