JPH0124141B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides the following formulas () and () having an allyl group or metaallyl group as a radically polymerizable group, (In the formula, R ₁ represents an alkyl group, an alkenyl group, an alkylphenyl group, an alkenylphenyl group, or a fatty acid residue, R ₂ represents a hydrogen atom or a methyl group, and A represents an alkylene group having 2 to 3 carbon atoms. ,n
represents a positive number from 0 to 100, and M represents a monovalent cation) A sulfosuccinic acid diester salt, which is a mixture of two structural isomers, and a method for producing the same, and a reactive interface containing the same Activator compositions. Conventionally, emulsion polymerization reactions have been carried out using non-reactive surfactants. However, in the emulsion produced by this method, the surfactant remains locally concentrated without being mixed with the polymer. was incorporated into
It was difficult to obtain a homogeneous polymer film. And this heterogeneity of the polymer film is
It has been known that it has an adverse effect on various properties such as dyeing properties, antistatic properties, weather resistance, and chemical resistance. In order to eliminate these drawbacks, in recent years, molecules have been developed that contain both a group with surfactant ability and a group with polymerizability, which not only acts as an emulsifier for monomers, but also gradually incorporates them into the polymer during polymerization. More and more reactive surfactants are being developed and used. As a result of intensive studies on reactive surfactants, the present inventors discovered that two types of structural isomers represented by the above formulas () and () have an allyl group or meta-allyl group as a radically polymerizable group in the molecule. The novel sulfosuccinic acid diester salt, which is a mixture, is a useful reactive surfactant, and this sulfosuccinic acid diester salt has a hydrocarbon group, which is a hydrophobic group, and a hydroxyl group or an ether bond, which is a hydrophilic group. We have completed the present invention by discovering that emulsion polymerization can be carried out under optimal conditions by changing the balance between hydrophilicity and lipophilicity depending on the monomer. The compounds represented by formulas () and () of the present invention are produced, for example, as follows. (In the formula, R ₁ , R ₂ , A and n are the same as above) When synthesizing the diester represented by the general formula () from the half ester represented by the general formula (), (meth)allyl glycidyl ether is reacted. When selected as a reagent, the reaction may be carried out with or without a solvent, but the reaction may be carried out at 90°C to 130°C, if necessary, using a catalyst such as triethylbenzylammonium hydrochloride. In the step of synthesizing the diester represented by the general formula (), a known polymerization inhibitor is used to inhibit the polymerization or copolymerization of a maleic acid or fumaric acid residue and an allyl group, such as hydroquinone monomethyl ether, hydroquinone, pyrogallol. , catechol, benzoquinone, anthraquinone, phenothiazine, p-phenylenediamine, benzidine, nitrobenzene and the like. Sulfonation of the diester represented by formula () can be carried out using a long-known reaction in which a sulfite is added to a maleate or fumarate. Water is usually used in sulfonation reactions to dissolve the sulfites. Furthermore, in order to shorten the reaction time and improve the yield, an organic solvent that dissolves the diester and is miscible with water may be used. Examples of organic solvents include methyl alcohol,
Solvents include alcohols such as ethyl alcohol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; and ethers such as dioxane and ethylene glycol dimethyl ether. The reaction rate of sulfonation is 50℃ to 200℃,
The temperature is preferably 70°C to 150°C, and it can be carried out either under normal pressure or under increased pressure. Furthermore, in order to suppress polymerization between the diesters of the raw materials, it is desirable to add a small amount of commonly used polymerization inhibitors such as hydroquinone, pyrogallol, sulfur-containing compounds, and phosphorus-containing compounds to the reaction system. In this sulfonation reaction, allyl group (or meta-allyl group) is used as described in Japanese Patent Publication No. 49-46291.
No addition of sulfite occurs, and selective addition of sulfite to the double bond of maleic acid or fumaric acid ester residues proceeds. Formulas () and () of the present invention thus obtained
Ethylenically unsaturated monomers that can be emulsion polymerized using the compound represented by as a reactive surfactant include styrene derivatives, vinyl esters, acrylic esters, methacrylic esters, acrylic acid, methacrylic acid, α such as crotonic acid,
β-unsaturated carboxylic acids or salts thereof; α,β-unsaturated amides such as acrylamide, methacrylamide, N-methylacrylamide, N-methylolacrylamide; acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride,
Conjugated dienes such as ethylene, α-olefin and butadiene, alkyl vinyl ethers, alkyl vinyl ketones, maleic anhydride, maleic esters, itaconic esters and the like are included. Also included are crosslinkable divinyl compounds such as divinylbenzene, ethylene glycol dimethacrylate, and methylene bisacrylamide. The amount of the reactive surfactant used in the present invention varies depending on the type of polymer, monomer composition, purpose, required performance, etc. When producing a hydrophobic polymer for the purpose of dyeing properties, antistatic properties, etc., the reactive surfactant of the present invention is usually added to the copolymer in an amount of 0.1 to 40% by weight (hereinafter simply expressed as %). , preferably in an amount of 0.2 to 30%. If it exceeds 40%, the affinity for water becomes too large, which is often disadvantageous. On the other hand, when producing hydrophilic polymers (for example, water-soluble resins), 10 to 80%, preferably 20 to 80%, of
It is best to set it to 60%. The reaction temperature when carrying out emulsion polymerization using the reactive surfactant of the present invention is 0°C to 100°C,
The temperature is preferably 20°C to 90°C, and polymerization can be carried out by adding a polymerization initiator and a polymerization regulator in an inert gas. The method of charging the polymerization initiator and the polymerizable ethylenically unsaturated monomer into the reactor is to charge the entire amount at the start of polymerization, or to charge it continuously as the polymerization reaction progresses. etc., but
These methods can be selected depending on the reactivity of the monomer and the composition of the desired copolymer. The present invention
Although it is possible to optionally use a common emulsifier in combination, a sufficiently stable emulsion can be obtained even with the reactive surfactant of the present invention alone, and even when used in combination, it can be used in a common emulsion polymerization method. A proportion smaller than the quantity is sufficient. As the polymerization initiator used in the present invention, any known water-soluble radical polymerization initiator can be used. For example, inorganic peroxides such as hydrogen peroxide, potassium persulfate, and ammonium persulfate; known water-soluble organic peroxides; This is a redox polymerization initiator system that uses iron in combination. By using the reactive surfactant of the present invention, it is possible to impart excellent dyeing properties, antistatic properties, water resistance, hydrophilicity, etc. to various polymers. That is, in the polymer produced using the reactive surfactant of the present invention, the hydrophilic groups caused by the surfactant are uniformly dispersed after polymerization, so that the above properties can be improved, especially permanent charging prevention, Pigment miscibility can be improved. Furthermore, even when the reactive surfactant of the present invention is used in large amounts for the purpose of modifying polymers, compared to known modifiers made of sulfo group-containing monomers,
There is no possibility that a water-soluble polymer will form and deteriorate water resistance. Furthermore, in the reactive surfactant of the present invention, the type of hydrocarbon group that is a hydrophobic group and the length of an alkyleneoxy group that is a hydrophilic group are adjusted to improve HLB
As a result of being able to change the value, it is possible to improve the mechanical stability of the emulsion during polymerization and contribute to the prevention of environmental pollution caused by residual surfactant in reaction waste water. Next, the present invention will be explained with reference to Examples. Example 1 9.8 g of maleic anhydride and 18.6 g of lauryl alcohol were placed in a glass reaction vessel equipped with a reflux condenser, a stirrer, and a thermometer, and the mixture was stirred at 90° C. for 3 hours. Next, 11.4 g of allyl glycidyl ether,
Benzyltriethylammonium hydrochloride 0.3g,
Add 14 mg of hydroquinone monomethyl ether,
The mixture was further stirred at 90°C for 5 hours. Then 10.4g of acidic sodium sulfite, 40mg of hydroquinone, 60ml of water,
Add 50ml of isopropyl alcohol,
The mixture was further stirred at 85°C for 6 hours. After the reaction solution became transparent, isopropyl alcohol was distilled out of the system to obtain an aqueous solution of the reaction product. Methanol was added to this aqueous solution to precipitate the reaction product, and the mixture was filtered under suction. The obtained supernatant was recrystallized from ethyl alcohol to obtain a white powder. nuclear magnetic resonance spectrum, infrared absorption spectrum,
From the measurement results of elemental analysis, bromine number, and anionic activator concentration, this product has the following formula: lauryl 2
-Hydroxy-3-allyloxy-1-propyl sulfosuccinate sodium salt was confirmed. as well as Elemental analysis: Calculated value as C ₂₂ H ₃₉ O ₉ SNa C: 52.58% H: 7.82%
S: 6.38% Na: 4.57% Measured value C: 52.62% H: 7.90%
S: 6.31% Na: 4.53% Unsaturated bond: (bromine number) Estimated value 31.8 Measured value 31.5 Anion active concentration: (mmol/g) Estimated value 1.88 Measured value 1.92 ¹ HNMR (D ₂ O) δ: Internal standard TMS 0.88 (3H, t, J = 7Hz) CH ₃ - (alkyl group) 1.1 - 1.5 (20H, m) -CH ₂ - (alkyl group) 3.20 (2H, d, J = 7.5Hz)

【formula】 3.5~3.6 (3H)

[Formula] (Glycerin residue) 3.9-4.3 (7H) -O-CH ₂ -, -O-CH ₂ -, -
O- _CH2 -C=,

[Formula] 5.0-5.5 (2H, m) = CH ₂ (allyl group) 5.6-6.3 (1H, m) -CH = (allyl group) IR: (KBr method) CH ₂ = CH-CH ₂ -: 1670, 1410, 920cm ^-1

[Formula] 1720, 1730 cm ^-1 -SO ₃ Na: 1170, 1190 cm ^-1 -OH: 3450 cm ^-1 Examples 2 to 10 Except for using the alcohol shown in Table 1 instead of lauryl alcohol in Example 1, The synthesis reaction was carried out under the same conditions as in Example 1.

[Table] Each reaction product was precipitated in the same manner as in Example 1, filtered, and purified by recrystallization. The analytical values of the purified product are shown in Table 2.

【table】

[Table] From the analysis results shown above, all the products obtained in Examples 2 to 10 have the same general formula as Example 1. (In the formula, R represents a group corresponding to the raw material alcohol in Table 1.) It was confirmed that it had the structure shown below. Example 11 Instead of allyl glycidyl ether in Example 1, 12.8 g of meta-allyl glycidyl ether was used,
Example 1 except that an aqueous solution of 9.9 g of ammonium bisulfite was used instead of acidic sodium sulfite.
Lauryl 2-hydroxy-3 was treated in the same manner as
-methallyloxy-1-propyl sodium succinate sulfonate was obtained.

[Table] Example 12 Stirrer, thermometer, reflux condenser, nitrogen inlet, 2
Add 130 g of water to a reaction vessel equipped with a dropping funnel.
g, ammonium persulfate 0.35 g, and sodium hydrogen carbonate 0.3 g, and replaced the system with nitrogen gas.
Raise the temperature to 70℃. A mixture of 70 g of butyl acrylate and 30 g of styrene is placed in one dropping funnel. The other dropping funnel is charged with an aqueous solution in which the emulsion polymerization surfactant shown in Table 3 is dissolved in 20 g of water. While stirring the inside of the reaction vessel, the substance in the dropping funnel was dropped over a period of 2 hours. After the addition is complete, the mixture is further stirred at 70°C for 2 hours to obtain an emulsion. The polymerization stability, polymerization conversion rate, mechanical stability, and measured values of surface tension of the obtained emulsion were examined, as well as the water resistance of the substance obtained by removing water from the emulsion. The results are shown in Table 3.

【table】

【table】

Claims (1)

[Claims] 1 The following equations () and (), (In the formula, R ₁ represents an alkyl group, an alkenyl group, an alkylphenyl group, an alkenylphenyl group, or a fatty acid residue, R ₂ represents a hydrogen atom or a methyl group, and A represents an alkylene group having 2 to 3 carbon atoms. ,n
represents a positive number from 0 to 100, and M represents a monovalent cation) A sulfosuccinic acid diester salt which is a mixture of two structural isomers. 2nd order formula () (In the formula, R ₁ represents an alkyl group, an alkenyl group, an alkylphenyl group, an alkenylphenyl group, or a fatty acid residue, R ₂ represents a hydrogen atom or a methyl group, and A represents an alkylene group having 2 to 3 carbon atoms. , n
represents a positive number from 0 to 100) The following formulas () and (), which are characterized by sulfonating a compound represented by _{Production of} sulfosuccinic acid diester salt which is a mixture of two structural isomers represented by Law. 3. The method for producing a sulfosuccinic acid diester salt according to claim 2, wherein the sulfonation reaction is carried out using an acidic sulfite, a metasulfite, or a mixture thereof. 4 The following equations () and (), (In the formula, R ₁ represents an alkyl group, an alkenyl group, an alkylphenyl group, an alkenylphenyl group, or a fatty acid residue, R ₂ represents a hydrogen atom or a methyl group, and A represents an alkylene group having 2 to 3 carbon atoms. , n
represents a positive number from 0 to 100, and M represents a monovalent cation) A reactive surfactant composition containing a sulfosuccinic acid diester salt which is a mixture of two structural isomers represented by