JP2002080506A - Surfactant composition for emulsion polymerization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a surfactant composition for an emulsion polymerization, providing a polymer emulsion having excellent stability during a polymerization and excellent physical properties of a coating film prepared from the formed polymer emulsion. SOLUTION: This surfactant composition for emulsion polymerization comprises at least one kind selected from sulfuric ester salts of formula (I) or formula (II). The method for producing the polymer emulsion comprises carrying out an emulsion polymerization by using the surfactant composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a surfactant composition for emulsion polymerization and a method for producing a polymer emulsion using the same.

[0002]

2. Description of the Related Art Polymer emulsions obtained by emulsion polymerization of vinyl monomers such as vinyl acetate and acrylic acid esters can be directly used in the fields of paints, adhesives, paper processing, textile processing and the like. Alternatively, the polymer is separated and widely used industrially as plastic and rubber. In emulsion polymerization, as an emulsifier,
Anionic surfactants such as alkyl sulfate salts, alkyl benzene sulfonates, polyoxyethylene alkyl ether salts, polyoxyethylene alkyl phenyl ether salts, and polyoxyethylene alkyl ethers;
Nonionic surfactants such as polyoxyethylene alkyl phenyl ether are used.

[0003] Emulsifiers in emulsion polymerization not only affect the initiation reaction and the growth reaction of the polymerization, but also the stability of the polymer emulsion during the polymerization, and the mechanical stability, chemical stability and freezing of the formed polymer emulsion. Influences stability, storage stability, and furthermore, the emulsion physical properties such as the particle size, viscosity, and foamability of the polymer emulsion, and further, when formed into a film, its water resistance, moisture resistance, heat resistance,
It has a significant effect on film properties such as adhesion and tackiness. In applications such as paints and adhesives, a polymer coating is formed by drying a polymer emulsion, but the emulsifier remaining in the polymer coating causes a decrease in water resistance, adhesion, weather resistance, heat resistance, etc. It is known. Further, in the production of synthetic rubber and the like, there is a problem that an emulsifier is contained in waste water when a polymer is taken out from a polymer emulsion by means such as salting out, and the burden of waste water treatment is increased.

[0004] In order to solve such a drawback, a method using a so-called reactive surfactant having an ethylenically unsaturated bond as a polymerizable group in the molecule has been proposed.
For example, JP-A-61-223011 discloses a method using a polyoxyalkylene ether sulfate salt having an allyl or methallyl group as a polymerizable group. Macromolecules, Vol. 32, p. 5967 (1999) discloses sodium oxyalkanesulfonate having a 3-methyl-3-butenyl group as a polymerizable group and 10- (3-methyl-3-butenyloxy) decane-1-. The results of emulsion polymerization using sodium sulfonate are described.

However, when these reactive surfactants are used alone as an emulsifier for emulsion polymerization, the stability during polymerization is often insufficient, and in this case, a conventional emulsifier must be used in combination. There is a problem. In addition, in the case of sodium 10- (3-methyl-3-butenyloxy) decane-1-sulfonate, there is a problem that the production of the sodium salt itself is not easy in terms of the reaction temperature, the yield and the like, and the economic efficiency is poor. is there.

An object of the present invention is to provide a surfactant composition for emulsion polymerization which provides a polymer emulsion having good stability in a polymer emulsion during polymerization, or a polymer coating film formed from the polymer emulsion formed, and has good physical properties. An object of the present invention is to provide a method for producing a polymer emulsion to be used.

[0007]

The present invention relates to a compound of the formula (I)
A surfactant composition for emulsion polymerization containing at least one selected from the sulfate salts represented by (II), and a method for producing a polymer emulsion in which emulsion polymerization is performed using the surfactant composition.

[0008]

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Wherein A is a linear or branched alkylene group having 3 to 18 carbon atoms, or a group represented by the formula (III) or (IV)

[0010]

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(Wherein, R represents a linear or branched alkyl group having 4 to 18 carbon atoms), EO is an oxyethylene group, a is 0 to 50, and b is 0. ２００200, and a and b do not become 0 at the same time.
M represents a cation. Note that a number of-(AO)-groups and b number of-(E
The O)-group may be a block bond or a random bond. In the case of a block bond, the sequence of the-(AO)-group and the-(EO)-group may be any order. The a- (AO)-groups may be the same or different. ]

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the above formula (I) or (II), the linear or branched alkylene group having 3 to 18 carbon atoms represented by A is propylene, ethylethylene, dimethylethylene, butylethylene, Octylethylene, decylethylene, dodecylethylene, tetradecylethylene, hexadecylethylene and the like can be mentioned. Examples of the linear or branched alkyl group having 4 to 18 carbon atoms represented by R in formula (III) or (IV) include butyl, pentyl, hexyl, octyl, 2-ethylhexyl, nonyl, and decyl. Group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and the like. a represents the average number of added moles of the oxyalkylene group or the alkoxymethyloxyethylene group, and is in the range of 0 to 50, preferably 0 to 20, and when no other surfactant is used in combination, the carbon number of A or R And a are particularly preferably numbers satisfying the formula (V).

5 ≦ (carbon number of A or R−2.8) × a ≦ 15 (V) b represents the average number of moles of oxyethylene groups added,
00, preferably in the range of 1 to 50, but a and b are not simultaneously 0. If a and b become 0 at the same time, the chemical stability becomes insufficient. Further, a-(AO)-group and b-(EO)-groups may be a block bond or a random bond.In the case of a block bond, the arrangement of-(AO)-group and-(EO)-group The order may be any. The a- (AO)-groups may be the same or different. Examples of the cation represented by M include alkali metal ions such as sodium and potassium, alkaline earth metal ions such as calcium and magnesium, ammonium ions, and ammonium ions substituted with an alkyl group having 1 to 4 carbon atoms.

The sulfate (I) according to the present invention or
(II) can be produced by a known method, for example, obtained by adding α-olefin epoxide or alkyl glycidyl ether to 3-methyl-3-buten-1-ol in the presence of a catalyst. Ether alcohol is added to the reaction product by adding ethylene oxide according to a conventional method, or after adding ethylene oxide to 3-methyl-3-buten-1-ol, adding α-olefin epoxide or alkyl glycidyl ether. Which is obtained by sulfated with a sulfating agent and neutralized with a basic substance. As the sulfating agent,
Examples include chlorosulfonic acid, sulfuric anhydride, and amidosulfuric acid. When using amidosulfuric acid, neutralization with a basic substance is not always necessary because an ammonium salt has already been formed.

The surfactant composition of the present invention contains at least one of the sulfate salts (I) and (II). From the viewpoint of the physical properties of the polymer coating film produced from the produced polymer emulsion, the sulfate ester salt ( It is preferred to contain I).

In the surfactant composition of the present invention, other anionic surfactants or nonionic surfactants can be used in combination, but the total content of the sulfate salt (I) or (II) can be used. Is preferably 5 to 100% by weight, and 20 to 100% by weight.
% Is more preferred.

The method for producing the polymer emulsion of the present invention is a method of emulsion-polymerizing a vinyl monomer using the surfactant composition according to the present invention. In the emulsion polymerization, the amount of the surfactant composition used is preferably 0.1 to 10% by weight based on the total amount of the vinyl monomer.

The vinyl monomers used in the present invention include aromatic vinyl monomers such as styrene, α-methylstyrene and chlorostyrene; methyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid 2
-(Meth) acrylates such as ethylhexyl;
(Meth) acrylic acid; vinyl halides and vinylidene halides such as vinyl chloride, vinyl bromide and vinylidene chloride; vinyl esters such as vinyl acetate and vinyl propionate; nitriles such as (meth) acrylonitrile; butadiene and isoprene These monomers may be polymerized singly or two or more of them may be copolymerized. The amount of the vinyl monomer to be used is preferably 40 to 60% by weight based on the whole system.

Examples of the initiator used in the emulsion polymerization of the present invention include inorganic peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide, t-butyl peroxide, and the like.
Organic peroxides such as cumene hydroxy peroxide and paramenthane peroxide; azo compounds such as azobisdiisobutylnitrile and 2,2′-azobis (2-amidinopropane) dihydrochloride;
Persulfates such as potassium persulfate and ammonium persulfate are preferred. Further, as a polymerization accelerator, sodium hydrogen sulfite, ferrous ammonium sulfate and the like can be used.

The method of adding the monomer includes a monomer dropping method,
Although a monomer batch charging method or a pre-emulsion method can be used, a pre-emulsion method is preferable from the viewpoint of polymerization stability. The dropping time is preferably 1 to 8 hours, and the aging time is preferably 1 to 5 hours. The polymerization temperature is adjusted depending on the decomposition temperature of the initiator, but in the case of persulfate, it is preferably from 70 to 80C.

[0021]

EXAMPLES The percentages in the examples are percentages by weight unless otherwise specified.

Examples 1 to 12 and Comparative Examples 1 to 3 The sulfates according to the present invention and conventional anionic surfactants produced by the following methods were blended in the proportions shown in Table 1 to produce the present invention. And comparative surfactant compositions were prepared. Using this surfactant composition, emulsion polymerization was carried out by the method shown below, and the performance was evaluated by the method shown below. Table 1 shows the results.

<Production Example of Sulfate Ester Salt> Sulfate ester salt [A-1] In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, and reflux tube, 3-methyl-3-buten-1-ol (Tokyo Kasei ( stock)
397 g (4.6 mol) and 3.11 g (0.0576 mol) of powdered sodium methoxide were charged at 130 ° C. in a nitrogen atmosphere at 130 ° C. with α-olefin epoxide having 12 or 14 carbon atoms (AOE X24, Daicel Chemical Industries, Ltd.). stock)
236.7 g (1.15 mol) was added dropwise over 4 hours and aged at this temperature for 12 hours. The reflux tube was replaced with a distillation tube, and unreacted 3-methyl-3-buten-1-ol was removed under reduced pressure. According to ¹ H-NMR, the average number of moles of α-olefin epoxide added was 1.32.
300 g of the obtained reaction mixture was charged into an autoclave, and 477 g of ethylene oxide was added at 140 ° C. and 0.3 MPa. Next, 87.8 g of a part of the obtained reaction mixture and 12.0 g of amidosulfuric acid were charged into a reaction vessel equipped with a stirrer and a thermometer, and the mixture was heated at 120 ° C.
Sulfation was performed by reacting for 0 minutes, and unreacted amidosulfuric acid was removed by pressure filtration to obtain a sulfate ester salt [A-1] represented by the following formula.

[0024]

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Sulfate ester salt [A-2] 310 g of 3-methyl-3-buten-1-ol (3.6 g) was placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux tube.
Mol), 1.95 g of powdered sodium methoxide (0.
0361 mol) at 130 ° C. under a nitrogen atmosphere.
223.6 g of ethylhexyl glycidyl ether (1.
2 mol) was added dropwise over 2.5 hours, and the mixture was aged at this temperature for 5 hours. The reflux tube was replaced with a distillation tube, and the unreacted 3-
Methyl-3-buten-1-ol was removed. ¹ H-N
According to MR, the average addition mole number of 2-ethylhexyl glycidyl ether was 1.53. 284 g of the obtained reaction mixture was charged into an autoclave,
Under a condition of 0.4 MPa, 438 g of ethylene oxide was added. Next, 88.4 g of a part of the obtained reaction mixture,
12.6 g of amidosulfuric acid was charged into a reaction vessel equipped with a stirrer and a thermometer, and reacted at 120 ° C. for 90 minutes in a nitrogen atmosphere to perform sulfation. The following sulfate salt [A-2] was obtained.

[0026]

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Sulfate ester salt [A-3] 1801 g of 3-methyl-3-buten-1-ol (2.10 g) was placed in a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux tube.
1 mol), 3.40 g of powdered sodium methoxide
(0.0629 mol) at 140 ° C. under a nitrogen atmosphere
Then, 273.4 g (2.1 mol) of butyl glycidyl ether was added dropwise over 2 hours, and the mixture was aged at this temperature for 7 hours. The reflux tube was replaced with a distillation tube, and unreacted 3-methyl-3-buten-1-ol was removed under reduced pressure. ¹ H-NMR
According to this, the average number of moles of butyl glycidyl ether added was 1.72. 368 g of the obtained reaction mixture was charged into an autoclave, and 558 g of ethylene oxide was added at 140 ° C. and 0.4 MPa. Next, 82.9 g of a part of the obtained reaction mixture, 11.4 amidosulfuric acid,
g in a reaction vessel equipped with a stirrer and a thermometer, and reacted under a nitrogen atmosphere at 120 ° C. for 90 minutes to perform sulfation. Unreacted amidosulfuric acid was removed by pressure filtration, and sulfuric acid represented by the following formula was obtained. An ester salt [A-3] was obtained.

[0028]

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Sulfate salt [A-4] In an autoclave, 390 g (4.5 mol) of 3-methyl-3-buten-1-ol and 7.58 g (0.135 g) of KOH were added.
1 mol) was added, 1621 g (22.5 mol) of 1,2-epoxybutane was added at 145 ° C. and 0.3 MPa, and then 1985 g (45 mol) of ethylene oxide at 150 ° C. and 0.3 MPa. Was added. Next, 261 g of a part of the obtained reaction mixture,
4.7 g was charged into a reaction vessel equipped with a stirrer and a thermometer,
Sulfation was performed by reacting at 120 ° C. for 90 minutes in a nitrogen atmosphere, and unreacted amidosulfuric acid was removed by pressure filtration to obtain a sulfate ester salt [A-4] represented by the following formula.

[0030]

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Sulfate [A-5] 3 in autoclave
-Methyl-2-buten-1-ol (Tokyo Chemical Co., Ltd.)
310 g (3.6 mol), 7.26 g (0.134 mol) of sodium methoxide powder, and 130 g
1,2-epoxybutane 12 at 0.3 ° C. and 0.3 MPa.
98 g (18 mol) were added, followed by 1586 g (36 mol) of ethylene oxide. Next, 84.7 g of a part of the obtained reaction mixture and 9.60 g of amidosulfuric acid were charged into a reaction vessel equipped with a stirrer and a thermometer, and reacted at 120 ° C. for 90 minutes in a nitrogen atmosphere to perform sulfation. Amidosulfuric acid in the reaction was removed by pressure filtration to obtain a sulfate ester salt [A-5] represented by the following formula.

[0032]

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Sulfate [A-6] 3 in autoclave
-Methyl-3-buten-1-ol 301 g (3.49
Mol), powdered sodium methoxide 11.3 g (0.
209 mol), and 2030 g (34.9 mol) of propylene oxide were added at 130 ° C. and 0.3 MPa, followed by 1537 g of ethylene oxide (34.34 mol).
9 mol) was added. Next, 81.1 g of a part of the obtained reaction mixture and 8.42 g of amidosulfuric acid were charged into a reaction vessel equipped with a stirrer and a thermometer, and the mixture was heated at 120 ° C. under nitrogen atmosphere at 90 ° C.
The reaction is carried out for 2 minutes to perform sulfation, and unreacted amidosulfuric acid is removed by filtration under pressure, and a sulfate ester salt represented by the following formula is obtained.
[A-6] was obtained.

[0034]

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Sulfate salt [A-7] An autoclave was charged with 340 g (3.95 mol) of 3-methyl-3-buten-1-ol and 6.40 g (0.118 mol) of powdered sodium methoxide. ,
1740 g of ethylene oxide under the condition of 0.3 MPa
(39.5 mol) was added. Next, 100 g of a part of the obtained reaction mixture and 19.9 g of amidosulfuric acid were charged into a reaction vessel equipped with a stirrer and a thermometer, and were heated at 120 ° C. under a nitrogen atmosphere.
For 90 minutes to perform sulfation, and unreacted amidosulfuric acid was removed by filtration under pressure to obtain a sulfate ester salt [A-7] represented by the following formula.

[0036]

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Sulfate ester [A-8] Sulfate ester salt [A-8] was placed in a reaction vessel equipped with a stirrer and a thermometer.
7] g (0.15 mol) of a 10-mol ethylene oxide adduct of 3-methyl-3-buten-1-ol obtained by the method shown in Production Example 7), and 0.243 g (0%) of powdered sodium methoxide. .0045 mol), and 24.7 g (0.12 mol) of α-olefin epoxide having 12 or 14 carbon atoms (AOE X24, manufactured by Daicel Chemical Industries, Ltd.) was added dropwise at 140 ° C. in a nitrogen atmosphere over 1 hour. The mixture was aged at this temperature for 4 hours. Next, 14.18 g of amidosulfuric acid was added, and the mixture was reacted at 120 ° C. for 90 minutes in a nitrogen atmosphere to perform sulfation, and unreacted amidosulfuric acid was removed by filtration under pressure.
[A-8] was obtained.

[0038]

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<Emulsion polymerization method> 5.5 g of a surfactant composition and 0.28 g of potassium persulfate were dissolved in 117.8 g of ion-exchanged water weighed in a beaker, and 2.8 g of acrylic acid was dissolved.
136.1 g of butyl acrylate and 136.1 g of methyl methacrylate were added, and the mixture was 5,000 r / min with a homomixer.
The mixture was emulsified for 10 minutes to obtain a monomer emulsion. 137.9 g of ion-exchanged water, 0.25 g of potassium persulfate, and 36.2 g of the above-mentioned monomer emulsion were charged into a separable flask, and the mixture was stirred for 15 minutes in a nitrogen stream. Next, while stirring in a nitrogen stream, the temperature of the flask was raised in a water bath until the internal temperature of the flask reached 80 ° C.
g from the dropping funnel over 3 hours, and after aging for 1 hour,
Upon cooling to room temperature, a polymer emulsion was obtained. During the addition and ripening, the temperature in the flask was kept at 80 ± 2 ° C. When the monomer emulsion to be dropped was separated in the dropping funnel, a small stirrer was inserted into the dropping funnel to maintain uniformity.

<Performance Evaluation Method> (1) Polymerization Stability The polymer emulsion was filtered through a 200-mesh stainless steel wire mesh, and aggregates adhered to the reactor walls and stirring blades after polymerization were collected and filtered in the same manner. After washing with water, drying and weighing were performed at 26.6 kPa and 105 ° C. for 2 hours to determine the amount of aggregates. The polymerization stability was expressed in terms of% by weight of the aggregate based on the total amount of the monomers used.

(2) Mechanical stability Polymer emulsion 50 neutralized with 25% aqueous ammonia
g in a Malon stability tester at 10 kgf and 1000 r / min.
Rotate for 2 minutes, the resulting aggregates are filtered through a 200 mesh stainless steel wire mesh, the filtration residue after washing with water 26.6 kPa, 105
C., dried and weighed, and expressed as a percentage by weight based on the polymer.

(3) Average Particle Size The average particle size of the polymer emulsion particles neutralized with 25% aqueous ammonia was measured using a dynamic light scattering particle size analyzer Coulter N4 Plus manufactured by Beckman Coulter, Inc. .

(4) Viscosity Using a B-type viscometer, the viscosity of the polymer emulsion neutralized with 25% aqueous ammonia was measured at a temperature of 25 ° C. and a rotation speed of 12 r / m.
Measured in.

(5) Water resistance of polymer film A polymer emulsion neutralized with 25% aqueous ammonia was applied on a slide glass plate and dried at 60 ° C to prepare a polymer film. It was immersed in ion-exchanged water at 25 ° C. to evaluate the whitening condition according to the following criteria. ◎: no whitening after 1 hour ○: slight whitening after 1 hour 時間: whitening in 10 to 30 minutes ×: whitening immediately

[0045]

[Table 1]

-06

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[0047]

When the surfactant composition of the present invention is used as an emulsifier for emulsion polymerization, polymerization stability and mechanical stability are good, and water resistance when formed into a polymer film is high.
Good polymer emulsion is obtained.

Continued on front page F term (reference) 4D077 AB15 AC01 DC01Y DC02Y DC19Y DC59Y DD29Y DD32Y DD33Y DE01Y DE02Y DE07Y DE29Y 4J002 CH05W CH05X 4J011 KA04 KA06

Claims (2)

[Claims] 1. A surfactant composition for emulsion polymerization comprising at least one selected from sulfate salts represented by the formula (I) or (II). Embedded image [Wherein A is a straight-chain or branched-chain alkylene group having 3 to 18 carbon atoms, or formula (III) or (IV)] (Wherein, R represents a straight-chain or branched-chain alkyl group having 4 to 18 carbon atoms).
EO represents an oxyethylene group, a represents a number of 0 to 50, b represents a number of 0 to 200, and a and b do not become 0 at the same time. M represents a cation. In addition, a-(AO)-group and b-(EO)-group may be a block bond or a random bond.In the case of a block bond, the-(AO)-group and the-(EO)-group The arrangement order may be any. The a- (AO)-groups may be the same or different. ] 2. A method for producing a polymer emulsion, wherein emulsion polymerization is performed using the surfactant composition according to claim 1.