JP2001002714A - New reactive surfactant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new reactive surfactant which is especially used on emulsion polymerization and is useful for producing synthetic resins having excellent water resistance, by including a specific compound. SOLUTION: This reactive surfactant comprises a compound of the formula [R1 is a 6 to 30C hydrocarbon; R2 is H or methyl; A is ethylene and/or propylene; (a) is 0, 1 to 15; (b) is 1 to 15; (c) is 0, 1 to 20; (m)+(n)=3; (n) is 1 or 2; M is H, an alkyl metal atom, an alkaline earth metal, or the like]. The reactive surfactant is obtained, for example, by reacting a polyoxyalkylene allyl ether with a polyoxyalkylene glycidyl ether, addition-reacting an alkylene oxide to the reaction product, reacting the reaction product with a phosphorylation agent to produce a phosphate ester, and then neutralizing the reaction product. The reactive surfactant is preferably used for the emulsion polymerization of a monomer such as acrylic acid or methyl methacrylate, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reactive surfactant which can provide a synthetic resin having excellent water resistance, particularly when used during emulsion polymerization.

[0002]

2. Description of the Related Art Conventionally, acrylic resins such as polyalkyl methacrylates, styrene resins such as ABS resins, synthetic rubbers, vinyl chloride resins and the like have been produced by a so-called emulsion polymerization method. As the emulsifier to be used, anionic surfactants such as alkyl benzene sulfonate, potassium rosinate, and alkyl sulfate, and nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene alkyl phenyl ether are generally used. I have. However, the synthetic resin obtained from the synthetic resin emulsion produced using the above surfactant as an emulsifier has problems such as poor water resistance and adhesiveness because the surfactant is present in a free state in the formed resin. It is pointed out. In recent years, paints have been shifted from solvent type to emulsion type due to environmental problems and safety problems, and improvement of the above-mentioned problems has been emphasized in synthetic resin emulsions for paints. So, in order to improve these problems,
For example, a number of reactive surfactants having a reactive group copolymerizable with various monomers for obtaining a synthetic resin as disclosed in JP-A-60-78993 have been proposed.

[0003]

However, a reactive surfactant which can solve the above problems has not yet been completed. Therefore, an object of the present invention is to provide a reactive surfactant for producing a synthetic resin having excellent water resistance.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, by using a reactive surfactant having a specific structure as an auxiliary for emulsion polymerization, water resistance and the like are improved. It has been found that a synthetic resin excellent in the above can be obtained, and the present invention has been achieved. That is, the present invention provides the following general formula (1)

Embedded image (However, R ¹ is a hydrocarbon group having 6 to 30 carbon atoms, R ^1
2 is a hydrogen atom or a methyl group, A is an ethylene group and / or a propylene group, a = 0 or an integer of 1 to 15,
b = 1 an integer of 1 to 15, c = 0 or an integer of 1 to 20, m
+ N = 3 and m = 1 or 2, n = 1 or 2,
M is a reactive surfactant containing a compound represented by a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an alkylamine residue or an alkanolamine residue or NH ₄ ). Since the reactive surfactant according to the present invention has a reactive group such as an allyl group in the molecule, it is excellent in copolymerizability with a polymerizable monomer such as an acrylic monomer. When used in emulsion polymerization, the surfactant present in a free state in the emulsion is significantly reduced due to copolymerization with the monomer, so that the water resistance of the synthetic resin is improved. Hereinafter, the present invention will be described in detail.

In the general formula (1) according to the present invention, R ¹ is a hydrocarbon group having 6 to 30 carbon atoms, such as an alkyl group, an alkenyl group, an aryl group and a cycloalkyl group. Examples of the alkyl group include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, tricosyl, pentacosyl, and heptacosyl groups. ~ 18 alkyl groups are preferred.

The alkenyl group includes, for example, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl and the like, with octadecenyl being most preferred.

As the aryl group, for example, phenyl,
Toluyl, xylyl, cumenyl, mesityl, benzyl,
Phenethyl, cinnamyl, benzhydryl, trityl,
Ethylphenyl, propylphenyl, butylphenyl,
There are pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl and the like, and an alkylphenyl group having 8 to 12 carbon atoms is preferred.

Examples of the cycloalkyl group include cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, octylcyclohexyl, nonylcyclohexyl and the like.
Most preferably, it is an octylcyclohexyl or nonylcyclohexyl group.

In the general formula (1), R ² is
Represents a hydrogen atom or a methyl group, and may be either.

The — (AO) _a — and — (AO) _b — parts represent a polyalkylene glycol chain obtained by copolymerizing ethylene oxide and / or propylene oxide, and a is 0 or an integer of 1 to 15. , B is 1
It is an integer of １５15. The — (AO) _c — part represents a polyalkylene glycol chain obtained by copolymerizing ethylene oxide and / or propylene oxide, where c is 0 or an integer of 1 to 20 and does not include propylene oxide alone. From the viewpoint of the effect of the present invention, (a + b + c) is preferably in the range of 5 to 20, and-(AO) _a -,-(AO) _b- and-(A
O) The proportion of moles of ethylene oxide in the entire _c -part is preferably 50 to 100%.

In the general formula (1), M represents a hydrogen atom, an alkali metal atom such as lithium, sodium and potassium, and an alkaline earth metal atom such as magnesium and calcium (where the alkaline earth metal atom is usually divalent). Therefore, 1/2), NH ₄ , ammonium of alkylamine such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine or monoethanolamine, diethanolamine, triethanolamine , An ammonium of an alkanolamine such as methyldiethanolamine and ethyldiethanolamine.

The reaction conditions for obtaining the reactive surfactant of the present invention are not particularly limited. For example, after a polyoxyalkylene allyl ether is reacted with a polyoxyalkylene alkyl glycidyl ether, a known method is used. After addition of the alkylene oxide, the reactive surfactant of the present invention can be easily obtained by phosphorylating with a phosphorylating agent such as phosphoric anhydride and neutralizing with an alkaline substance as necessary.

The monomers applicable to various emulsion polymerizations using the reactive surfactant according to the present invention include:
For example, acrylic monomers such as acrylic acid, methyl acrylate, butyl acrylate, methyl methacrylate, acrylonitrile, acrylamide, aromatic monomers such as styrene, olefin monomers such as ethylene, butadiene, chloroprene, vinyl chloride, and vinylidene chloride. Examples include, but are not limited to, these monomers. As the polymerization initiator, for example, known initiators such as hydrogen peroxide, potassium persulfate, ammonium persulfate, azobisisobutylnitrile and benzoyl peroxide can be used. Redox polymerization may be performed using a reducing substance such as sodium hydrogen sulfite, sodium thiosulfate, and ferrous sulfate. The amount of the reactive surfactant of the present invention varies depending on the type of the monomer, but is usually in the range of 0.1 to 10% by weight based on the total monomers, and 0.3 to 5% by weight. % Is preferred. Further, another anionic or nonionic surfactant may be used in combination.

Thus, by using the reactive surfactant represented by the general formula (1) according to the present invention, a synthetic resin having excellent water resistance can be obtained. Although the mechanism has not been elucidated, it is considered that the specific phosphate ester structure and the hydrophilic group linked to the terminal reactive group exert the desired effect. .

[0015]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Synthesis Examples of Compounds of the Present Invention Synthesis Example 1 After charging 190 g (1 mol) of poly (3 mol) oxyethylene allyl ether in an autoclave and adding a boron trifluoride ethyl ether complex as a catalyst, poly (3 mol) Ethylene dodecyl glycidyl ether 374
g (1 mol) at 90 ± 5 ° C. for 4 hours.
After dropping, the mixture was aged at 90 ° C. for 3 hours. Perform vacuum dehydration,
At a pressure of 2.0 kg / cm ³ and a temperature of 140 ° C., 220 g (5 mol) of ethylene oxide was added to obtain an intermediate (1). Next, 784 g (1 mol) of the intermediate (1) was charged into a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, and heated to 40 ° C. under a small amount of N ₂ gas.
71 g (0.5 mol) of phosphoric anhydride while maintaining 0-60 ° C
Was charged for about 15 minutes, and then reacted at the same temperature for 3 hours. Next, after adding 9 g (0.5 mol) of ion-exchanged water, the mixture was heated to 80 ° C. and aged for 3 hours. Thereafter, the resultant was neutralized with an aqueous ammonia solution to obtain a compound (1) of the present invention.

Synthesis Examples 2 to 17 Compounds (2) to (17) of the present invention were obtained according to Synthesis Example 1. Details are shown in Table 1.

[0017]

[Table 1]

2. Example 1 A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel was charged with 430 g of ion-exchanged water and 6 g of the compound (1) of the present invention, and the system was purged with nitrogen gas. Separately, 150 g of methyl methacrylate and 150 g of butyl acrylate
g of the mixed monomer and 60 g of the mixed monomer and 2 parts of ion-exchanged water.
A solution prepared by dissolving 0.6 g of ammonium persulfate in 0 g was added to the reaction vessel, and the temperature was raised to 80 ° C. to perform pre-polymerization. From 10 minutes after the start of the polymerization, the remaining mixed monomer was added dropwise over 3 hours, and the mixture was aged for 1 hour to obtain a synthetic resin emulsion. About the obtained synthetic resin emulsion, the amount of agglomerates, surface tension, foaming property, and water resistance of a film formed from the emulsion were evaluated. The results are shown in Table 2.

Examples 2 to 17 Emulsions were prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 2.

Comparative Examples A to C In the same manner as in Example 1, as an emulsifier, sodium alkylbenzene sulfonate (hard type) (Comparative Example A), poly (9 mol) oxyethylene nonylphenyl ether sodium phosphate (Comparative Example B), And poly (40 mol) oxyethylene nonyl phenyl ether (Comparative Example C)
A synthetic resin emulsion was obtained. The same evaluation as in Example 1 was performed for this synthetic resin emulsion, and the results are shown in Table 2.

Comparative Example D According to the method disclosed in JP-A-60-78993,
A reactive surfactant was prepared as described below. A reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer was charged with 616 g (1 mol) of poly (9 mol) oxyethylene nonylphenyl ether and heated to 40 ° C. under N ₂ gas introduction.
While maintaining the temperature at 40 to 60 ° C., 71 g (0.5 mol) of phosphoric anhydride was added over about 15 minutes, and then the mixture was reacted at the same temperature for 3 hours. Next, after adding 9 g (0.5 mol) of ion-exchanged water, the temperature was raised to 80 ° C., and the reaction was continued for 3 hours. Furthermore, after cooling to 60 ° C., 117 g of methacrylic glycidyl ester was added dropwise over 2 hours and aged at the same temperature for 4 hours to obtain Comparative Product D. Using Comparative Product D, an emulsion was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are shown in Table 2.

Comparative Example E The same reaction as in Comparative Example D was carried out using poly (2 mol) oxyethylene dodecyl ether instead of poly (9 mol) oxyethylene nonylphenyl ether to obtain Comparative Product E. An emulsion was prepared using Comparative Product E in the same manner as in Example 1, and the same evaluation was performed.
Shown in

[0023]

[Table 2]

Measurement / Evaluation Methods (1) Amount of Aggregate The emulsion was filtered with a 100 mesh nylon cloth, the residue on the nylon cloth was dried at 105 ° C., and the weight of the residue was measured and expressed as a percentage by weight based on all monomers. (2) Surface tension Measured by Wilhelmy method. (3) Foaming property A solution obtained by diluting the emulsion twice with ion-exchanged water is
50 ml was taken in a measuring cylinder having a 00 ml stopper, shaken 20 times, and immediately after standing, 1 minute and 5 minutes later, the amount of foam was measured. (4) Water resistance A 0.1 mm thick film was formed on a glass plate, and the time until whitening when immersed in water was indicated.

[0025]

The effect of the present invention is as shown in Table 2.
When preparing a synthetic resin emulsion by the emulsion polymerization method,
By using the reactive surfactant according to the present invention, it is possible to provide a synthetic resin having remarkably excellent water resistance.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4D077 AB15 BA13 CA03 CA04 CA13 CA15 DB10Z DC08Z DD04X DD32X DD32Z DD33X DD33Z DE02X DE07X DE32X 4J011 KA05 KA06 KB29

Claims (1)

[Claims] 1. A compound of the general formula (1) (However, R ¹ is a hydrocarbon group having 6 to 30 carbon atoms, R ^1
2 is a hydrogen atom or a methyl group, A is an ethylene group and / or a propylene group, a = 0 or an integer of 1 to 15,
b = 1 an integer of 1 to 15, c = 0 or an integer of 1 to 20, m
+ N = 3 and m = 1 or 2, n = 1 or 2,
M is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an alkylamine residue or an alkanolamine residue or NH ₄ ).