JPH10128095A - Method for producing reactive emulsifier and aqueous polymer - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To have excellent copolymerizability and good emulsion polymerization stability.
It can improve the physical properties such as water resistance of the polymer produced from the obtained emulsion, and there is no restriction on the coagulant and the reduction of the emulsifier mixed in the wastewater when the emulsion is broken and the polymer is taken out. Provide a reactive emulsifier that exhibits an effect. A reactive emulsifier comprising a compound having an alkenylamide group and a carboxyl group in one molecule, and a method for producing an aqueous polymer using the reactive emulsifier.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a reactive emulsifier comprising a compound having an alkenylamide group and a carboxyl group in one molecule, and a method for producing an aqueous polymer using the reactive emulsifier.

[0002]

2. Description of the Related Art
In the emulsion polymerization, as an emulsifier, an anionic surfactant such as an alkylbenzene sulfonate or an alkyl sulfate, a nonionic surfactant such as a polyoxyalkylene alkyl ether, a polyoxyalkylene fatty acid ester, or a polyoxyalkylene sorbitan is used. Used alone or in a mixed system. However, these surfactants have a problem that physical properties such as water resistance when a coating film is formed from the obtained polymer emulsion are reduced. In addition, when a polymer is taken out by breaking an emulsion in the production of synthetic rubber, an emulsifier is mixed into waste water, and there is a problem that a load of wastewater treatment increases.

[0003] In order to solve these problems, a technique of using a reactive emulsifier to incorporate the emulsifier into a polymer has been disclosed. The reactive emulsifiers include, for example, a reactive emulsifier having an acrylic ester group (Japanese Patent Application Laid-Open No. 63-77530) and a reactive emulsifier having a styryl group (Japanese Patent Application Laid-Open No. 4-53802). And reactive emulsifiers having an allyl ester group (JP-A-4-68013 and JP-A-5-65316) are known. However, anionic reactive emulsifiers in which the hydrophilic group is a sulfonic acid salt type or sulfate ester type have low polymer recoverability when the polymer emulsion is broken using an acid as a coagulant, or when the hydrophilic group is nonionic. There was a problem that the stability at the time of polymerization was low and the formed polymer emulsion was coarse. In addition, a reactive emulsifier having an acrylic ester group as a reactive group has excellent copolymerizability but poor stability at the time of emulsion polymerization, and when the reactive group is a styryl group, the copolymerizability of the obtained polymer is low. There have been problems such as poor water resistance and adhesiveness, and in the case of an allyl ester group, under acidic or alkaline conditions, the ester group is decomposed to destabilize polymerization.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a polymer prepared from the obtained emulsion has excellent copolymerizability, excellent emulsion polymerization stability, and excellent emulsion polymerization stability. Found a reactive emulsifier that can improve the physical properties such as water resistance of water, and has no restriction on the coagulant and is effective in reducing the emulsifier mixed in the wastewater when the polymer is taken out by breaking the emulsion. Thus, the present invention has been completed.

That is, the present invention provides the following general formula (I)
And / or a reactive emulsifier comprising a compound represented by (II), and a method for producing an aqueous polymer, which comprises emulsion-polymerizing an unsaturated monomer in the presence of the reactive emulsifier. It is.

[0006]

Embedded image

Wherein R ₁ is a hydrocarbon group having 5 to 30 carbon atoms or a hydrocarbon group having 5 to 30 carbon atoms having a substituent, R ₂ is a hydrogen or methyl group, M is a monovalent or divalent hydrocarbon group. Represents a cation or a mixture thereof.)

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The reactive emulsifier comprising the compound represented by the above general formula (I) and / or (II) will be specifically described below.

In the general formulas (I) and (II), R ₁ is a hydrocarbon group having 5 to 30, preferably 10 to 20 carbon atoms, or a substituted or unsubstituted hydrocarbon group having 5 to 30, preferably 10 to 20 carbon atoms. Although it is a hydrocarbon group, specific examples of the hydrocarbon group include linear or branched hydrocarbon groups such as an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylaryl group, and an aralkyl group. Examples of the hydrocarbon group having a substituent include a hydroxyl group, a halogen group,
Examples include a hydrocarbon group to which a substituent such as a carboxyl group, a nitrile group, an amide group, or an amino group is bonded. Among these, a linear or branched alkyl group or alkenyl group is preferred. R ₂ is hydrogen or a methyl group.

M represents a monovalent or divalent cation or a mixture thereof.
Examples thereof include an alkaline earth metal, ammonium, and an amine cation alone or a mixture thereof, and further, a mixture of a hydrogen ion and an alkali metal, an alkaline earth metal, ammonium, an amine cation, and the like. Among them, M is preferably sodium, potassium, ammonium or a lower amine cation. In the case of a mixture with hydrogen ions, the mixing ratio of hydrogen ions is preferably 5% by weight or less.

The method for synthesizing the compounds represented by the above general formulas (I) and / or (II) is not particularly limited.
The method shown in the following reaction formula is exemplified. That is, the general formula (I
The alkenyl succinic anhydride represented by II) is reacted with alkenyl amine to obtain a compound represented by the general formula (IV), and the compound represented by the general formula (IV) is hydrolyzed with one equivalent of an alkali or the like. By performing the decomposition, the compound represented by the general formula (I) and / or (II) can be obtained.

[0012]

Embedded image

The unsaturated monomer which can be emulsion-polymerized using the reactive emulsifier of the present invention is not particularly limited, but may be an acrylic acid such as ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate. Esters, methacrylic esters such as methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, and glycidyl methacrylate; α, β-unsaturated carboxylic amides such as acrylamide and N-methylolacrylamide; acrylonitrile; methacryloyl Α, such as nitrile,
β-unsaturated nitriles, styrene, styrene derivatives such as α-methylstyrene, vinyl chloride, vinylidene chloride,
Halogen-containing unsaturated monomers such as chloroprene, diene derivatives such as butadiene and isoprene, and crosslinkable monomers such as polyethylene glycol diacrylate and polyethylene glycol dimethacrylate are used. These unsaturated monomers are used for emulsion polymerization as one kind or a mixture of two or more kinds.

As a method of emulsion-polymerizing an unsaturated monomer using the reactive emulsifier of the present invention, a known emulsion polymerization method can be used. As the polymerization initiator, conventionally known initiators may be used, for example, hydrogen peroxide, potassium persulfate, inorganic peroxides such as ammonium persulfate, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide and the like. Organic initiators such as organic peroxides, azo initiators such as azobisdiisobutyronitrile and methoxybenzenediazomercaptonaphthalene; or sodium hydrogen sulfite, sodium thiosulfate and ferrous sulfate as peroxides and oxidizing agents And a redox polymerization initiator system using a reducing agent such as sugar in combination.

The reactive emulsifier of the present invention is generally used in an amount of 0.1 to 20% by weight, preferably 0.2 to 5% by weight, based on all unsaturated monomers.

Although the reactive emulsifier of the present invention alone can form a good polymer emulsion alone,
If necessary, two or more reactive emulsifiers of the present invention may be used, and other emulsifiers or protective colloid agents may be used in combination. Other emulsifiers in this case include dodecylbenzene sulfonate, alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, dialkyl sulfosuccinates, polyoxyethylene alkyl ethers , Polyoxyethylene alkylphenyl ethers, etc., as protective colloid agents,
Examples include polyvinyl alcohol and hydroxyethyl cellulose. However, considering the physical properties such as water resistance of the polymer formed by emulsion polymerization and the load of wastewater treatment, the amount of these emulsifiers used is preferably 50% by weight or less, more preferably 20% by weight or less of the total emulsifier.

[0017]

EXAMPLES The present invention will be specifically described below with reference to synthesis examples and examples, but the present invention is not limited to these examples. Further, “%” in the examples is based on weight unless otherwise specified.

The physical properties of the polymers obtained in the following examples were evaluated by the following methods. <Evaluation method> 1. Polymerization stability The polymer latex after completion of polymerization is filtered through a 100-mesh wire gauze, the filtration residue is washed with water, dried at 105 ° C and 200 mmHg overnight, weighed, and weighed based on the amount of monomer used.
Displayed with.

2. Particle size The particle size of the polymer latex after filtration through a 100 mesh wire gauze was measured using Coulter N-4.

3. Mechanical stability 50 g of polymer latex after filtration through a 100-mesh wire mesh is rotated by a Malon mechanical stability tester under the conditions of 10 kw and 1000 rpm for 5 minutes, and the formed aggregates are filtered through a 100-mesh wire mesh. After washing with water and drying overnight at 105 ° C. and 200 mmHg, it was weighed and indicated as a percentage by weight based on the polymer.

4. Water resistance (film whitening test) 76 × 2 polymer latex after filtration through 100 mesh wire mesh
Spread 125mm thick on 6mm slide glass, 100 ℃,
A film was formed for 5 minutes and cooled to room temperature to obtain a test piece. The slide glass to which the film was attached was immersed in a petri dish containing water at room temperature provided with 8-point type newspaper underneath, and the time until the type became unreadable was measured.

5. Total organic carbon (TOC) 20 g of polymer latex after filtration through a 100 mesh wire mesh
6 ml of a 0.1 mol / l sulfuric acid aqueous solution was added, and the mixture was left at room temperature for 3 hours. The resulting polymer was filtered through a 100-mesh wire gauze, washed with 5 ml of a 0.1 mol / L KOH aqueous solution, and the combined filtrate and washing solution were analyzed for total organic carbon.

First, a synthesis example of the reactive emulsifier of the present invention is shown below. Synthesis Example 1 Hexenyl succinic anhydride was placed in a 1-liter glass reaction vessel equipped with a stirrer, a cooler, a nitrogen inlet tube, and a dropping funnel.
364g was charged. Under ice-cooling, 136 g of allylamine was added dropwise using a dropping funnel. After completion of the addition, the reaction was carried out at 60 ° C. for 4 hours. The product was heated to 60 ° C. under reduced pressure to remove excess allylamine to obtain N-allylhexenyl succinimide in a yield of 85%. Hydrolysis was performed with a 1N aqueous solution of potassium hydroxide at 60 ° C., and the desired 1-allylamido-
A mixture of potassium hexenyl succinate and potassium 4-allylamido-hexenyl succinate (hereinafter, referred to as potassium allyl amide-hexenyl succinate) was obtained.

Synthesis Example 2 Octenyl succinic anhydride was placed in a 1-liter glass reactor equipped with a stirrer, a cooler, a nitrogen inlet tube and a dropping funnel.
210g was charged. Under ice-cooling, 68 g of allylamine was added dropwise using a dropping funnel, and after completion of the addition, the reaction was carried out at 60 ° C. for 4 hours. The product was heated to 60 ° C. under reduced pressure to remove excess allylamine to obtain N-allyloctenylsuccinimide in a yield of 87%. The mixture is hydrolyzed with a 1N aqueous solution of potassium hydroxide at 60 ° C., and a mixture of the desired potassium 1-allylamido-octenylsuccinate and potassium 4-allylamido-octenylsuccinate (hereinafter referred to as allylamide-
Octenyl succinate).

Synthesis Example 3 Dodecenyl succinic anhydride was placed in a 1-liter glass reactor equipped with a stirrer, a cooler, a nitrogen inlet tube, and a dropping funnel.
266 g were charged. Under ice-cooling, 68 g of allylamine was added dropwise using a dropping funnel, and after completion of the addition, the reaction was carried out at 60 ° C. for 4 hours. The product was heated to 60 ° C. under reduced pressure to remove excess allylamine to obtain N-allyldodecenyl succinimide with a yield of 91%. The mixture is hydrolyzed with a 1N aqueous solution of potassium hydroxide at 60 ° C., and a mixture of target potassium 1-allylamido-dodecenylsuccinate and potassium 4-allylamido-dodecenylsuccinate (hereinafter, allylamide-
(Called potassium dodecenyl succinate).

Synthesis Example 4 324 g of hexadecanylsuccinic anhydride was charged into a 1-liter glass reactor equipped with a stirrer, a cooler, a nitrogen inlet tube and a dropping funnel. Under ice-cooling, 68 g of allylamine was added dropwise using a dropping funnel, and after completion of the addition, the reaction was carried out at 60 ° C. for 4 hours. The product was heated to 60 ° C. under reduced pressure to remove the excess allylamine to obtain N-allylhexadecanesuccinimide at a yield of 88%. The mixture is hydrolyzed with a 1N aqueous solution of potassium hydroxide at 60 ° C., and a mixture of the target potassium 1-allylamido-hexadecanesuccinate and potassium 4-allylamido-hexadecanylsuccinate (hereinafter, allylamide-hexadecanyl) is used. Potassium succinate).

Synthesis Example 5 364 g of nonadecenyl succinic anhydride was charged into a 1-liter glass reactor equipped with a stirrer, a cooler, a nitrogen inlet tube and a dropping funnel. Under ice-cooling, 68 g of allylamine was added dropwise using a dropping funnel, and after completion of the addition, the reaction was carried out at 60 ° C. for 4 hours. The product was heated to 60 ° C. under reduced pressure to remove excess allylamine to obtain N-allylinonadecenyl succinimide with a yield of 93%. Hydrolysis was performed with a 1N aqueous solution of potassium hydroxide at 60 ° C., and the desired potassium 1-allylamido-nonadecenylsuccinate and 4-allylamido-
A mixture of potassium nonadecenyl succinate (hereinafter, referred to as potassium allylamide-nonadecenyl succinate) was obtained.

Synthesis Example 6 Dodecenyl succinic anhydride was placed in a 1-liter glass reaction vessel equipped with a stirrer, a cooler, a nitrogen inlet tube, and a dropping funnel.
266 g were charged. Under ice cooling, 85 g of isobutenylamine was added dropwise using a dropping funnel, and after completion of the addition, the reaction was carried out at 60 ° C. for 4 hours. The product was heated to 60 ° C. under reduced pressure to remove excess isobutenylamine to obtain N-isobutenyldodecenyl succinimide in a yield of 90%. Hydrolysis with 1N aqueous potassium hydroxide solution at 60 ° C.
A mixture of potassium isobutenylamide-dodecenylsuccinate and potassium 4-isobutenylamide-dodecenylsuccinate (hereinafter referred to as potassium isobutenylamide-dodecenylsuccinate) was obtained.

Next, examples and comparative examples in which an aqueous polymer was produced using the reactive emulsifier of the present invention or a conventional emulsifier are shown below. Examples 1 to 6 and Comparative Examples 1 to 6 Emulsion polymerization was carried out using the reactive emulsifier of the present invention shown in Table 1 according to the following emulsion polymerization formula-1 to obtain a polymer emulsion and a polymer emulsion obtained from the polymer emulsion. The physical properties of the obtained film were evaluated. An example using a conventional emulsifier was similarly evaluated as a comparative example. Table 1 shows the results. (Emulsion polymerization recipe-1) 1 g of emulsifier, 149 g of water, 5 g of n-butyl acrylate were placed in a 0.5-liter glass reactor equipped with a thermometer, a stirrer, a cooler, a nitrogen inlet tube, and a dropping funnel.
g and potassium persulfate 0.2 g. The inside of the reaction system was replaced with nitrogen, and the temperature was raised while stirring. 95 g of n-butyl acrylate was added dropwise over 3 hours from the time when the temperature reached 70 ° C. After completion of the dropwise addition, the temperature was raised to 80 ° C., and aging was performed for 2 hours.

[0030]

[Table 1]

Examples 7 to 12 and Comparative Examples 7 to 11 Emulsion polymerization was carried out using the reactive emulsifier of the present invention shown in Table 2 according to the following emulsion polymerization recipe-2. And the amount of emulsifier mixed in the wastewater (TOC was measured) was evaluated. An example using a conventional emulsifier was similarly evaluated as a comparative example. Table 2 shows the results.

(Emulsion polymerization recipe-2) The emulsifier 5 was placed in a 1-liter autoclave equipped with a thermometer, a stirrer, and a cooler.
g, water 200 g, paramenthane hydroperoxide 0.1
g, ferrous sulfate heptahydrate 0.05 g, ethylenediaminetetraacetic acid 0.07 g, dodecyl mercaptan 0.2 g, sodium triphosphate dodecahydrate 0.8 g, and styrene 30 g. Subsequently, 70 g of liquefied butadiene was charged and air was removed. The temperature was raised to 5 ° C. while stirring. When the temperature reached 5 ° C., the reaction was carried out to a polymerization conversion of 67 to 73%, and a polymerization terminator was added to terminate the polymerization. Subsequently, the remaining monomers were removed under reduced pressure.

[0033]

[Table 2]

[0034]

As described above, according to the present invention, the emulsion polymerization stability is improved by using the compound represented by the general formula (I) and / or (II) as the emulsifier in the emulsion polymerization. In addition, the water resistance of the polymer film prepared from the obtained emulsion is also good. Further, it is effective in reducing organic substances mixed in the wastewater when the emulsion is broken and the polymer is taken out.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // (C08F 212/08 236: 06)

Claims (3)

[Claims] 1. A reactive emulsifier comprising a compound represented by the following general formula (I) and / or (II). Embedded image (Wherein, R ₁ is a C 5-30 hydrocarbon group or a C 5-30 hydrocarbon group having a substituent, R ₂ is a hydrogen or methyl group, M is a monovalent or divalent cation or Represents a mixture thereof.) 2. The method according to claim 1, wherein in the general formulas (I) and / or (II), M is an alkali metal, alkaline earth metal, ammonium or amine cation.
The reactive emulsifier according to the above. 3. In the presence of the reactive emulsifier according to claim 1,
A method for producing an aqueous polymer, comprising subjecting an unsaturated monomer to emulsion polymerization.