JPH06239908A - Reactive emulsifying agent - Google Patents

Abstract

PURPOSE:To obtain a reactive emulsifying agent, excellent in hydrolytic resistance, reactive within a wide pH region and capable of enhancing the bleeding and water resistance of a resin by reacting dicarboxylic acids with amino group- containing sulfonates and an unsaturated compound reactive with the carboxylic acids. CONSTITUTION:This emulsifying agent is obtained by reacting (A) a dicarboxylic acid or an anhydride thereof (e.g. dodecenylsuccinic anhydride) with (B) sulfonates having primary or secondary amino group (e.g. sodium salt of N- methyltaurine) and (C) an ethylenically unsaturated compound having a functional group reactive with the carboxylic acid (e.g. glycidyl methacrylate) at molar ratio within the range of 1:(0.8-1.2):(0.8-1.2) of the components (A):(B):(C) under temperature conditions of 50-200 deg.C in the presence or absence of a catalyst to afford the objective reactive emulsifying agent, excellent in hydrolytic resistance, applicable to the emulsion polymerization within a wide pH range, especially within an acidic region and capable of reducing the COD of polymerization waste water and simultaneously enhancing the bleeding and water resistance of a resin produced by the emulsion polymerization.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a reactive emulsifier, and more particularly to a reactive emulsifier useful as an emulsifier for emulsion polymerization or suspension polymerization of vinyl compounds.

[0002]

Emulsifiers are widely used in resin production processes such as emulsion polymerization and suspension polymerization. Since the emulsifiers usually used for these applications are non-reactive, when a resin is produced by emulsion polymerization using these emulsifiers, the emulsifier is mixed into the resin and the emulsifier migrates to the resin surface after molding, This causes poor resin appearance and deterioration of water resistance of the resin. In order to prevent this, a method of salting out the resin obtained by emulsion polymerization and removing the emulsifier has been used. However, since most of the emulsifier used flows out into this wastewater, the COD of the wastewater is high. Therefore, it causes big problems such as increase of wastewater treatment cost and pollution of environment. As a means to solve this, by introducing a polymerizable double bond in the emulsifier molecule and preventing it from flowing into the washing wastewater by copolymerizing with the resin, the migration of the emulsifier to the resin surface is prevented, and bleeding resistance is improved. Attempts have been made to improve the water resistance of resins and resins. The emulsifier used here is a so-called reactive emulsifier, and is a compound having a functional group capable of copolymerizing with a monomer in the polymerization system in the molecule and having a molecular structure having emulsifying ability.
Examples of such reactive emulsifiers include Japanese Patent Publication No.
6291 publication, sulfosuccinate compound having an allyl group, sulfoalkyl fumarate salt disclosed in JP-A-51-30285, JP-B-55
-41684, alkyl ether compounds of alkylene oxide adducts of (meth) acrylic acid, sulfuric acid ester salts of alkylene oxide adducts of allyl alcohol disclosed in JP-A-61-223011, JP-A-1-99638. , A sulfate ester salt of a reaction product of α-olefin oxide and allyl alcohol,
JP-A-3-76765 discloses a sulfonated product of an allyl glycidyl ether adduct of maleic acid monoalkyl ester.

[0003]

However, among these reactive emulsifiers, few are capable of simultaneously satisfying the emulsifying ability, copolymerizability, and hydrolysis resistance. Emulsion polymerization using these reactive emulsifiers is not possible. When this is carried out, problems such as a decrease in the stability of the latex, an outflow of unreacted emulsifier into the washing waste liquid, and a decrease in the polymerization stability due to hydrolysis of the emulsifier during the polymerization occur. Especially in an emulsion polymerization system such as a redox initiator system which needs to be carried out in a low pH range of pH 2 to 3, none of these three conditions can be sufficiently satisfied. The present invention, in a wide pH range, even in a particularly low pH range, high copolymerizability, excellent emulsifying ability, and an object of the present invention is to provide a reactive emulsifier having excellent hydrolysis resistance. is there.

[0004]

Means for Solving the Problems As a result of intensive research to solve this problem, the present inventors have found that a sulfonate compound having a specific ethylenically unsaturated double bond has an excellent emulsifying ability even in a low pH range. It was found that they have high copolymerizability and excellent hydrolysis resistance, and have completed the present invention based on this finding.

That is, the present invention relates to (A) a dicarboxylic acid or a dicarboxylic acid anhydride, (B) a sulfonate having a primary or secondary amino group, and (C) an ethylene having a functional group capable of reacting with a carboxylic acid. It is a reactive emulsifier comprising a compound obtained by reacting with an unsaturated unsaturated compound.
The (A) dicarboxylic acid or dicarboxylic acid anhydride (hereinafter referred to as A component) used in the present invention is an aliphatic dicarboxylic acid having 2 to 30 carbon atoms, an aliphatic dicarboxylic acid anhydride having 3 to 30 carbon atoms, or 8 carbon atoms. The aromatic dicarboxylic acid having 30 carbon atoms and the aromatic dicarboxylic acid anhydride having 8 to 30 carbon atoms. Carbon number 2
Examples of the aliphatic dicarboxylic acid of -30 include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, carboxyoctadecanoic acid,
Examples include saturated aliphatic dicarboxylic acids such as alkylsuccinic acids having 5 to 30 carbon atoms. Examples of the aliphatic dicarboxylic acid anhydride having 3 to 30 carbon atoms include succinic anhydride, glutaric anhydride, and alkyl succinic anhydride. further,
Unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, alkenylsuccinic acid having 5 to 30 carbon atoms and unsaturated aliphatic dicarboxylic acid anhydrides such as maleic anhydride, fumaric anhydride and alkenylsuccinic anhydride It can be used preferably. Examples of the aromatic dicarboxylic acid having 8 to 30 carbon atoms include phthalic acid, terephthalic acid, and 9 to 30 carbon atoms.
30 alkyl and alkenyl phthalic acids and the like.
As the aromatic dicarboxylic acid anhydride having 8 to 30 carbon atoms,
Examples thereof include phthalic anhydride, alkyl and alkenyl phthalic anhydride having 9 to 30 carbon atoms. When a dicarboxylic acid is used as the component A, it is preferably used as an acid halide. Examples of (B) sulfonates having a primary or secondary amino group (hereinafter referred to as component B) used in the present invention include taurine, alkyl or alkenyl taurine having 3 to 30 carbon atoms and salts thereof.

Examples of the (C) ethylenically unsaturated compound having a functional group capable of reacting with a carboxylic acid (hereinafter referred to as C component) used in the present invention include (meth) allyl alcohol, acetylene alcohol and hydroxystyrene. Unsaturated alcohol, ethylene glycol mono (meth)
Unsaturated alcohols and polyhydric alcohols such as allyl ether, propylene glycol mono (meth) allyl ether, 1,6 hexanediol mono (meth) allyl ether, glycerol mono (meth) allyl ether, pentaerythritol mono (meth) allyl ether Partial etherification product with, ethylene oxide 2 to 40 mol adduct of (meth) allyl alcohol, propylene oxide 2 to 40 mol adduct of (meth) allyl alcohol, ethylene oxide 1 to 40 mol propylene oxide 1 to (meth) allyl alcohol 40 moles of block addition polymer or random addition polymer, hydroxystyrene having 2 to 4 carbon atoms
Unsaturated alcohol alkylene oxide adduct such as alkylene oxide 2 to 40 mol adduct, ethylene glycol mono (meth) acrylate, 1,4 butanediol mono (meth) acrylate, 1,6 hexanediol mono (meth) acrylate , Glycerin mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate,
Unsaturated carboxylic acids and polyhydric alcohols such as pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, sorbitan mono (meth) acrylate, sorbitol di (meth) acrylate, triethanolamine mono (meth) acrylate, etc. Epoxy groups such as partial esterification products, allyl glycidyl ethers, glycidyl etherification products of alkylene oxide adducts of (meth) allyl alcohol, glycidyl etherification products of alkylene oxide adducts of (meth) acrylic acid, glycidyl (meth) acrylate, etc. Unsaturated amines such as (meth) allylamine and the like can be used. Among these, an ethylenically unsaturated compound having an epoxy group can be particularly preferably used.

The emulsifier of the present invention is selected from component A 1
Obtained by reacting one or more dicarboxylic acids or dicarboxylic anhydrides with one or more compounds selected from component B and one or more compounds selected from component C . The ratio of each of A, B, and C components is not particularly limited, but A component: B component: C component =
It is preferably in the range of 1: 0.8 to 1.2: 0.8 to 1.2 mol. As a method of reacting the component B or the component C with the component A, a known synthesis method can be applied, and if an appropriate method is selected for reacting the functional group of the component B or the component C and the carboxyl group. Good. For example, when the esterification method or the amidation method is applied, the A component and the B component or the C component are esterified or amided with a carboxyl group in the presence or absence of a catalyst under a temperature condition of 50 ° C to 200 ° C. There is a method of making it. Furthermore, when the epoxy ring-opening addition reaction is applied, 50 ° C to 120 ° C
There is a method of ring-opening addition of an epoxy group to a carboxyl group in the presence or absence of a catalyst under the above temperature condition. When a compound having a (meth) acryloyl group is used as the C component, it is desirable to carry out the reaction in the presence of a radical polymerization inhibitor for protecting the terminal vinyl group during the reaction, for example, hydroquinone monomethyl ether. The inhibitor is usually 500 with respect to the reactive emulsifier of the present invention.
It is used in an amount of 0 ppm or less, preferably 500 ppm or less.
The reactive emulsifier of the present invention thus obtained is used as it is or after diluted with a solvent such as water or an organic solvent. The reactive emulsifier of the present invention is 0.01 to 20% by weight, preferably 0.05 to 5% by weight, based on the total amount of monomers to be polymerized.
A proportion of 10% by weight can be used. The monomer for emulsion polymerization to which the reactive emulsifier of the present invention is applied is not particularly limited, but a vinyl compound is preferable, for example, vinyl ester monomer such as vinyl acetate, (meth) acrylic acid, (meth) acrylic acid ester, acrylonitrile,
Acrylic monomers such as acrylamide; Aromatic vinyl compounds such as styrene and divinylbenzene; Butadiene
Conjugated diolefins such as isoprene and chloroprene; halogen-containing vinyl compounds such as vinyl chloride and vinylidene chloride; and ethylene, maleic anhydride, maleic acid ester, fumaric acid ester and itaconic acid ester. When emulsion polymerization or suspension polymerization is performed using the reactive emulsifier of the present invention, known polymerization initiators and polymerization accelerators are used. Examples of the polymerization initiator include hydrogen peroxide, persulfate, organic peroxide, azobisisobutyronitrile, and the like, and examples of the polymerization accelerator include bisulfite, thiosulfate, iron sulfate and the like. .
The reactive emulsifier of the present invention alone can be a good emulsifier in emulsion polymerization or suspension polymerization, but other emulsifiers or emulsion stabilizers can be used in combination as long as the characteristics of the present invention are not impaired.

[0008]

EXAMPLES The present invention will be described in more detail by way of examples. The reactive emulsifiers (No. 1 to No. 8) of the present invention comprising the components A, B and C shown in Table 1, and the sulfonate compound having no primary or secondary amino group as the component (B). Comparative Example Reactive Emulsifier (No. 9, No. 10)
Using the conventional reactive emulsifier (No. 11 to No. 13) and the non-reactive emulsifier (No. 14), the emulsifying ability test,
A hydrolysis resistance test, a copolymerization test and a water resistance test were conducted.

[0009]

[Table 1]

(1) Emulsification test Acrytonitonil (50 g), water (300 g) and emulsifiers (Nos. 1 to 14 shown in Table 1) (0.5 g) were placed in a beaker, and TK Auto manufactured by Tokushu Kika Co., Ltd. Homo mixer 1 at 3000 rpm
The emulsification was performed at room temperature for 0 minutes. Immediately after that, the emulsion was transferred to a graduated cylinder, sealed, and placed in a constant temperature bath at 50 ° C.
After 60 minutes, the volume of the separated aqueous layer was determined. The better the emulsifying ability of the emulsifier, the less water is separated. The results obtained are shown in Table 2.

[0011]

[Table 2]

Note 1) Gelation occurred at the initial stage of polymerization and stable latex could not be obtained, so that water resistance could not be evaluated. (2) Hydrolysis resistance test At room temperature, in a test tube with a capacity of 100 ml, water 79.2 was added.
g, 0.8 g of each of the reactive emulsifier of the present invention and the emulsifier of the comparative example, and mixed well.
Was set to 2.0. Then, 1 g of a sample was taken from each test tube and immediately titrated with a 0.1N aqueous potassium hydroxide solution at room temperature to determine the total molar amount of acid present in the system, which was taken as the initial acid amount. After that, each test tube was sealed, left to stand for 6 hours while shaking in a constant temperature bath at 60 ° C., and then the total molar amount of acid in the system was determined in the same manner, which was taken as the late acid amount. The hydrolysis rate was calculated from the following equation based on the amount of the late-stage acid, the amount of the initial acid, and the theoretical amount of acid assuming that the emulsifier was 100% hydrolyzed. Hydrolysis rate (%) = [(late acid amount-initial acid amount) / theoretical acid amount] The results are shown in Table 2.

(3) Copolymerizability test Emulsion polymerization was carried out, and the copolymerizability of the emulsifier was evaluated from the COD value of the filtrate. Reflux condenser, stirrer, dropping funnel,
A reaction vessel equipped with a thermometer was charged with 600 g of water, 0.6 g of potassium persulfate and 0.002 g of ferrous sulfate, and charged with 1N sulfuric acid.
After adjusting the pH to 2.0, raise the temperature to 60 ° C under a nitrogen atmosphere,
While stirring, 1.2 g of each of the emulsifiers of the present invention and the emulsifiers of Comparative Examples shown in Table 1 was preliminarily mixed with 50 g of styrene, and the mixture was added dropwise over 2 hours to carry out emulsion polymerization at the same temperature for 30 minutes. It was 10 in the resulting reaction solution
% Sodium sulfate aqueous solution (100 ml) was added for salting out, the polymer was filtered off, and then the filtrate was boiled at normal pressure to remove unreacted monomers and concentrate. When the total amount of the concentrated solution decreased to 400 g, the filtration was performed again, and the COD of the filtrate was measured by the method described in JIS 0102K by the consumption amount of potassium permanganate at 100 ° C. for 30 minutes. The results are shown in Table 2.

(4) Water resistance test A reaction vessel equipped with a reflux condenser, a stirrer, a dropping funnel and a thermometer was charged with 600 g of water, 0.6 g of potassium persulfate and 0.002 g of ferrous sulfate and charged with 1N sulfuric acid. After adjusting the pH to 2.0, the mixture was heated to 60 ° C. under a nitrogen atmosphere and stirred to obtain a mixed solution of 3.2 g of each of the emulsifiers of the present invention and the emulsifiers of Comparative Examples shown in Table 1 and 80 g of acrylonitrile. The mixture was added dropwise over 2 hours, and emulsion polymerization was carried out at the same temperature for 30 minutes.
The obtained resin emulsion was diluted with water to a resin content of 10% by weight, poured into a glass petri dish at a depth of 1 mm, and allowed to dry at 30 ° C. for 48 hours in the atmospheric atmosphere to dry the resin. A film was formed. Drop a drop of water on this resin film, cover the petri dish with a glass plate to prevent the drop of water from drying, and observe with the naked eye from above this drop of water until the 8 point type placed under the dish cannot be read. Was measured. Since the resin film having poor water resistance easily absorbs water, the portion where water drops exist becomes white and becomes opaque in a short time. Therefore, it was evaluated that the longer the time for maintaining the transparency, the better the water resistance of the resin film. The results are shown in Table 2. From Table 2, the reactive emulsifier of the present invention is excellent in emulsifying ability, hydrolysis resistance, polymerization stability, and water resistance of the obtained resin. Furthermore, since the COD of the polymerization wastewater is low, the copolymerizability is excellent. Nos. 9 and 10 of the comparative examples do not have the amino group of the component B, but the hydrolysis resistance is poor and the COD of the waste water is high. Comparative Examples Nos. 11 to 13 are known reactive emulsifiers, but have emulsifying ability, hydrolysis resistance, and COD of polymerization wastewater.
Is also high. Further, Comparative Examples No. 11 and No. 13 have poor polymerization stability. No. 14 of Comparative Example is a non-reactive emulsifier, but it has poor emulsifying ability, high COD of polymerization wastewater, and poor water resistance of the obtained resin.

[0015]

Since the reactive emulsifier of the present invention has excellent hydrolysis resistance, it can be applied to emulsion polymerization in a wide pH range, particularly in an acidic range, and COD of polymerization wastewater generated after emulsion polymerization. And the bleed resistance and water resistance of the resin obtained by emulsion polymerization can be improved.

Claims (1)

[Claims] 1. An ethylenic unsaturation having a functional group capable of reacting with (A) a dicarboxylic acid or a dicarboxylic acid anhydride, (B) a sulfonate having a primary or secondary amino group, and (C) a carboxylic acid. A reactive emulsifier comprising a compound obtained by reacting with a compound.