KR102486937B1 - Emulsifier composition for reducing coagulum in the emulsion polymerization - Google Patents

Abstract

The present invention relates to an emulsifier composition used in the production of polymers through emulsion polymerization, and by using an emulsifier in the form of an alkali salt of a fatty acid containing a hydroxyl group or an alkali salt of a branched fatty acid alone or in combination, the coagulum generated during emulsion polymerization An emulsifier composition capable of reducing the production amount can be provided.

Description

Emulsifier composition for reducing coagulum in the emulsion polymerization}

The present invention relates to an emulsifier composition used in the production of polymers through emulsion polymerization, and by using an emulsifier in the form of an alkali salt of a fatty acid containing a hydroxyl group or an alkali salt of a branched fatty acid alone or in combination, the coagulum generated during emulsion polymerization It relates to an emulsifier composition capable of reducing the production amount.

In order to remove the coagulum generated during the production of polymers through emulsion polymerization, the reactor must be cleaned periodically, which causes a problem in that productivity is lowered. In order to solve this problem, polymerization methods for reducing coagulum generated during various polymerization reactions have been introduced.

First, as a polymerization method for reducing coagulum, in the method for producing nitrile rubber (Patent Document 1), in the method for producing nitrile rubber, a sulfonate emulsifier and a bifunctional initiator are added to the monomers constituting the nitrile rubber to obtain a coagulated product. A way to reduce it is suggested. In addition, in the manufacturing method of acrylonitrile butadiene-based latex and the acrylonitrile-butadiene-based copolymer prepared therefrom (Patent Document 2), a method of reducing coagulation using ethylene oxide-based sulfonate as an emulsifier along with an existing emulsifier is proposed. did However, these sulfonate-type emulsifiers have a problem in that a large amount of bubbles are generated in the polymerization process, and there is a problem in that the coagulation efficiency is low in the emulsifier coagulation process after emulsion polymerization.

As another polymerization method for reducing coagulum, the method for producing rubber latex with excellent stability (Patent Document 3) claims to reduce the formation of coagulum by adding a reactive emulsifier to the conjugated diene compound monomer and performing emulsion polymerization in the manufacture of rubber latex. . In addition, in the method for producing acrylonitrile-butadiene-styrene latex having a high total solid content (Patent Document 4), an aromatic vinyl compound and a vinyl cyan compound are added to polybutadiene rubber latex, and the graft is then emulsion-polymerized under the addition of a reactive emulsifier. A method for reducing the generation of coagulum during polymerization was proposed. However, in the case of using the reactive emulsifier described above in the polymerization process, there are disadvantages in that raw material costs increase due to an increase in the price of the emulsifier and that reactive emulsifiers specialized for each type of polymer must be used.

Therefore, the technical problem to be achieved by the present invention is to reduce the generation of bubbles in the emulsification process, increase the coagulation efficiency in the emulsifier coagulation process, and reduce the amount of coagulum during emulsion polymerization to improve productivity and to provide an emulsifier usable for various polymer emulsion polymerization. is to do

Republic of Korea Patent No. 1471742 Republic of Korea Patent No. 1133965 Korean Registered Patent No. 0409088 Republic of Korea Patent Publication No. 2002-0036556

Accordingly, the inventors of the present invention use an emulsifier in the form of an alkali salt of a fatty acid containing a hydroxyl group (-OH) or an alkali salt of a branched fatty acid alone or in combination to reduce the amount of coagulum produced during emulsion polymerization to improve productivity and to perform emulsion polymerization of various types of polymers. It was found that it can be used for, and the present invention was completed.

Accordingly, an object of the present invention is to provide an emulsifier composition that improves productivity by reducing the amount of coagulum produced during emulsion polymerization.

In addition, another object of the present invention is a latex manufacturing method for reducing coagulated product, comprising the step of preparing latex by adding 0.1 part by weight to 20 parts by weight of the emulsifier to 100 parts by weight of monomers constituting the latex. It is to provide a method for producing latex to do.

As a means for solving the above problems, the present invention provides an emulsifier composition comprising at least one selected from the group consisting of an alkali salt of a fatty acid satisfying the following formula (1) and an alkali salt of a fatty acid satisfying the following formula (2):

[Formula 1]

[Formula 2]

In the above formula, m and n represent integers of 1 to 20, M represents an integer selected from the group consisting of Li, K, Na and NH ₃ , and R represents an alkyl group having 1 to 18 carbon atoms.

As another means for solving the above problems, the present invention is a latex manufacturing method for reducing the coagulated product, by adding 0.1 to 20 parts by weight of the emulsifier to 100 parts by weight of the monomers constituting the latex. It provides a method for producing a latex comprising the step of preparing a.

The emulsifier composition according to the present invention uses an alkali salt of a hydroxyl group (-OH)-containing fatty acid or an alkali salt of a branched fatty acid alone or in combination of two or more emulsifiers to reduce the amount of coagulum generated during emulsion polymerization. can

The present invention relates to an emulsifier composition containing alone or two or more alkali salts of branched fatty acids or alkali salts of fatty acids containing a hydroxyl group (—OH).

Hereinafter, the present invention will be described in more detail.

The present invention provides an emulsifier composition comprising at least one selected from the group consisting of alkali salts of fatty acids satisfying Formula 1 below and alkali salts of fatty acids satisfying Formula 2 below:

[Formula 1]

[Formula 2]

In the above formula, m and n represent integers of 1 to 20, M represents an integer selected from the group consisting of Li, K, Na and NH ₃ , and R represents an alkyl group having 1 to 18 carbon atoms.

In the present invention, the fatty acid is 12-hydroxyl stearic acid, isostearic acid, 11-methyl lauric acid, 12-methyltetradecanoic acid (12 -methyl tetradecanoic acid, 13-methyl myristic acid, 14-methyl hexadecanoic acid and 15-methyl hexadecanoic acid. It may be one or more selected from the group consisting of, but is not limited thereto.

In one embodiment, the composition may include an alkali salt of a fatty acid or an alkali salt of a branched fatty acid containing a hydroxyl group (-OH) alone or in combination of two or more as an emulsifier.

In the present invention, the composition may be included in 0.1 part by weight to 20 parts by weight, for example, 0.1 part by weight to 10 parts by weight, based on 100 parts by weight of the total monomers. By adjusting the content of the composition within the above range during emulsion polymerization, it is possible to provide an emulsifier composition usable for emulsion polymerization of various polymers and reducing generation of coagulum.

In one embodiment, the emulsifier composition may be used for the preparation of Acrylonitrile-Butadien-Styrene (ABS) latex.

The emulsifier composition according to the present invention can efficiently reduce coagulum generated during emulsion polymerization. In one embodiment, the coagulum product according to the following general formula 1 may be produced at 0.001% to 0.05%.

[Formula 1]

In addition to the components described above, the emulsifier composition according to the present invention may further include additives such as a conventional polymerization initiator and a molecular weight regulator.

The polymerization initiator is not particularly limited, but examples include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium persulfate, and hydrogen peroxide; t-butyl hydroperoxide, cumene hydroperoxide, p-mentane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl organic peroxides such as peroxide, 3,5,5-trimethylhexanol peroxide, t-butyl peroxyisobutyrate, and diisopropylbenzene hydroperoxide; nitrogen compounds such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyrate (butylate)methyl.

The molecular weight modifier is for controlling the molecular weight characteristics of the final latex, dodecanethiol, butanethiol, isooctyl-3-mercaptopropionate (IOMP), 2-methyl-5-t-butylthiophenol, carbon tetra Chloride, and/or carbon tetrabromide and the like may be used as the molecular weight modifier.

In addition, the present invention is a latex manufacturing method for reducing the coagulated product, the latex comprising the step of preparing a latex by adding 0.1 part by weight to 20 parts by weight of the emulsifier to 100 parts by weight of the monomers constituting the latex Provides a manufacturing method of.

The production of the latex may be prepared through an emulsion polymerization method, and may be performed at a reaction temperature of 20 to 90 ° C. for a reaction time of 5 to 15 hours.

In the present invention, the emulsifier may be applied in the same manner as the emulsifier composition described above.

In one embodiment, in the method for preparing the latex, the emulsifier and the surfactant may be used alone or in combination of two or more. The surfactant is an anionic surfactant including fatty acid sodium, monoalkyl sulfate, alkyl polyoxyethylene sulfate, alkylbenzene sulfonate, monoalkyl phosphate, polyoxyethylene alkyl ether, fatty acid sorbitan ester, fatty acid diethanolamine, It may be one or more selected from the group consisting of nonionic surfactants including alkyl monoglyceryl ether, but is not limited thereto, and general surfactants may be used.

Advantages and characteristics of the present invention, and methods for achieving them will become clear with reference to experimental examples and manufacturing examples described later in detail. However, the present invention is not limited to the experimental examples and preparation examples disclosed below, and will be implemented in various different forms, only to ensure that the disclosure of the present invention is complete, and that those skilled in the art in the art to which the present invention belongs It is provided to fully inform the person of the scope of the invention.

Example One

100 parts by weight of ion-exchanged water was put into a reactor and the inside was substituted with nitrogen gas. 0.8 parts by weight of a sodium salt of 12-hydroxystearic acid (20% solid content) as an emulsifier and 50 parts by weight of polybutadiene latex having a diameter of 3000A and a gel content of 70% were added thereto, and the temperature of the reactor was raised to 50 ° C. 10 parts by weight of styrene and 5 parts by weight of acrylonitrile as monomers, 0.2 parts by weight of tertiary dodecylmercaptan as a molecular weight regulator, 0.3 parts by weight of dextrose, and 0.12 parts by weight of dibenzoyl peroxide as a polymerization initiator were added, and the temperature was raised to 60°C. A solution obtained by mixing 3 parts by weight of pure water with 0.1 part by weight of 4-sodium pyrophosphate and 0.003 part by weight of ferrous sulfate was put into a reactor, and then the temperature was raised to 70 ° C to obtain 25 parts by weight of styrene monomer, 10 parts by weight of acrylonitrile, and tertiary dodecane. 0.1 part by weight of silmercaptan and 0.21 part by weight of dibenzoyl peroxide were continuously added. The prepared ABS latex was passed through a mesh filter to obtain a coagulum. The obtained coagulum was washed, completely removed from moisture in a 130° C. reduced pressure oven, and weighed.

Example 2

It was carried out in the same manner as in Example 1 except for the emulsifier, and 0.8 parts by weight of potassium salt of 12-hydroxystearic acid (solid content: 20%) was used as the emulsifier.

Example 3

It was carried out in the same manner as in Example 1 except for the emulsifier, and 1.6 parts by weight of sodium salt of isocystearic acid (solid content 10%) was used as the emulsifier.

Example 4

It was carried out in the same manner as in Example 1 except for the emulsifier, and 0.8 parts by weight of sodium salt of 11-methyllauric acid (solid content: 20%) was used as the emulsifier.

Example 5

It was carried out in the same manner as in Example 1 except for the emulsifier, and 0.8 parts by weight of the potassium salt of 12-hydroxystearic acid (20% solid content) and 0.8 parts by weight of the sodium salt of isostearic acid (10% solid content) were used as emulsifiers.

Example 6

It was carried out in the same manner as in Example 1 except for the emulsifier, and as emulsifiers were 0.5 parts by weight of potassium salt of 12-hydroxystearic acid (20% solid content) and 0.3 parts by weight of sodium salt of 11-methyllauric acid (20% solid content). Part, 0.2 parts by weight of potassium salt of stearic acid (solids content: 20%) was used.

comparative example One

It was carried out in the same manner as in Example 1 except for the emulsifier, and 1.6 parts by weight of potassium salt of stearic acid (solid content 10%) was used as the emulsifier.

comparative example 2

It was carried out in the same manner as in Example 1 except for the emulsifier, and 0.8 parts by weight of sodium salt of oleic acid (solid content 20%) was used as the emulsifier.

comparative example 3

It was carried out in the same manner as in Example 1 except for the emulsifier, and 0.8 parts by weight of potassium salt of lauric acid (20% solid content) was used as the emulsifier.

comparative example 4

It was carried out in the same manner as in Example 1 except for the emulsifier, and 0.6 parts by weight of potassium salt of stearic acid (20% solid content) and 0.2 part by weight of sodium salt of oleic acid (20% solid content) were used as emulsifiers.

Experimental example One. coagulum product comparison

The coagulum obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were measured and compared in terms of coagulum production (%) according to the following general formula 1. The results are shown in Table 1 below.

[Formula 1]

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Congeal content (%) 0.01 0.02 0.01 0.02 0.01 0.03 0.15 0.10 0.12 0.09

As a result, as shown in Table 1 above, in the case of Examples 1 to 6, in which alkali salts of fatty acids or alkali salts of branched fatty acids containing a hydroxyl group (-OH) were used alone or in combination, the product content of the coagulum was 0.01 to 0.03%. As, compared to Comparative Examples 1 to 4 used in the form of a fatty acid alkali salt, it was confirmed that it was significantly less.

Claims (8)

An emulsifier composition comprising at least one selected from the group consisting of alkali salts of fatty acids satisfying Formula 1 below and alkali salts of fatty acids satisfying Formula 2 below:
[Formula 1]

[Formula 2]

In the above formula, m and n represent integers of 1 to 20, M represents an integer selected from the group consisting of Li, K, Na and NH ₃ , and R represents an alkyl group having 1 to 18 carbon atoms.
According to claim 1,
The fatty acid is 12-hydroxyl stearic acid, isostearic acid, 11-methyl lauric acid, 12-methyl tetradecanoic acid ), selected from the group consisting of 13-methyl myristic acid, 14-methyl hexadecanoic acid and 15-methyl hexadecanoic acid One or more emulsifier compositions.
According to claim 1,
The composition is an emulsifier composition included in 0.1 part by weight to 20 parts by weight based on 100 parts by weight of the total monomers.
According to claim 1,
The composition is for the preparation of acrylonitrile-butadiene-styrene (Acrylonitrile-Butadiene-Styrene, ABS) latex, emulsifier composition.
According to claim 1,
An emulsifier composition having a coagulum product of 0.001% to 0.05% according to the following general formula 1:
[Formula 1]

.
In the manufacturing method of latex for reducing the coagulation product,
A method for producing latex comprising the step of preparing latex by adding 0.1 to 20 parts by weight of the emulsifier according to claim 1 to 100 parts by weight of the monomers constituting the latex.
According to claim 6,
The step of adding an emulsifier is a step of adding one or more emulsifiers selected from the group consisting of alkali salts of fatty acids satisfying Formula 1 below and alkali salts of fatty acids satisfying Formula 2 below:
[Formula 1]

[Formula 2]

In the above formula, m and n represent integers of 1 to 20, M represents an integer selected from the group consisting of Li, K, Na and NH ₃ , and R represents an alkyl group having 1 to 18 carbon atoms.
According to claim 6,
The step of preparing the latex is an anionic surfactant including fatty acid sodium, monoalkyl sulfate, alkyl polyoxyethylene sulfate, alkylbenzene sulfonate, monoalkyl phosphate; and adding one or more surfactants selected from the group consisting of polyoxyethylene alkyl ethers, fatty acid sorbitan esters, fatty acid diethanolamines, and nonionic surfactants including alkyl monoglyceryl ethers. manufacturing method.