JP2000344805A - Reactive surfactant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel reactive surfactant for emulsion polymerization which can improve the water resistance of synthetic resins and which can be obtained by reacting a glycidyl compound such as an acrylic glycidyl ester or allyl glycidyl ether with a phosphate compound obtained by reacting a polyoxyalkylene alkylcyclohexyl ether with a phosphorylating agent such as phosphoric anhydride. SOLUTION: A reactive surfactant is a phosphate of the formula, an alkali metal salt, an alkaline earth metal salt, an alkanolamine salt or an ammonium salt thereof. In the formula, R is a 6-12C alkyl group; A is an ethylene group and/or a propylene group with the proviso that all the A's cannot be propylene groups; n is an integer of 1-50; q+r+s=3 and q is 1 or 2, r is 1 or 2 and s is 0 or 1; and X is a methacryloyl group, an acryloyl group or an allyl group.

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 alkylbenzene sulfonate, potassium rosinate, and alkyl sulfate, and nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether are generally used. 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 issues, and improvement of the above-mentioned problems has been emphasized in synthetic resin emulsions for paints. So, in order to improve these problems,
Many reactive surfactants having a reactive group copolymerizable with various monomers for obtaining a synthetic resin have been proposed.

[0003]

However, at present, a reactive surfactant which can solve the above problems has not been completed yet. 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 conducted 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 is improved. The inventors have found that a synthetic resin having excellent properties and the like can be obtained, and have reached the present invention. That is, the present invention
The following general formula (1)

Embedded image (However, R is an alkyl group having 6 to 12 carbon atoms, A is an ethylene group and / or a propylene group, provided that there is no propylene group alone, n is an integer of 1 to 50, and q + r + s = 3
And q = 1 or 2, r = 1 or 2, s = 0 or 1, X represents a methacryloyl group, an acryloyl group or an allyl group. ), Or a reactive surfactant which is an alkali metal salt, an alkaline earth metal salt, an alkanolamine salt or an ammonium salt thereof. Since the reactive surfactant according to the present invention has a reactive group such as a methacryloyl group in the molecule, it has excellent copolymerizability with a polymerizable monomer such as an acrylic monomer. Since the surfactant existing in a free state is significantly reduced,
The water resistance of the synthetic resin is improved. Hereinafter, the present invention will be described in detail.

In the general formula (1), the substituent R is an alkyl group having 6 to 12 carbon atoms, for example, a hexyl group,
Examples include a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group. Effectively, an octyl group or nonyl group having 8 or 9 carbon atoms is most preferable.
The-(AO) _n -part in the general formula (1) represents a polyalkylene glycol chain obtained by addition polymerization of ethylene oxide and / or propylene oxide. The polymerization number n is in the range of 1 to 50, and in the case of ethylene oxide alone, n is preferably in the range of 5 to 10,
In the case of copolymerization of ethylene oxide and propylene oxide, it is preferable that n is in the range of 5 to 15 and the ethylene oxide / propylene oxide is copolymerized in a molar ratio of 5/1 to 1/1. Either random or block copolymerization of ethylene oxide and propylene oxide is not effectively changed.

The compound of the general formula (1) according to the present invention is
It can be easily obtained by reacting a phosphoric ester compound obtained by reacting a polyoxyalkylene alkylcyclohexyl ether with a phosphorylating agent such as phosphoric anhydride with a glycidyl compound such as acrylic glycidyl ester or allyl glycidyl ether.

Further, 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 kind 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 effective and economical. % 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 presence of a specific phosphate ester structure and the presence of an alkylcyclohexyl group as a hydrophobic group exerts the desired effect. . Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

[0009]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Synthesis Example of Compound of the Present Invention Synthesis Example (1) In a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, poly (8 mol) oxyethylene nonylhexyl ether 57 was added.
8 g (1 mol) were charged, and a small amount of N ₂ gas was introduced.
After the temperature was raised to 40 ° C, phosphoric anhydride 7
1 g (0.5 mol) was charged over about 15 minutes, and then reacted at the same temperature for 3 hours. Then 9 g (0.5 mol) of water
After the addition, the temperature was raised to 80 ° C., and the reaction was continued for 3 hours.
Furthermore, after cooling to 60 ° C., acrylic glycidyl ester 1
57 g was added dropwise over 2 hours, and the mixture was aged at the same temperature for 4 hours to obtain a compound (1) of the present invention.

Synthesis Examples (2) to (8) According to Synthesis Example (1), compounds (2) to (2) according to the present invention
(8) was obtained. Details are shown in Table 1.

[0011]

[Table 1]

2. Example Example (1) In a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, 430 g of ion-exchanged water and 6 g of the compound (1) of the present invention were charged, and the system was replaced with nitrogen gas. Separately, 150 g of methyl methacrylic acid and 150 g of butyl acrylate
g of ammonium persulfate.
6 g was added to the reaction vessel, and the temperature was raised to 80 ° C. to perform pre-polymerization. 10 minutes after the start of polymerization, the remaining mixed monomer was
The mixture was added dropwise over a period of time, and the mixture was aged for 1 hour to obtain a synthetic resin emulsion. The obtained emulsion was evaluated for the amount of aggregates, foaming property, surface tension, and water resistance of a film prepared from the emulsion. Table 2 shows the results.

Examples (2) to (8) The compounds (2) to (8) of the present invention were prepared in Example (1).
An emulsion was prepared by the same operation as described above, and the same evaluation was performed. The results are shown in Table 2 as Examples (2) to (8).

[0014]

[Table 2]

Description of evaluation method Aggregate amount: The synthetic resin emulsion is filtered through 100 mesh, and the weight of the residue is evaluated in terms of% by weight based on all monomers. Foaming property: The emulsion is diluted twice with water, and a graduated cylinder with a stopper. And shake it for 20 seconds, and measure the amount of foam when left still. Surface tension: measured by Wilhelmy method. Water resistance: A film having a thickness of 0.1 mm was formed on a glass plate, and the time until whitening when immersed in water was evaluated.

Comparative Examples (1) to (3) In the same manner as in Example (1), as an emulsifier, sodium alkylbenzene sulfonate (hard type) [Comparative compound (1)], poly (9 mol) oxyethylene nonyl Phenyl ether [Comparative compound (2)] and poly (50
Mol) nonylphenyl ether [Comparative compound (3)] was used to obtain a synthetic resin emulsion. This emulsion was evaluated in the same manner as in Example 1, and Comparative Example (1)
Table 2 shows the results of (3) to (3).

[0017]

As shown in Table 2, the use of the reactive surfactant according to the present invention in the preparation of a synthetic resin emulsion by the emulsion polymerization method makes it possible to obtain a synthetic resin having extremely excellent water resistance. Can be.

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Claims (1)

[Claims] 1. A compound represented by the following general formula (1): (However, R is an alkyl group having 6 to 12 carbon atoms, A is an ethylene group and / or a propylene group, provided that there is no propylene group alone, n is an integer of 1 to 50, and q + r + s = 3
And q = 1 or 2, r = 1 or 2, s = 0 or 1, X represents a methacryloyl group, an acryloyl group or an allyl group. A) a reactive surfactant which is a phosphoric acid ester or an alkali metal salt, an alkaline earth metal salt, an alkanolamine salt or an ammonium salt thereof represented by