JPS5928201B2 - Method of manufacturing emulsion composition - Google Patents

Description

Detailed Description of the Invention In the present invention, the reaction operation of emulsion polymerization is easy, and the obtained emulsion has good viscosity stability and mechanical stability, and has excellent water resistance and heat resistance by heating or adding a crosslinking agent. This invention relates to a method for producing a vinyl polymer emulsion that can be made into a coating film.

Conventionally, nonionic or anionic surfactants have been used as emulsifiers in the emulsion polymerization of vinyl monomers such as vinyl acetate, but the polymerization operation is complicated and the resulting emulsion generally has a low viscosity. The water resistance of the film is also insufficient.

The present inventors have determined that (B) a unit based on an octa-olefin, a unit based on a maleic imide or an N-substituted maleimide, and an (O-unsaturated carboxylic acid, an ester thereof or an amide thereof) in the main chain. As a result of emulsion polymerization of unsaturated monomers such as vinyl monomers using a water-soluble multi-component copolymer containing the base unit as a constituent component as a protective colloid, a stable emulsion can be obtained by a simple emulsion polymerization operation and is water resistant. The present inventors have discovered that an excellent coating film can be obtained, and have completed the present invention.

That is, the main chain contains (units based on Alα-olefin, (B) units based on maleic imide or N-substituted maleic imide, and (units based on O-unsaturated carboxylic acid, its ester, or its amide) as constituent components. According to the emulsion polymerization method of the present invention using a water-soluble multi-component copolymer containing as a protective colloid, emulsion polymerization can be easily carried out by a monomer dropping method or a monomer bulk initial charging method, and moreover, a stable polymer can be obtained. You can get an emulsion.

In addition, an emulsion of any viscosity can be obtained by changing the degree of polymerization and the amount added of the multi-component copolymer constituting the protective colloid, and the emulsion obtained by the method of the present invention has
It has good mechanical stability and storage stability, and has good applicability with little foaming. Furthermore, by adding a crosslinking agent or coexisting a crosslinking monomer to the polymerization system of the present invention, the above-mentioned multi-component polymer constituting the protective colloid can be crosslinked, resulting in a coating film with excellent water resistance and heat resistance. be able to. used as a protective colloid in the method of the invention,
The main chain contains units based on (Alα-olefin, ([maleic acid imide or N-substituted maleic imide), and (q-unsaturated carboxylic acid, its ester or its amide) as constituent components. The water-soluble multi-component copolymer is represented by the following general formula.

．． However, in the formula, R1 and R2 are the same group or different groups selected from the group consisting of a hydrogen atom, an alkyl group, and an alkenyl group, and R3 is a hydrogen atom, a halogen atom, an alkyl group that may contain a hydroxyl group, and an alkenyl group. A group selected from the group consisting of P. Q
．． At least one of R and S is a group selected from the group consisting of a carboxyl group, an ester thereof, and an amide thereof, and the others are hydrogen atoms or alkyl groups.

In the above general formula, the α-olefins that can constitute (7!) include ethylene, propylene, 1-butene, isobutene,
1-pentene, 1-hexene, 1-heptene, 2-methyl-1-hexene, 1-octene, 1-nonene, styrene, α-methylstyrene, 1,3-butadiene, isoprene, etc. Further, as the N-substituted maleic acid imide that can constitute (B), the hydrocarbon carbon number is from 1 to 18
N-substituted maleic imides that are N-substituted with saturated or unsaturated hydrocarbon groups or derivatives thereof, benzene, N-substituted maleic imides that are N-substituted with compounds having a naphthalene skeleton, N-halogen maleic acid imide,
Contains N-hydroxyalkyl maleic acid imide and the like. Furthermore, unsaturated carboxylic acids, esters thereof, or amides thereof that may constitute 0 include acrylic acid, methacrylic acid,
Maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monobutyl maleate, monohexyl maleate,
Monooctyl maleate, monostearyl maleate, fumaric acid, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monohexyl fumarate, monooctyl fumarate, monostearyl fumarate, Acrylamide, monomethylacrylamide, monoethylacrylamide, dimethylacrylamide, diethylacrylamide, hydroxyethylacrylamide,
Included are water-soluble monomer derivatives such as maleic acid amide, fumaric acid amide, and hydroxyethyl acrylate.

x. y,. Regarding the composition of z, y is x+y+z100
When the value is 55 or less, z is often included as a value that makes the multi-component copolymer a water-soluble polymer,
Its value is not particularly limited. The degree of polymerization of the multi-component copolymer used in the present invention greatly affects the viscosity of the emulsion obtained by emulsion polymerization, but is not particularly limited in the present invention. There are two main methods for producing these multi-component copolymers.

One is a method of copolymerizing maleic imide or N-substituted maleic imide, α-olefin, and unsaturated carboxylic acid, its ester, or its amide. That is, an α-olefin, an N-substituted maleimide or an N-substituted maleimide, and an unsaturated carboxylic acid,
The ester or amide thereof in a solvent such as benzene, toluene, xylene, tetrahydrofuran, dioxane, methyl ethyl ketone, cyclohexanone, acetone, ethanol, n-butanol, t-butanol, ethylene glycol, chloroform, ethyl acetate, etc. It is obtained by polymerization at a temperature of 0 to 100°C using a radical initiator such as benzoyl peroxide or azobisisobutylnitrile. Another method is to prepare a copolymer of maleic anhydride and d-olefin, react it with ammonia or amine to produce an amide or ammonium salt of the copolymer, and then heat the copolymer at 100°C to 300°C, preferably at 150°C. This is a method in which the amide or ammonium salt is partially ring-closed by heat treatment at a temperature of .degree. C. to 250.degree. C. to form an imide group. In addition, this ring-closing reaction is as follows when ammonia is reacted. (However, in the formula, H or NH4 is used.) The amount of the water-soluble multi-component copolymer used in the present invention greatly affects the viscosity of the emulsion and its physical properties, and is preferably 2% by weight or more based on the monomer to be emulsion polymerized. It is 3% by weight or more.

If the amount is less than 2% by weight, it becomes difficult to obtain a stable emulsion.

In the present invention, commonly used emulsion stabilizers can be used in combination. Furthermore, water-soluble polymers such as cellulose derivatives and polyvinyl alcohol can also be used as protective colloids. The amount of these added is preferably 50% by weight or less based on the multi-component copolymer. If it is added in an amount of 50% by weight or more, it is not preferable because it gives an unstable emulsion, deteriorates the physical properties of the emulsion, and deteriorates performance such as water resistance of the coating film.

Examples of unsaturated monomers that can be used in the emulsion polymerization method of the present invention include vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, and vinyl versatate; methyl acrylate;
Acrylic esters such as ethyl acrylate, butyl acrylate, or 2-ethylhexyl acrylate, methacrylic esters such as methyl methacrylate, ethyl methacrylate, or butyl methacrylate, and halogens represented by vinyl chloride. Vinyl chloride, vinylidene halides represented by vinylidene chloride, ethylene,
α- such as propylene, isobutylene or octene etc.
Olefins, unsaturated monobasic acids and their salts such as acrylic acid, methacrylic acid, crotonic acid, vinylsulfonic acid or vinyltoluenesulfonic acid, unsaturated dibasic acids such as itaconic acid, maleic acid or fumaric acid, etc. Salts and half esters thereof, nitrogen-containing vinyl compounds such as N-vinylpyrrolidone, acrylonitrile or acrylamide, hydroxyl group-containing vinyl compounds such as β-hydroxyethyl methacrylate or N-methylolacrylamide, triallylcyanurate , allyl compounds such as trimethylolpropane diallyl ether or diallyl phthalate, epoxy group-containing unsaturated compounds such as glycidyl methacrylate, divinyl compounds such as divinylbenzene, cyclopentadiene or butadiene, styrene hemethylstyrene, dimethyl Examples include one or a mixture of two or more styrene derivatives such as styrene, ethylstyrene, vinylstyrene, isopropylstyrene, phenylstyrene, chlorostyrene, and the like.

The polymerization method for obtaining the emulsion composition of the present invention includes:
The reaction operation is very simple because the most common polymerization method of adding a polymerization initiator to the aqueous solution of the multi-component copolymer and adding the monomers at once or dropwise polymerization can be adopted. .

Examples of polymerization initiators include peroxides such as persulfates and hydrogen peroxide, organic peroxides such as tertiary butyl hydroperoxide and cumene hydroperoxide, and redox combinations of these peroxides and reducing agents. Well-known initiators such as system catalysts can be used. The emulsion concentration of the present invention can be changed as appropriate within the range of 25 to 70% depending on the application.

Additionally, additives can be added during or before or after emulsion polymerization, if necessary. These additives include plasticizers, solvents, fillers, and pigments, and in some cases, latex produced by other methods may also be added.

The emulsion composition thus obtained can be heated or added with a crosslinking agent to significantly improve the water resistance and heat resistance of the emulsion film. As the crosslinking agent used in this case, isocyanate compounds, epoxy compounds, urea resins, melamine resins, or polyvalent metal compounds are effective. Thus, the emulsion composition obtained according to the present invention can be used as an adhesive, paint, laundry starch, non-woven fabric binder, fiber processing agent such as carpet backing, as well as for paper processing such as internal addition to paper and reinforcing agent for corrugated cardboard. It has various uses such as soil stabilizer, dust preventive agent, etc.
Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples.

Example 1 Isobutylene 447 and maleic anhydride 707 were copolymerized in toluene using a polymerization catalyst (benzoyl peroxide) 0.6 t and a chain transfer agent at 68 to 70°C, and the molar ratio of isobutylene to maleic anhydride was 1. :1 copolymer (1) powder 1
I got 10y.

30 of the copolymer in dimethylformamide (DMF).
The intrinsic viscosity measured at °C was 0.45 d1/t. 100f of the above copolymer (1) was placed in a 3-tube flask (No. 11) and while stirring, a nitrogen mixed gas containing 40% ammonia gas was added from one flask to 30 to 50 ml per minute.
A copolymer (3) was obtained in which the units based on maleic anhydride in the copolymer were replaced by units based on maleic acid amide or ammonium salt. The copolymer (11
) was investigated for units based on maleic acid amide or ammonium salt in the copolymer by elemental analysis and nuclear magnetic resonance method, and it was found that 72% of the units based on maleic anhydride were units based on maleic acid amide or ammonium salt. It turns out that there is. The copolymer (n) thus obtained was placed in a flask equipped with a condenser and heated to 185°C, and the produced water was distilled off. 6. Distilled water has the original weight.
Heating was stopped when the temperature reached 5%. The copolymer gradient thus obtained was hydrolyzed with an aqueous solution under acidic hydrochloric acid to convert the amide and ammonium salt into carboxylic acid, and then
The composition of the copolymer (e) was investigated by potentiometric titration, nuclear magnetic resonance method, and elemental analysis, and it was found that the copolymer (e) had the following composition. (However, R is -C-CH2-, and is H or v▲↓0NH4)
．． , Incidentally, the intrinsic viscosity when measured at 30°C in dimethylformamide (DMF) is 0.
It was 4d1/y.

0.87 ammonium persulfate was added as an initiator to 240 t of a 10% aqueous solution of the above multi-component copolymer, and monomers of vinyl acetate and butyl acrylate mixed at various mixing ratios or vinyl chloride 1507 were polymerized dropwise.

The polymerization reaction was completed in about 4 hours at 80 to 85°C, and an emulsion was obtained. The obtained emulsion was cast on a glass plate to a film thickness of 0.5 mm, and then heat treated at 150° C. for 3 minutes, and the water resistance of the film was measured. Table 1 shows the results. Example 2 15k of 20% aqueous solution of the multi-component copolymer used in Example 1
g, 36t of ammonium persulfate, 6k9 of water, and 3k9 of vinyl acetate are charged into a polymerization tank, and the internal temperature is raised to 80 to 85°C.

Once the polymerization has started, the remaining vinyl acetate 12k9 is continuously added. Polymerization is completed in about 4 hours. After adjusting the pH of the emulsion thus obtained to 5 to 6 with ammonia water, various performances of the emulsion and the emulsion film were measured.

The results are shown in Table 3. In addition, the polymerization conditions of Examples 2 to 7 are summarized in Table 2. Example 3 Polymerization was carried out in the same manner as in Example 2 except that 7.5 kg of the multi-component copolymer aqueous solution used in Example 2 was used and the water was changed to 13.5k9.

The results are shown in Table 3. Example 4 The isobutylene-maleic anhydride copolymer (1) in Example 1 was produced in the same manner as in Example 1 except that the amount of chain transfer agent used was changed, and the intrinsic viscosity at 30°C in DMF was 1.1 d1. An isobutylene-maleic anhydride copolymer of /7 was produced.

Ammonia gas treatment and heat treatment were performed in the same manner as in Example 1, and the intrinsic viscosity at 30°C in DMF was 1.0 d1/
In step 7, a copolymer having the same composition as the multi-component copolymer casing of Example 1 was prepared. Emulsion polymerization was carried out in the same manner as in Example 2 except that the multi-component copolymer thus obtained was used as a protective colloid.

The results are shown in Table 3. Example 5 The internal temperature in Example 2 was changed to 60° C., and the ammonium persulfate was changed to 1% hydrogen peroxide and 10% Longalite aqueous solution, and both were added continuously.

Note that the amount of water used for adding the catalyst is subtracted from the amount of water used for initial charging. Polymerization was carried out in the same manner as in Example 2, and the results are shown in Table 3.

Example 6 Add 5% crosslinker/emulsion to the emulsion of Example 2.

゛The results are shown in Table 3.

Example 7 Measuring method (1) Mechanical stability: 1 coagulated material was measured using a Maron tester.
Autoclave 101 minutes using a wire mesh with 0 mesh. Charge 5.0k9 of hetoluene, 600t of maleic anhydride, 4.57% of polymerization initiator (α・α″-azobisisobutyronitrile), and chain transfer agent, and dissolve thoroughly. After removing oxygen in the system by blowing in nitrogen gas, ethylene gas was added until the internal pressure reached 20k9/Cd, and polymerization was carried out at 68°C for 10 hours.

The resulting polymer had an ethylene/maleic anhydride molar ratio of 1:1 and an intrinsic viscosity of 0.4 at 30°C in DMF.
It was a copolymer of 2d1/t. This copolymer powder 10
Introduce ammonia gas to 07, then 180 to 185
The mixture was heated to 0.degree. C. to obtain a multi-component copolymer having the following components.
(However, in the formula, R' represents CH, -CH2, and v represents H or NH4. This multi-component copolymer is
The intrinsic viscosity measured at 30°C was 0.40 d1/7.

240 tons of a 10% aqueous solution of this multi-component copolymer was prepared, and then a polymerization initiator (ammonium persulfate) was added to it.
．． After adding 87, vinyl acetate 1507 was added dropwise, and 80~
Emulsion polymerization was carried out at 85°C for 4 hours. The obtained emulsion was subjected to various evaluations in the same manner as in Example 1.

The results are shown in Table 3. As is clear from Table 3, the emulsion using a multicomponent copolymer containing at least isobutene and maleic acid imide units as an emulsion stabilizer has excellent stability and can provide a film with good water resistance. Example 8 11? Polymerization solvent (isopropyl acetate) 5007, isobutylene 447, maleic acid imide 327, methacrylic acid 357, and polymerization catalyst (α
0.87 of l-azobis-isobutyronitrile) was charged in a nitrogen atmosphere and polymerized at 68°C for 10 hours.

The obtained polymer was precipitated as a white powder. The composition of the polymer was investigated by elemental analysis and electrodifferential titration, and it was found to be a copolymer containing 49, 25, and 26 mol% of units based on isobutylene, maleic acid imide, and methacrylic acid, respectively. . This copolymer 107,2
A copolymer aqueous solution was prepared by mixing 37 y of 5% ammonia water and 87 y of water.

This aqueous solution 1007 and vinyl acetate 707 were added dropwise to emulsion polymerization at 80 to 85°C. Note that potassium persulfate was used as a polymerization catalyst. The polyvinyl acetate aqueous emulsion thus obtained had a concentration of 47.0% and a viscosity of 1200 cp. The pH was 5.3 and the mechanical stability was 3.1%.

In addition, both the freezing stability and the stability when left at 5° C. for 30 days were good. Example 9 Multi-component copolymer l []) 10007 prepared in Example 1,
507 ml of methanol, 333 ml of water, and 17 ml of 25% ammonia water were placed in a 3-bottle flask equipped with a stirrer and a reflux condenser, and heated at 85° C. for 3 hours to obtain a homogeneous solution.

When a portion of this solution was sampled and the copolymer was investigated by potentiometric titration and elemental analysis, 71% of the maleic anhydride-based units in the multicomponent copolymer were monomethyl esters, and 29% were maleic esters. It was found that it was an acid or its ammonium salt.

The above copolymer aqueous solution 1007, vinyl acetate 1507, water 957, and catalysts (ammonium persulfate and Rongarit) were charged and emulsion polymerization was carried out.

Claims (1)

[Claims] 1 In the main chain, (A) a unit based on an α-olefin, (B
) units based on maleic acid imide or N-substituted maleic acid imide, and (C) units based on unsaturated carboxylic acid, its ester, or its amide, as a protective colloid. A method for producing an emulsion composition, comprising emulsion polymerization of monomers.