JPS62205108A - Production of vinyl polymer - Google Patents

Abstract

PURPOSE:In subjecting a vinyl monomer to suspension polymerization, to produce an imide group-containing vinyl polymer suitable as a binder resin for toner continuously, stably and in high yield, by dissolving a specific amount of a water-soluble polymerization inhibitor in an aqueous medium and polymerizing the vinyl monomer. CONSTITUTION:In subjecting a vinyl monomer (e.g. compound shown by formula V, formula VI, etc.) shown by formula I (R<1> is H or CH3; R<2> is 1-6C alkylene or cyclic hydrocarbon-containing group; R<3> is group shown by formula II-formula IV, etc.; X is -COO- or -CONH-) in an aqueous medium (preferably water) containing a dispersant (e.g. gelatin, tragacanth gum, etc.), >=10ppm based on the vinyl monomer of a water-soluble polymerization inhibitor (e.g., sodium nitrite, cupric chloride, etc.) is predissolved in the aqueous medium. EFFECT:Adhesion of a polymer to a reactor during polymerization and clogging of a filter in filtering process of the polymer are prevented.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to the production of a vinyl polymer useful as a binder resin used in toners for developing electrostatic images used in fields such as electrophotography and electrostatic recording. Regarding the method.

(Prior Art) Vinyl rubber used in toner for developing electrostatic images. Among these polymerization methods, the suspension polymerization method has advantages such as not using a solvent, easy reaction control, and easy separation of binder resin, and is suitable for producing binder resin for toner. This is the method I followed.

(Problems to be Solved by the Invention) However, when trying to produce the vinyl polymer of the present invention by the conventional suspension polymerization method, as the polymerization time progresses, the vinyl resin is mixed with the thermometer, stirring rod, etc. in the reaction vessel. Furthermore, the polymerization may be deposited on various parts such as the inner wall of the pot at the liquid interface, making it impossible to continue polymerization, or a cleaning process is required for each batch, reducing work efficiency. 'JJ in over process! &
There were problems such as clogging of the X11 aircraft. The reason for this is presumed to be that a part of the monomer undergoes emulsion polymerization due to water solubilization, and that the emulsion polymer binds the suspended particles.

An object of the present invention is to provide a method for producing a vinyl polymer useful as a binder resin for toner, which solves the above-mentioned problems.

(Means for Solving the Problems) The present invention is based on the general formula (I): [wherein R1 represents hydrogen or a methyl group, and R2 is an alkylene group having 1 to 6 carbon atoms or a group having a cyclic hydrocarbon] In a method for producing a vinyl polymer by suspension polymerizing -CH2CH2-1-C)I=CH- or a vinyl monomer in an aqueous medium containing a dispersant, R3 is preliminarily dissolved in the aqueous medium. 10pp of polymerization inhibitor based on all vinyl monomers
The present invention relates to a method for producing a vinyl polymer, which is characterized in that n+ or more are dissolved.

The vinyl monomer used in the present invention has the general formula (I
The imide group-containing vinyl monomer represented by ) may be used alone, or the imide group-containing vinyl monomer and another monomer copolymerizable therewith may be used in combination. The effect of the method of the present invention is that the general formula (1) occupies all vinyl monomers.
This is noticeable when the proportion of the imide group-containing vinyl monomer is large, especially when it is 10i% or more.

Imide group-containing vinyl monoCH2- of the general formula (I)
♂--Crystal-NHC2H40-○-H('';;,'fJ3
−t=ts.

Other vinyl monomers that can be copolymerized with the co-imide group-containing vinyl monomer include the following compounds.

[In the formula, R1 represents hydrogen or a methyl group, RS represents hydrogen, an alkyl group or alkenyl group having 1 to 4 carbon atoms, a halogen or a hydroxyl group], and R
@i is hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, or -R'7-Ar (here, R7 represents an alkylene group having 1 to 4 carbon atoms, and Ar represents an aryl group) , R'F-0R8 or -(R70)n OR
8 (Here, R7 represents the above, R8 represents hydrogen or an alkyl group or aryl group having 1 to 4 carbon atoms,
n indicates the repeating number and represents an integer from 1 to 10), or represents R9, RIO and R1+ each independently hydrogen,
represents an alkyl group, an alkoxy group, an alkoxyalkoxy group, or an acetoxy group having 1 to 4 carbon atoms),
or -(R7)□-(Ar)p -N (where R7 and Ar represent the above, and two R8
each independently represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group, m and l each indicate the number of repeats and represent an integer of 0 or 1, but both do not represent 0, always represents 1), or 0 represents the above, R12 represents an alkylene group having 2 to 3 carbon atoms or an unsaturated hydrocarbon group)] or each independently hydrogen, 1 to 3 carbon atoms 4 represents an alkyl group, alkoxy group, acetoxy group, alkoxyalkoxy group, or halogen), or -〇N or -N (wherein, each of the two R8s independently represents the above)
, or], (in the formula, R1 and n represent the above, and R2 represents an alkylene group having 1 to 6 carbon atoms), or a reaction product of trivalent or higher valent glycol and acrylic acid or methacrylic acid I can name things.

Specific examples of other vinyl monomers are shown below,
The present invention is not limited to these. styrene,
Hydroxystyrene, methylstyrene, butylstyrene, chlorstyrene, bromostyrene, divinylbenzene, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, hebutyl methacrylate, Decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, glycidyl methacrylate, methoxyethyl methacrylate, propoxyethyl methacrylate, butoxyethyl methacrylate, methoxydiethylene glycol methacrylate, ethoxydiethylene glycol methacrylate, methoxyethylene glycol methacrylate, butoxy methacrylate Triethylene glycol, methoxydipropylene glycol methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxytetraethylene glycol methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, methacrylic acid 2-Hydroxy-3-phenyloxypropyl, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, acrylic Decyl acid, undecyl acrylate, dodecyl acrylate, glycidyl acrylate, methoxyethyl acrylate, propoxyethyl acrylate, butoxyethyl acrylate, methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxyethylene glycol acrylate, butoxytriacrylate Ethylene glycol, methoxydipropylene glycol acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxytetraethylene glycol acrylate, benzyl acrylate, cyclohexyl acrylate, trimethoxysilylpropyl methacrylate, trimethoxyethoxysilylbrobyl methacrylate , dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diphenylaminopropyl methacrylate,
N-vinylcarbazole, N-vinylpyrrolidone, N-
Vinylimidazole, N-vinylmorpholine, vinyldichloromethylsilane, vinyldimethylethoxysilane,
Tetrahydrofurfuryl methacrylate, glycidyl methacrylate, acrylonitrile, methacrylaterile, 2-maleimidoethyl methacrylate, 2-methacrylate
-Succinimide ethyl, ethylene glycol dimethacrylate, 1.3-butylene glycol dimethacrylate, 1.4-butanediol dimethacrylate, 1.5
-bentanediol dimethacrylate, 1,6-hexanethiol dimethacrylate, neopentyl glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, neopentyl glycol hydroxypivalate ester dimethacrylate,
Trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, pentaerydrift trimethacrylate, pentaerydrift tetramethacrylate, trismethacryloxyethyl phosphate,
Bis(methacryloyloxyethyl)hydroxyethyl isocyanurate, tris(methacryloyloxyethyl)isocyanurate, ethylene glycol diacrylate), i,3-butylene glycol diacrylate, 1
, 4-butanediol diacrylate, 1.5-bentanediol diacrylate, 1.6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, tripropylene diacrylate Preferred vinyl monomers include acrylate, neopentyl hydroxypivalate glycol diacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerydrift triacrylate, pentaerydrift tetraacrylate, bis(methacryloyloxyethyl)hydroxyethyl , vinyl monomers having one vinyl group in one molecule include styrene, styrene derivatives, methacrylic acid esters, acrylic acid esters, and especially methacrylic acid or ' ) @ is preferably an alkyl ester of acrylic acid.For vinyl monomers having two or more vinyl groups in one molecule, divinylbenzene, dimethacrylate and diacrylate of methylene glycol having 2 to 6 carbon atoms, etc. are preferred. ,
These are used in an amount of 0 to 20@f1% of the total vinyl monomers.

As a polymerization initiator, acetyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, peroxide 2.
Diacyl peroxide such as 4-dichlorobenzoyl, ketone peroxide such as methyl ethyl ketone peroxide, cyclohexanone peroxide, di-tert-buty, ruberoxy-3,3
,5-)limethylcyclohexane, 2,2-bis(te
Peroxyketals such as rt-butylperoxy)octane, dialkyl peroxides such as dicumyl peroxide and di-tert-butyl peroxide, hydroperoxides such as tert-butyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, and diisopropylbenzene hydroperoxide Peroxides, peroxyesters such as tert-butylperoxy-2-ethylhexanoate, tert-butylperoxylaurate, tert-butylperoxybenzoate, peroxyesters such as diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, etc. dicarbonate),
2.2''-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2.2'-azobis(2,4-dimethylvaleronitrile), (1-phenylethyl)azodiphenylmethane, 2.2'- Azobisisobutyronitrile, dimethyl-2,21-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile),
1.1'-azobis(1-cyclohexanecarbonitrile), 2-(carbamoylazo)-isobutyronitrile, 2.21-azobis(2,4,4-)limethylpenkune), 2-phenylazo-2,4- Dimethyl-4-methoxyvaleronitrile, 2.2'-azobis(2-methylpropane), 2.2@-azobis(N,N"-dimethyleneisobutyramicin), 4.4'-azobis(4- Azo compounds such as cyanobentanoin acetate) can be used.

It is preferable to use these polymerization initiators in an amount of 0.1 to 15% by weight based on the total amount of vinyl monomers, and it is also preferable to use these polymerization initiators by dissolving them in the vinyl monomers.

Furthermore, known chain transfer agents can be used as appropriate.

Dispersants used in the present invention include gelatin, gum tragacanth, starch, methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, partially saponified polyvinyl alcohol, partially acetalized polyvinyl alcohol, polyacrylic acid or its salt, alginate, etc. Easily soluble organic dispersant, barium sulfate, calcium sulfate, calcium carbonate, barium carbonate, magnesium carbonate, tricalcium phosphate, talc, bentonite,
Conventionally known dispersants such as diatomaceous earth, clay, and other water-insoluble inorganic dispersants can be used. These usage amounts are
For the total amount of vinyl monomers, 1x10-3 to 5% by weight for TrII dispersants and 1x10-5% for inorganic dispersants.
Preferably, it is 2 to 3% by weight.

In addition, as a dispersing agent, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, "alkyl sulfonates in which 5OiNa is directly bonded to the alkyl group, β-tetrahydronaphthalene sulfonates, N-isopropylcyclohexylamide sulfonic acid" Anionic surfactants such as amidosulfonates such as sodium salts and higher fatty acid salts such as sodium oleate can be used in combination with the above dispersants.Especially when using an inorganic dispersant as a dispersant, dispersion It is preferable to use an auxiliary agent in combination.The dispersion auxiliary agent should be used in an amount of 1
Preferably, it is used in an amount of 0-' to 0.01% by weight.

In the present invention, examples of the water-soluble polymerization inhibitor include sodium nitrite, potassium nitrite, and ferric chloride.

The amount of these added is 10% based on the total amount of vinyl monomer.
ppm or more, preferably 50 ppm or more, and 10 p
If it is less than pm, emulsion polymerization cannot be sufficiently suppressed, and the above-mentioned problems are likely to occur. On the other hand, even if a large amount of polymerization inhibiting IJ is added, the effect of suppressing emulsion polymerization is saturated, so the upper limit of addition 9 is preferably 1×10'ppm. It is preferable that the polymerization inhibitor is added after being dissolved in an aqueous medium in advance.

In the present invention, water is mainly used as the aqueous medium.

The above-mentioned dispersant, a dispersion aid if necessary, and a water-soluble polymerization inhibitor are added to this medium.

In the present invention, the ratio of the total amount of vinyl monomers to the aqueous medium is preferably 20 to 60% by weight in order to perform suspension polymerization more smoothly and from the viewpoint of productivity.

Furthermore, in the present invention, an electrolyte such as potassium chloride, sodium chloride, calcium chloride, sodium sulfate, aluminum potassium sulfate, etc. may be added to the aqueous medium. These reduce the solubility of vinyl monomers in water, but
On the other hand, it may destroy the suspended layer, so sufficient care must be taken when using it. The amount of electrolyte added is preferably 0.5% by weight or less based on the total amount of vinyl monomer when a dispersant that is easily soluble in water is used, and when a dispersant that is sparingly soluble in water is used, Saturation amount (relative to water)
But sometimes it's okay.

(Example) Next, the present invention will be described in detail based on Examples, but the present invention is not limited thereto.

Example 1 (1) Aqueous medium 11 dish water 100
Partially saponified polyvinyl alcohol 3 (trade name Denka Poval W-24, manufactured by Denki Kagaku Kogyo Co., Ltd.) Sodium nitrite (200 ppm relative to vinyl monomer 0.2-) (2) Vinyl monomer Sunalene 500 Butyl acrylate 15ON- Methacryloyloxyethylene phthalimide 350 Benzoyl peroxide 25 Into a reaction vessel, put the aqueous medium of (1) in which a dispersant and a water-soluble polymerization inhibitor are dissolved in water and the vinyl monomer having the composition of (2).
Polymerization was carried out at ℃ for 6 hours. Polymerization was carried out smoothly, and the amount of adhesion to the reaction vessel was less than 1% (based on the vinyl monomer).

Next, use a centrifuge (manufactured by International Centrifuge ■, the opening of the r cloth is approximately 4
When the resin was fractionated using a 0.00 mesh filter, it was possible to filter the resin without causing clogging, and a granular resin with a particle size of approximately 1.0 mm was obtained at a yield of 98%.

Example 2 (1) Aqueous medium] Dish water 1500
Partially saponified polyvinyl alcohol 1 (trade name Denka Poval W-24) Sodium nitrite (30 ppm to vinyl monomer 0.015-) Potassium nitrite (20 ppm to vinyl monomer 0.01) (2) Vinyl monomer styrene 350 acrylic Butyl acid 75 Diethylaminoethyl methacrylate 25N-methacryloyloxyethylene phthalimide 502.21-
Azobis(2,4-dimethylvaleronitrile) An aqueous medium having the composition (1) was put into a reaction vessel to form a homogeneous solution, and then the vinyl monomer (2) was added to
Zero-polymerization, which was carried out at a temperature of 5 hours, was carried out smoothly, and the amount of adhesion to the reaction vessel was 1% or less.

Next, when the resin was fractionated using the same centrifuge as in Example 1, it passed without clogging, and granular resin with a particle size of about 1 Tsuru could be obtained at a yield of 96%.

Example 3 (1) Aqueous medium ■1 dish water 1300
Partially saponified polyvinyl alcohol 2 (trade name Denka Poval W-24) Sodium nitrite (400 ppm+ for vinyl monomer 0.28) Potassium nitrite (400 ppm+ for vinyl monomer 0.28) Steel chloride (for vinyl monomer 0.28) 2 for 0.14
(00ppm) (2) Vinyl monomer - Styrene 490 Butyl acrylate 7ON-Acryloyloxyethylene phthalimide 7ON-Methacryloyloxyethylene phthalimide 70 Benzoyl peroxide 14 Di-tert-Butylperoxy-3°3.5-)limethylcyclohexane
2 The aqueous medium of (1) above and the monomer of (2) were mixed and polymerized in the same manner as in Example 1. The polymerization was carried out smoothly, and the amount of adhesion to the reaction vessel was 1% or less. Ta.

Next, when the resin was fractionated using the same centrifuge as in Example 1, it passed without clogging, and granular resin with a particle size of about 1 day was obtained at a yield of 98%.

Example 4 (1) Aqueous medium 11 dish water 1237
10% solution of trilucium phosphate 70 (trade name Supertite-10, manufactured by Nihon Kagaku Kogyo ■) Sodium dodecyl sulfonate 0.042 Sodium nitrite (vinyl monomer 0.07-101)
00pp Potassium chloride (50ppm relative to vinyl monomer 0.035) (2) and Nyl monomer Styrene 470 Butyl acrylate 9ON-methacryloyloxyethylene phthalimide 100N-methacryloyloxyethylenetetrahydrophthalimide 40 Benzoyl peroxide 15 Aqueous solution of (1) above The medium and the vinyl monomer (2) were mixed and polymerized in the same manner as in Example 1. The zero polymerization was carried out smoothly, and the amount of adhesion to the reaction vessel was 1% or less.

Next, the resin was fractionated using the same centrifuge as in Example 1, and it passed through without clogging, and the particle size was about 1 m.
It was possible to obtain granular resin with a yield of 98%.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that sodium nitrite was omitted. After raising the temperature to 90'C, about 2
Over time, the adhesion to the stirring rod, thermometer, and inner wall of the reaction vessel increased, making temperature control and stirring power difficult.As a result of interrupting the polymerization and examining the amount of adhesion to the reaction vessel at this point, It was 8%.

Additionally, the centrifuge caused clogging.

(Effects of the Invention) According to the present invention, the polymer does not adhere to the reaction vessel during polymerization, and the passing through process of the polymer does not cause clogging of the passing unit. An imide group-containing vinyl polymer can be obtained continuously and stably in high yield.

Claims (1)

[Claims] 1. General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 represents hydrogen or a methyl group, and R^2 represents a carbon atom number of 1 to 1. 6 is a group having an alkylene group or a cyclic hydrocarbon, and R^3 has ▲mathematical formula, chemical formula, table, etc.▼, ▲mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, R^4 is -CH_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, -
CH_2CH_2-, -CH=CH- or ▲Represents mathematical formulas, chemical formulas, tables, etc.▼), ▲Represents mathematical formulas, chemical formulas, tables, etc.▼ or ▲Represents mathematical formulas, chemical formulas, tables, etc.▼ or represents derivatives of these , X represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼] is suspended and polymerized in an aqueous medium containing a dispersant to form a vinyl polymer. A method for producing a vinyl polymer, characterized in that a water-soluble polymerization inhibitor is dissolved in the aqueous medium in an amount of 10 ppm or more based on the total vinyl monomers. 2. The method for producing a vinyl polymer according to claim 1, wherein the water-soluble polymerization inhibitor is at least one compound selected from sodium nitrite, potassium nitrite, and ferric chloride.