JPH07165806A - Emulsifying agent for emulsion polymerization - Google Patents

Abstract

PURPOSE:To obtain an agent which, in polymerization, acts as an emulsifying agent and at the same time serves as a monomer to be incorporated into the polymer. CONSTITUTION:This agent has radical-polymerizable double bond (s) in the molecule and is represented by the formula (wherein A is 2-4C alkylene; R is a 8-24C hydrocarbon radical or acyl; m is 0 to 50; and M<1> and M<2> may be the same or different and are each H, an alkali metal, an alkaline earth metal, ammonium or 1-4C hydroxyalkylammonium).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an emulsifier for emulsion polymerization.

[0002]

2. Description of the Related Art Generally, in emulsion polymerization, anionic surfactants such as alkyl sulfates, alkylbenzene sulfates, polyoxyethylene alkyl ether sulfates, etc., as an emulsifier, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene Nonionic surfactants such as ethylene fatty acid ester and Pluronic type surfactant are used.

The emulsifier for emulsion polymerization is involved not only in the initiation reaction and the formation reaction of the polymerization but also in the mechanical stability, the chemical stability, the freezing stability and the storage stability of the produced emulsion. It is known that the physical properties of the emulsion such as the particle size, viscosity, and foaming property, and the film physical properties such as water resistance when formed into a film, weather resistance, adhesiveness, and heat resistance are greatly affected.

[0004]

However, an emulsion obtained by emulsion polymerization using an ordinary emulsifier has high foaming of the emulsion due to the emulsifier, and when the emulsion is formed into a film, the emulsifier is in a free state. Since it remains in the film, problems such as deterioration of film physical properties such as adhesiveness, water resistance, weather resistance and heat resistance have been pointed out.

Therefore, an object of the present invention is to provide an emulsifier for emulsion polymerization which does not have the above-mentioned drawbacks and acts as an emulsifier during the polymerization and is incorporated into the polymer as a monomer.

[0006]

That is, the present invention has the general formula

[Chemical 2] (In the formula, A is an alkylene group having 2 to 4 carbon atoms,
R is a hydrocarbon group having 8 to 24 carbon atoms or an acyl group, m is a number of 0 to 50, and M ¹ and M ² are hydrogen atoms, alkali metals, alkaline earth metals, ammonium or the number of carbon atoms. 1 to 4 hydroxyalkylammonium, and M ¹ and M ² may be different or the same) and emulsified with a radically polymerizable double bond in the molecule It relates to emulsifiers for polymerization.

[0007]

The emulsifier for emulsion polymerization of the present invention is characterized in that it has a double bond capable of radical polymerization in the molecule and not only acts as an emulsifier during polymerization but also forms a chemical bond with the polymer as a monomer. .

The emulsifying agent for emulsion polymerization of the present invention can be produced, for example, as follows. That is, allyl glycidyl ether and the general formula HO- (AO) _m -R (2) (wherein R is a hydrocarbon group having 8 to 24 carbon atoms or an acyl group, and A is 2 to 4 carbon atoms). Is a alkylene group, m is a number of 0 to 50, preferably 0 to 20), a tertiary amine, a quaternary ammonium salt, a boron trifluoride ether complex salt, zinc borofluoride , Tin tetrachloride,
In the presence of a known catalyst such as alumina chloride, sodium hydroxide, potassium hydroxide, etc., at 50 ° C to 160 ° C for 3 hours-
React for 20 hours until the epoxy group disappears

[Chemical 3] (Wherein A, R and m have the same meanings as described above).

As the hydroxyl compound or acid corresponding to the moiety represented by R in the general formulas (2) and (3), for example, octanol, nonanol, decanol, undecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, Natural or synthetic alcohols such as oleyl alcohol and eicosanol,
Alkylphenols such as octylphenol, nonylphenol, dinonylphenol, and further acids (or acid halogens such as caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, arachidic acid) Compounds, reactive derivatives such as acid anhydrides).

As an example of producing the compound represented by the general formula (1), there is a method in which the compound represented by the general formula (3) is phosphorylated by a known method using phosphorus pentoxide, polyphosphoric acid and the like. .

Preferred as M ₁ and M ₂ in the above formula (1) are alkali metal and ammonium, and more preferred is sodium.

The ethylenically unsaturated monomers which can be emulsion polymerized by using the emulsifier for emulsion polymerization of the present invention include vinyl ester monomers such as vinyl acetate, acrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile and acrylamide. The acrylic monomers, aromatic monomers such as styrene, olefinic monomers such as ethylene, butadiene and chloroprene, and halogen-containing monomers such as vinyl chloride and vinylidene chloride can be used. The examples are not particularly limited, and known crosslinkable monomers can be optionally used to improve the physical properties of the polymer.

When emulsion polymerization is carried out using the emulsifier for emulsion polymerization of the present invention, the reaction temperature is 0 to 100 ° C., and a polymerization initiator and a polymerization regulator can be added and reacted in an inert gas. .

As the polymerization initiator, water-soluble inorganic peroxides such as hydrogen peroxide, potassium persulfate and ammonium persulfate, azo compounds such as azobisisobutyronitrile, organic peroxides such as benzoyl peroxide and peracetic acid. Known initiators can be used, such as sodium bisulfite,
Redox polymerization may be carried out using a reducing substance such as sodium thiosulfate or ferrous sulfate.

The use of the polymerization regulator is optional, but when it is used, known regulators such as mercaptans and halides can be used.

The amount used when emulsion polymerization is carried out using the emulsifier for emulsion polymerization of the present invention can be varied depending on the type of polymer and the composition of the monomer, but is usually 0.1 to 20.
It is in the range of% by weight (based on solid content of resin emulsion). Further, within the scope of the object of the present invention, it is also possible to use ordinary anionic and nonionic surfactants in combination.

[0017]

The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples. Example 1 A 1 liter glass four-necked flask was charged with 440 g of nonylphenol and 4.4 g of NaOH and charged to 105 ± 5.
Dehydration was carried out for 30 minutes at a temperature of 10 ° C. and a reduced pressure of 10 mmHg or less. The pressure was returned to normal pressure with nitrogen, the temperature was cooled to 90 ° C., and 228 g of allyl glycidyl ether was added dropwise using a dropping funnel.
After dropping, the mixture was aged at 90 ± 5 ° C for 5 hours. 200 g of the product obtained in 1. was placed in a 500 ml four-neck glass flask, and 35 g of phosphorus pentoxide was added at 40 ° C. After charging, the mixture was heated to 60 ° C., reacted for 2 hours, and further aged at 80 ° C. for 2 hours. Then, it neutralized with sodium hydroxide aqueous solution and obtained the product as a soda salt.

Example 2 The same reaction as in Example 1 was carried out using dovanol 23 (manufactured by Mitsubishi Petrochemical Co., Ltd., mixed alcohol having 12 and 13 carbon atoms, average molecular weight 195) instead of nonylphenol. 200 g of the product obtained in 1. was placed in a 500 ml glass four-necked flask, and 37 g of phosphorus pentoxide was added at 40 ° C. After the addition, the mixture was heated to 60 ° C., reacted for 2 hours, and further aged at 80 ° C. for 2 hours. Then, it neutralized with sodium hydroxide aqueous solution and obtained the product as a soda salt.

Example 3 A product was obtained in the same manner as in Example 2, except that the aqueous solution was neutralized.

Example 4 A product was obtained in the same manner as in Example 2, except that the aqueous solution of potassium hydroxide was used for neutralization.

Example 5 A product was obtained by the same reaction as in Example 1 except that 30 mol of ethylene oxide adduct of nonylphenol was used in place of nonylphenol.

EXAMPLE 6 Lauric acid 40 was added to a 1 liter glass four-necked flask.
Charge 0 g and NaOH 4.4 g, 105 ± 5 ℃, 10
Dehydration was performed for 30 minutes under a reduced pressure of mmHg or less. The pressure was returned to normal pressure with nitrogen, the temperature was cooled to 90 ° C., and 228 g of allyl glycidyl ether was added dropwise using a dropping funnel. 90 after dropping
It was aged at ± 5 ° C for 5 hours. 200 g of the product obtained in 1. was placed in a 500 ml glass four-necked flask, and 40 g of phosphorus pentoxide was added at 40 ° C. After the addition, the mixture was heated to 60 ° C., reacted for 2 hours, and further aged at 80 ° C. for 2 hours. Then, it neutralized with sodium hydroxide aqueous solution and obtained the product as a soda salt.

Comparative Example 1 Ethylene oxide 40 mol adduct of nonylphenol Comparative Example 2 Sodium alkylbenzene sulfonate

Reference Example 1 (Example of Using Emulsifier for Emulsion Polymerization) Using the compounds obtained in Examples 1 to 6 and the compounds of Comparative Examples 1 to 2, an emulsion polymerization reaction was carried out using ethyl acrylate as a monomer. With respect to the obtained polymer emulsion, the solid content, mechanical stability, foamability and water resistance of the polymer film obtained from the polymer emulsion were measured. The results are shown in Table 1.

Polymerization method 120 g of water was charged into a reaction vessel equipped with a reflux condenser, a stirrer, a dropping funnel and a thermometer, and the system was replaced with nitrogen gas. Separately, emulsifier for emulsion polymerization 4 in 80 g of ethyl acrylate
g was dissolved, and 8.4 g of this was dissolved and potassium persulfate 0.0
8 g and 0.04 g of sodium hydrogen sulfite were added to the reaction vessel, and polymerization was started at 50 ° C. And the remaining monomers
The emulsifier mixture for emulsion polymerization was continuously added dropwise to the reactor over 2 hours, and after completion of the addition, the mixture was aged for 2 hours to obtain an emulsion.

Measurement / Evaluation Method (solid content) About 1 g of emulsion was precisely weighed and dried at 105 ± 5 ° C. for 2 hours, and then the dry weight was measured and expressed in% by weight. (Mechanical stability) 50 g of the emulsion was rotated for 5 minutes under the conditions of 10 kg and 1000 rpm in a Maron stability tester, and the produced agglomerate was filtered through a 100 mesh wire mesh,
The filtration residue was washed with water and then dried at 105 ° C. for 2 hours, and this weight is represented by% by weight based on the solid content. (Effervescent) Dilute the emulsion twice with water, put 20 ml of this diluted emulsion in a 100 ml graduated test tube, and measure the foam height when shaken up and down for 10 seconds to obtain ml.
Display with. (Water resistance of film) Depending on the time required for whitening the 0.2 mm polymer film by the water immersion method, ◎: 1 day or more,
◯: Evaluated on the basis of 1 hour or more and x: less than 1 hour.

[0027]

[Table 1]

Reference Example 2 (Example of Using Emulsifier for Emulsion Polymerization) Using the compounds obtained in Examples 1 to 6 and the compounds of Comparative Examples 1 to 2, styrene and butyl acrylate (weight ratio 1/1).
Was used as a monomer, emulsion polymerization was carried out in the same manner as in Reference Example 1, and the obtained polymer emulsion was measured in the same manner. The results are shown in Table 2.

[0029]

[Table 2]

[0030]

The emulsion prepared by using the emulsifier for emulsion polymerization of the present invention has the adhesive property, water resistance, weather resistance and heat resistance of the polymer film because the emulsifier molecule is chemically bonded to the polymer molecule. Without deteriorating the physical properties of the polymer,
The foaming of the emulsion is also low. Also, the emulsion was flocculated, the polymer was filtered off, the unreacted monomer was evaporated and recovered from the filtrate, and then the chemical oxygen demand (COD) was measured to measure the amount of organic matter, but it was almost zero. ,
It was found that the emulsifying agent for emulsion polymerization used was contained in the polymer and did not require wastewater treatment. Further, as is apparent from the solid content%, the emulsifier for emulsion polymerization of the present invention hardly behaves as a polymerization inhibitor, and hardly lowers the yield of the polymer.

Claims (1)

[Claims] 1. A general formula: (In the formula, A is an alkylene group having 2 to 4 carbon atoms,
R is a hydrocarbon group having 8 to 24 carbon atoms or an acyl group, m is a number of 0 to 50, and M ¹ and M ² are hydrogen atoms, alkali metals, alkaline earth metals, ammonium or the number of carbon atoms. 1 to 4 hydroxyalkylammonium, and M ¹ and M ² may be different or the same) and emulsified with a radically polymerizable double bond in the molecule Emulsifier for polymerization.