JPS6391130A - Reactive surfactant - Google Patents

Abstract

PURPOSE:To obtain the title reactive surfactant especially useful as the emulsifier for the emulsion polymerization of vinyl compds. by allowing a polyamine compd. having >=2 primary and/or secondary amino groups in the molecule to react with two kinds of specified compds. CONSTITUTION:(a) The polyamine compd. (e.g., polyuethyleneimine) having >=2 primary and/or secondary amino groups in the molecule is allowed to react with (b) the compd. shown by formula I [R is 4-28C hydrocarbons, X is epoxy, carbonyl, (meth)acryloyl, an atomic group having isocyanato, or a halogen atom, and (n) is 0 or 1-30 integer] and the compd. (e.g., vinyl ether compds.) shown by formula II [X' is epoxy, carboxyl, (meth)acryloyl, isocyanato, and a halogen atom, and R' is an atomic group having a polymerizable unsaturated group] to obtain the cationic reactive surfactant.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to an emulsifier for emulsifying or dispersing various oily substances, resinous substances, organic or inorganic powders in an aqueous medium;
Regarding reactive surfactants that can be used as surfactants such as dispersants, and are particularly useful as emulsifiers for emulsion polymerization of vinyl compounds, etc., more specifically, they contain polymerizable unsaturated groups and primary and The present invention relates to a novel reactive surfactant having at least two different reactive groups with/or a second group amino group.

(Prior Art and Problems to be Solved by the Present Invention) Various types of cationic surfactants have been synthesized heretofore. Compounds that have a hydrophobic group and a hydrophilic group in their molecules and have been proposed as cationic surfactants include compounds obtained by reacting polyethyleneimine with α-olefin epoxide, dodecyltrimethylammonium chloride, and stearyltrimethylammonium chloride. Examples include quaternary ammonium salts such as delammonium chloride.

However, when a vinyl compound is emulsion polymerized using these cationic surfactants as an emulsifier, the film obtained by scattering water from the emulsion polymer is a vinyl polymer produced by a polymerization reaction with the surfactant used as an emulsifier. Because it has a low affinity with other components and undergoes microphase separation, it absorbs a large amount of water and causes whitening when immersed in water.

The purpose of the present invention is to develop a novel reactive surfactant that eliminates the above-mentioned drawbacks of conventional cationic surfactants and can significantly improve the water resistance of a film obtained by scattering water from an emulsion polymer. Our goal is to provide the following.

(Means and effects for solving the problem) The present inventors have developed a polyamine compound having two or more primary and/or second group amino groups in the molecule and a polymerizable compound having a hydrophobic group. A new reactive surfactant obtained by reacting a compound with an unsaturated group exhibits excellent surfactant ability,
Moreover, when the reactive surfactant is used during emulsion polymerization, the polymerizable unsaturated group contained in the reactive surfactant reacts with the polymer produced by emulsion polymerization, and in addition, The present invention was achieved by discovering that by blending an epoxy compound, the primary and/or second group amino groups contained in the reactive surfactant can react efficiently with the epoxy group.

That is, the present invention provides a polyamine compound (A) having primary and/or secondary amino groups in the molecule, which has the general formula % (wherein R represents a hydrocarbon group having 4 to 28 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, X represents an atomic group having an epoxy group, a carboxyl group, a (meth)acryloyl group or an isocyanate group, or a halogen atom,
n represents O or an integer of 1 to 30. ) and the general formula (wherein X- represents an epoxy group, carboxyl group, (meth)acryloyl group, isocyanate group or halogen atom, and R' represents an atomic group having a polymerizable unsaturated group) show.)
The present invention relates to a reactive surfactant obtained by reacting a compound (C) represented by:

The polyamine compound (A) having primary and/or secondary amino groups in the molecule used in the present invention (hereinafter referred to as polyamine compound (A)) has primary and/or secondary amino groups in the molecule. Amines having two or more amino groups or derivatives thereof, such as polyalkyleneimines obtained by polymerization or copolymerization of alkyleneimines such as polyethyleneimine obtained by polymerization of ethyleneimine; ethylenediamine, diethylenetriamine, triethylenetetramine, (Poly)alkylene polyamines such as tetraethylenepentamine and pentaethylenehexamine; polyamide polyamines obtained by condensation of polyalkylene imines and/or (poly)alkylene polyamines with polybasic acids such as adipic acid; polyalkylene imines and/or Examples include polyurea polyamines obtained by reacting (poly)alkylene polyamines and/or alkylene imines with urea; and polyamide polyester polyamines obtained by copolymerizing alkylene imines with acid anhydrides such as phthalic acid.

In addition, examples of polyamine derivatives include alkylene oxides such as ethylene oxide and propylene oxide, (meth)acrylic esters such as butyl acrylate and methyl methacrylate, and α,β-unsaturated acid amide compounds such as acrylamide, etc. Examples include addition-reacted products. In the present invention, it is preferable to use polyethyleneimine or a derivative thereof as the polyamine compound (A) in order to obtain an excellent surfactant. In addition, considering the solubility in water, the viscosity of the solution, and the surfactant ability of the reactive surfactant obtained, the molecular weight is 500.
It is preferable to use polyethyleneimine having a molecular weight of 0 or less.

Compound (B) (hereinafter referred to as compound (B)) used in the present invention and represented by the general formula % (in the formula, R, A, X and n are the same as above)
In the formula, the hydrocarbon group having 4 to 28 carbon atoms corresponding to R in the formula includes a linear or branched alkyl group having 4 to 28 carbon atoms, (alkyl)aryl group, (alkyl)
Examples include hydrogenated aryl groups and (alkyl)aralkyl groups. As the compound (B), the number of moles of alkylene oxide added, such as ethylene oxide, propylene oxide, and isobutylene oxide, is 1 to 3.
Primary alkyl polyoxy such as 0 n-octyl polyoxyalkylene glycidyl ether, n-nonyl polyoxyalkylene glycidyl ether, lauryl polyoxyalkylene glycidyl ether, stearyl polyoxyalkylene glycidyl ether, 2-ethylhexyl polyoxyalkylene glycidyl ether Alkylene glycidyl ethers; 1 to 30 alkylene oxides added to a mixture of secondary alcohols having 12 to 14 carbon atoms
Secondary alkyl polyoxyalkylenes, such as those obtained by adding 1 to 30 moles of alkylene oxide to a mixture of secondary alcohols having 10 to 12 carbon atoms and further converting them into glycidyl ethers. Glycidyl ethers; alkylphenyls such as octylphenyl polyoxyalkylene glycidyl ether, nonylphenyl polyoxyalkylene glycidyl ether, lauryl phenyl polyoxyalkylene glycidyl ether, stearyl phenyl polyoxyalkylene glycidyl ether, etc., with the number of moles of alkylene oxide added from 1 to 30 Polyoxyalkylene glycidyl ethers; octylcyclopentyl polyoxyalkylene glycidyl ether, octylcyclohexyl polyoxyalkylene glycidyl ether, nonylcyclopentyl polyoxyalkylene glycidyl ether, nonylcyclohexyl polyoxyalkylene glycidyl ether, with an added mole number of alkylene oxide of 1 to 30; Alkyl cycloalkyl polyoxyalkylene glycidyl ethers such as lauryl cyclopentyl polyoxyalkylene glycidyl ether, lauryl cyclohexyl polyoxyalkylene glycidyl ether, stearyl cyclopentyl polyoxyalkylene glycidyl ether, stearyl cyclohexyl polyoxyalkylene glycidyl ether; number of moles of alkylene oxide added Alkylbenzyl polyoxyethylene glycidyl ethers such as ophthylbenzyl polyoxyalkylene glycidyl ether, nonylbenzyl polyoxyalkylene glycidyl ether, laurylbenzyl polyoxyalkylene glycidyl ether, and stearylbenzyl polyoxyalkylene glycidyl ether having 1 to 30: octyl glycidyl Glycidyl ethers of higher alcohols such as ether, lauryl glycidyl ether, stearyl glycidyl ether, 2-edylhexyl glycidyl ether; glycidyl ethers of alkyl phenols such as octylphenyl glycidyl ether, nonylphenyl glycidyl ether, lauryl phenyl glycidyl ether, stearyl phenyl glycidyl ether; Class; octylcyclopendelglycidyl ether,
Octylcyclohexylglycidyl ether, nonylcyclopentylglycidyl ether, nonylcyclohexylglycidyl ether, laurylcyclopentylglycidyl ether, laurylcyclohexylglycidyl ether, stearylcyclopentylglycidyl ether,
Glycidyl ethers of alkylcycloalkanols such as stearylcyclohexylglycidyl ether; glycidyl ethers of alkylbenzyl alcohols such as octylbenzylglycidyl ether, nonylbenzylglycidyl ether, laurylbenzylglycidyl ether, stearylbenzylglycidyl ether: carbon number 12 or 14 α-olefin epoxide, α-olefin epoxide having 16 or 18 carbon atoms, etc.
- Epoxy alkanes; alkyl isocyanates such as octyl isocyanate, decyl isocyanate, and octadecyl isocyanate; alcohols such as octatool, lauryl alcohol, and stearyl alcohol, or alkylene oxide adducts of these alcohols and diisocyanates such as tolylene diisocyanate; Monoisocyanate compounds obtained by the reaction of alcohols such as octatool, lauryl alcohol, stearyl alcohol, or alkylene oxide adducts of these alcohols, with the terminal hydrogen group being substituted with a halogen atom such as chlorine, bromine, or iodine. Halides: Saturated fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid; Unsaturated fatty acids such as oleic acid, linoleic acid, lylunic acid, and eleostearic acid; (meth)
Examples include ac(meth)acrylic acid esters, and one or more selected from these groups can be used. The amount of the compound (B) to be used is not particularly limited, but in order to express sufficient surface activity, the amount of the compound (B) should be 0.01 to 0.9 molecules per active amine hydrogen of the polyamine compound (Δ). Preference is given to using B).

In the compound (C) (hereinafter referred to as compound (C)) represented by the general formula (wherein R' and X' are the same as above) used in the present invention, R' in the formula corresponds to Examples of the polymerizable unsaturated group in the atomic group include (meth)acryloyl group, (meth)allyl group,
Examples of the compound (C) include vinyl groups, 2-chloroethyl (meth)acrylate, (meth)
(Meth)acrylic acid esters that have a group that reacts with an amino group in the molecule, such as glycidyl acrylate and 2-isocyanate ethyl (meth)acrylate; Vinyl ethers having; (meth)allyl chloride,
(meth)allyl bromide, (meth)allyl isothiocyanate, allyl (meth)acrylate, half ester of (meth)allyl alcohol and dicarboxylic acid anhydride such as phthalic anhydride or succinic anhydride, (meth)allyl glycidyl ether (Meth)allyl compounds such as: Styrene derivatives having a group that reacts with an amino group in the molecule such as chloromethylstyrene and α-methylchloromethylstyrene; Groups that react with an amino group in the molecule such as vinyl chloroacetate Vinyl esters of acids having the following can be mentioned, and one or more kinds selected from these groups can be used. In the present invention, it is preferable to use vinyl ethers, (meth)allyl compounds, styrene derivatives, and vinyl esters of acids as the compound (C) in order to obtain a reactive surfactant in good yield. Further, the amount of the compound (C) used is not particularly limited, but it is preferably 0.01 to 0.9 molecules per active amine hydrogen of the polyamine compound (A>).

The reaction conditions for obtaining the reactive surfactant of the present invention are not particularly limited, and for example, the polyamine compound (Δ) and the compound (
It can be synthesized by reacting B) and compound (C) as they are, or diluting them with a solvent if necessary, preferably at room temperature to 200°C, more preferably at 50 to 100°C.

At this time, it is preferable that the solvent used as necessary be capable of dissolving the polyamine compound (A), compound (B) and compound (C), and be inert to them. Further, during the reaction, a catalyst may be freely used to promote the reaction.

The reactive surfactant of the present invention thus obtained can be mixed with an acid to form a salt. It is preferable to use a salt because it improves solubility in water.

Acids that can be blended include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as formic acid, acetic acid and (meth)acrylic acid.

(Effects of the Invention) The reactive surfactant of the present invention is a polyamine compound (A) having primary and/or secondary amino groups in the molecule.
It is obtained by reacting a compound (B) having a hydrophobic group and a compound (C) having a polymerizable unsaturated group. It contains at least two different reactive groups with primary and/or secondary amino groups. Therefore, the reactive surfactant of the present invention is particularly useful as an emulsifier for emulsion polymerization of vinyl compounds, etc., and various emulsions can be stably produced, and emulsions using the reactive surfactant can be used. The resulting film or coating has improved compatibility with polymer particles because the polymerizable unsaturated groups contained in the reactive surfactant adjuvant react with the polymer produced by emulsion polymerization to form a graft. There is.

Therefore, the property of conventionally known cationic emulsifiers, which tends to be localized on the particle fusion surface of the film or coating after film formation, is eliminated, and the emulsifier provides high film strength and excellent water resistance. Furthermore, the reactive surfactant has a first
and/or secondary amino groups, so a compound that is reactive with amino groups, such as an epoxy compound, must be copolymerized or blended in advance during emulsion polymerization, or immediately before film formation. By blending, it is possible to form a crosslinked structure in the film or coating after film formation,
Film strength and water resistance are greatly improved.

In addition, after emulsifying or dispersing various oils, resins, organic or inorganic powders in an aqueous medium using the reactive surfactant, the polymerizable unsaturated group of the reactive surfactant or the amine By forming a crosslinked structure using groups,
It is possible to encapsulate the substance within the capsule of the reactive surfactant. In this way, the reactive surfactant can also be used to encapsulate various substances.

(Example) Examples of the present invention are shown below, but these are given for the purpose of illustration and are not intended to limit the scope of the present invention. Further, in the following, parts and % represent parts by weight and mold %, respectively.

Example 1 Polyethyleneimine (Epomin 5P-006, manufactured by Nippon Shokubai Chemical Co., Ltd.) was added as a polyamine compound to a flask equipped with a stirrer, a reflux condenser, a nitrogen blowing tube, and a thermometer.
Average molecular weight 600) 100 parts, α with 12 and 14 carbon atoms
-Mixture of olefin epoxides (AOE-X24, manufactured by Daicel Chemical Industries, Ltd., average molecular weight 196.3) 65
．． 4 parts of allyl glycidyl ether and 76 parts of allyl glycidyl ether were added thereto and heated to 80° C. with stirring under a nitrogen stream. 4 at the same temperature
Stirring was continued for an hour to complete the reaction. 18 N of reactant
It was confirmed by MR measurement that the reaction was complete and that the allyl group had been introduced. The surface tension (20° C.) of a 0.1% aqueous solution of the reactive surfactant [1] synthesized in this way was 35.1 d V ne / cm. Further, the surface tension of a 0.1% aqueous solution of an amine salt (adjusted to PH = 5.0) by adding acetic acid as an organic acid was 40.7 dyne/cm.

Examples 2 to 4 The same procedure as in Example 1 was carried out except that the type of polyamine compound (A) and the usage ratio of compound (B) and compound (C) were as shown in Table 1. Reactive surfactants [2] to [4] were obtained. Their properties were as shown in Table 1.

Example 5 In a reaction vessel similar to Example 1, 100 parts of polyethyleneimine (Evomin 5P-012, manufactured by Nippon Shokubai Chemical Co., Ltd., average molecular weight 1200), 80 parts of lauryl acrylate, and 74°7 parts of allyl acrylate were added. was heated slowly while stirring under a nitrogen stream, and the temperature rose from room temperature to 80°C in 1 hour.
The temperature rose to

Stirring was continued for 1 hour at the same temperature to complete the reaction. 'HN MR measurement of the reactant revealed that the peak of the allyl group was observed, but the peak of the acryloyl group had completely disappeared, indicating that the reactive surfactant [5
] was confirmed to have been synthesized. The properties of this product are shown in Table 1.
It was as shown.

Example 6 In a reaction vessel similar to Example 1, 100 parts of polyethyleneimine (Epomin 5P-012), 65.4 parts of α-olefin epoxide (AOE-X24), 30.5 parts of chloromethylstyrene, and as a polymerization inhibitor were added. Add 0.015 part of P-methoxyphenol, and add 0.015 part of P-methoxyphenol, and add 8
The temperature was raised to 0°C. Stirring was continued for 30 hours using the same III to complete the reaction. The properties of the obtained reactive surfactant [6] were as shown in Table 1.

Example 7 195.8 parts of pure water, 3 parts of the reactive surfactant [1] obtained in Example 1, and emulsification were placed in a flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser. 1.2 parts of acetic acid was added to improve stability during polymerization, and the mixture was heated to 65° C. while slowly blowing nitrogen gas. 10 parts of a monomer mixture consisting of 55 parts of butyl acrylate and 45 parts of methyl methacrylate were injected therein. followed by 2
．． Polymerization was initiated by injecting 4 parts of a 5% aqueous solution of 2'-azobis(2-amidinopropane) dihydrochloride. Twenty minutes after starting the polymerization, 90 parts of the remaining monomer mixture was added dropwise over 1.5 hours. During the dropwise addition, the temperature was maintained at 65 to 70°C, and after the completion of the dropwise addition, the mixture was stirred at the same temperature for 1 hour to complete the polymerization. An aqueous resin dispersion with good stability during polymerization and a non-volatile content of 35.7% with very few lumps was obtained. The film obtained from this aqueous resin dispersion had high strength and good water resistance, with little whitening in water and virtually no elution.

21 Example 8 The reactive surfactant obtained in Example 6 as an emulsifier [6
] was repeated in the same manner as in Example 7, except that the same amount of the following was used to obtain an aqueous resin dispersion with good stability during polymerization and a non-volatile content of 35.8% with very little lumps. The film obtained from this aqueous resin dispersion had little whitening in water, good water resistance, and excellent strength.

Comparative Example 1 The same operation as in Example 7 was repeated except that the same amount of dodecyltrimethylammonium chloride was used as the emulsifier and acetic acid was not used, and the non-volatile content was reduced to 3.
A 5.7% aqueous resin dispersion was obtained. The film obtained from this has a high water absorption rate.

The bleaching in the water was significant.

Example 9 In Example 7, the first stage polymerization was carried out using 5 parts of butyl acrylate and 5 parts of glycidyl methacrylate as the monomer mixture, and 50 parts of butyl acrylate and methacrylate as the monomer mixture for dropping. The same operation as in Example 7 was repeated except for using 40 parts of methyl acid, and the nonvolatile content was 35.8%.
An aqueous resin dispersion was obtained. The film obtained from this aqueous resin dispersion had a crosslinked structure, showed no whitening in water, had very good water resistance, and had high scratches.

Claims (1)

[Claims] 1. A polyamine compound (A) having two or more primary and/or second group amino groups in the molecule with the general formula R-(OA)-_nX (wherein R is the number of carbon atoms) represents a hydrocarbon group having 4 to 28 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, X represents an atomic group having an epoxy group, a carboxyl group, a (meth)acryloyl group or an isocyanate group, or a halogen atom;
n represents 0 or an integer of 1 to 30. ) and the compound (B) represented by the general formula R'-X' (wherein X' represents an epoxy group, a carboxyl group, a (meth)acryloyl group, an isocyanate group, or a halogen atom, and R' is a polymerizable unsaturated group )
A reactive surfactant obtained by reacting a compound (C) represented by: 2. The reactive surfactant according to claim 1, wherein the polyamine compound (A) having two or more primary and/or second class amino groups in the molecule is polyethyleneimine or a derivative thereof. . 3. The reactive surfactant according to claim 1 or 2, wherein the compound (C) represented by the general formula R'-X' is a vinyl ether compound, an allyl compound, a styrene derivative, or a vinyl ester of an acid. .