JPH06298813A - Production of chloroprene polymer - Google Patents

Abstract

PURPOSE:To produce a chloroprene polymer for a less colorable polychloroprene adhesive. CONSTITUTION:A chloroprene polymer is produced by polymerizing chloroprene or its mixture with a copolymerizable monomer in an alkaline water-base emulsion by using a light-colored rosin acid and/or its salt having a Gardner color number of 4 or lower as the emulsifier and a mixture of diethylhydroxylamine with a phenolic antioxidant as the polymn. stopper.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a chloroprene polymer with little coloring, which is preferably used as an adhesive.

[0002]

2. Description of the Related Art Conventionally, a method for producing a chloroprene polymer is carried out by polymerizing chloroprene alone or a mixture of chloroprene and a monomer copolymerizable with chloroprene in an alkaline aqueous emulsion.

In this case, examples of the emulsifier include anionic emulsifiers such as rosin acid salts, alkyl fatty acid salts and alkylbenzene sulfonates, nonionic emulsifiers such as alkyl polyethylene glycol and polyvinyl alcohol, and cationic emulsifiers such as quaternary ammonium salts. Etc. are used.

Among them, rosinate is known to have good strength during freeze-coagulation and drying after completion of polymerization as compared with other emulsifiers, and to prevent excessive shrinkage and breakage during drying of the film (Chemical Engineering). Progress, 43
(8), 391 (1947).).

For these reasons, it is most common and preferable to use a rosin acid salt as an emulsifier in the production of chloroprene polymer.

Rosin acids are classified into types such as gum rosin, wood rosin, tall oil rosin, and disproportionated rosins obtained by disproportionating them, depending on the production method. In the production of the chloroprene polymer, all rosin acids can be used. However, when any rosin acid is used, the produced polymer is colored from yellow to brown.

Further, in the production of chloroprene polymer, if the polymerization rate is too high, a component insoluble in an organic solvent is produced and the physical properties of the obtained chloroprene polymer are impaired. Generally, a polymerization terminator is added to terminate the polymerization.

As the polymerization terminator for terminating the polymerization, for example, phenothiazine, tetraethylthiuram disulfide and the like are used, but the coloring component contained in them may also color the produced polymer.

[Problems to be Solved by the Invention]

The chloroprene polymer produced by the conventional method as described above has the following problems because it is generally colored by the influence of the coloring component in the rosin acid salt or the polymerization terminator. There is.

For example, a chloroprene polymer is also used as a raw material rubber for a solvent type adhesive, but the coloring of the chloroprene polymer has a great influence on the color tone of an adhesive produced using the same. Adhesives made with colored chloroprene rubber are also colored. When various products are manufactured using such an adhesive, the adhesive is conspicuous because the adhesive is colored, and the appearance of the product is deteriorated.

Under these circumstances, it is desired to lighten the color of the adhesive, and for that reason, it is desired to suppress the coloring in the chloroprene polymer of the raw rubber.

As a result of various studies aimed at solving such problems, the present invention established a method for producing a chloroprene polymer with little coloring.

[Means for Solving the Problems]

That is, according to the present invention, chloroprene alone or a mixture of chloroprene and a monomer copolymerizable with chloroprene is polymerized in an alkaline aqueous emulsion to produce a chloroprene polymer. The method for producing a chloroprene polymer is characterized by using the following lightened rosin acid and / or lightened rosin acid salt. Further, the present invention relates to the above method for producing a chloroprene polymer, characterized in that a mixture of diethylhydroxylamine and a phenolic antioxidant is added as a polymerization terminator to terminate the polymerization.

In the present invention, the use of a light-colored rosin acid and / or a light-colored rosin acid salt as the emulsifier can greatly improve the coloration of the chloroprene polymer. By using a polymerization terminator containing an inhibitor as a component, the effect is further enhanced, and a chloroprene polymer with little coloring can be obtained.

The procedure of the method for producing the chloroprene polymer in the present invention may be the same as the ordinary production method, and the polymerization is carried out by emulsifying chloroprene alone or a mixture of chloroprene and a monomer copolymerizable with chloroprene together with a molecular weight modifier. I do.

The monomer copolymerizable with chloroprene is not particularly limited and, for example, 2,3-dichloro-1,3-
Examples thereof include butadiene, 1-chloro-1,3-butadiene, butadiene, isoprene, styrene, acrylonitrile, acrylic acid and its esters, methacrylic acid and its esters, and if necessary, two or more kinds may be used. Absent.

The molecular weight modifier is not particularly limited as long as it is one generally used in the production of chloroprene polymers. For example, long-chain alkyl mercaptans such as n-dodecyl mercaptan and tert-dodecyl mercaptan,
Known chain transfer agents such as dialkylxanthogen disulfides such as diisopropylxanthogen disulfide and diethylxanthogen disulfide, and iodoform can be used.

As the emulsifier, a lightened rosin acid and / or a lightened rosin acid salt is used. The light-colored rosin acid used here is one in which a normal rosin acid soap is treated by distillation, column chromatography or the like to remove coloring components, and the Gardner color number is 4.0 or less. Further, the light-colored rosin acid salt is a light-colored rosin acid salt, and examples thereof include alkali metal salts, alkaline earth metal salts, and ammonium salts, and sodium salts and potassium salts are preferably used.

The amount of the light-colored rosin acid and / or the light-colored rosin acid salt used is the same as in the case of ordinary rosin acid,
Generally, it is preferable to use about 0.1 to 10 parts by weight in terms of rosin acid per 100 parts by weight of all monomers.

At this time, it is not preferable to use an ordinary rosin acid in combination, because the resulting product is colored, but an emulsifier such as a fatty acid or an alkylbenzene sulfonic acid or a sodium salt of a condensate of naphthalene sulfonic acid and formaldehyde is stabilized. The combined use of agents is possible within a range that does not impair the effects of the present invention.

The polymerization may be carried out in the same manner as the polymerization of a general chloroprene polymer, but the polymerization temperature is preferably in the range of 0 to 55 ° C.

As the polymerization initiator, organic or inorganic peroxides used in the usual emulsion polymerization method of chloroprene, for example, benzoyl peroxide, potassium persulfate, ammonium persulfate and the like are used.

As the polymerization terminator, a commonly used terminator such as phenothiazine or tetraethylthiuram disulfide may be used, but in order to obtain a higher light-coloring effect, a mixture of diethylhydroxylamine and a phenolic antiaging agent is used. Preference is given to using.

Examples of the phenol anti-aging agent used in the present invention include 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-.
Ethylphenol, mono (α-methylbenzyl) phenol, di (α-methylbenzyl) phenol, tri (α
-Methylbenzyl) phenol, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol),
2,2'-methylenebis (4-methyl-6-tert-
Butylphenol), 4,4'-butylidene bis (3-
Methyl-6-tert-butylphenol), 4,4 '
-Thiobis (3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone and the like can be used.

[0025]

The present invention will be described in detail with reference to the following examples.

Example 1 Using a reactor having an internal volume of 10 liters, 4000 g of chloroprene monomer and 10 g of n-dodecyl mercaptan were distilled together with ordinary rosin acid soap to distill low-boiling components and high-boiling components. Lightened rosin acid 12 obtained by removal
g, 3 g of sodium hydroxide and 4800 g of distilled water were emulsified, and polymerization was carried out at 10 ° C. under a nitrogen atmosphere using potassium persulfate as an initiator. When the polymerization rate reached 70%, an emulsion of phenothiazine was added to terminate the polymerization.
Then, unreacted monomers were removed by a conventional steam stripping method, and chloroprene polymer chips were obtained from the obtained latex by a conventional freeze-coagulation drying method. The obtained polymer chips are Z-Σ8 manufactured by Nippon Denshoku Industries Co., Ltd.
The color tone was examined with a 0 colorimetric color difference meter.

Example 2 Diethylhydroxylamine as a polymerization terminator and 4,
Polymerization was performed in the same manner as in Example 1 except that a mixture of 4'-thiobis (3-methyl-6-tert-butylphenol) was used.

Comparative Example A chloroprene polymer was obtained by carrying out the polymerization in the same manner as in Example 1 except that disproportionated rosin (Longis R manufactured by Arakawa Chemical Co., Ltd.) was used as an emulsifier.

Table 1 shows the results of the color tone inspection of the rubber chips synthesized in the above Examples and Comparative Examples.

[0030]

[Table 1]

[0031]

As described above, the method for producing a chloroprene polymer of the present invention makes it possible to produce a chloroprene polymer with much less coloration than the chloroprene polymer produced by the conventional method.

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[Procedure amendment]

[Submission date] May 10, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

As the emulsifier, a lightened rosin acid and / or a lightened rosin acid salt is used. The light-colored rosin acid used here is, for example, an ordinary rosin acid soap treated by distillation, column chromatography, or the like to remove coloring components, and the Gardner color number of 4.0 or less. Further, the light-colored rosin acid salt is a light-colored rosin acid salt, and examples thereof include alkali metal salts, alkaline earth metal salts, and ammonium salts, and sodium salts and potassium salts are preferably used.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

Example 1 Using a reactor having an internal volume of 10 liters, 4000 g of chloroprene monomer and 10 g of n-dodecyl mercaptan were distilled together with ordinary rosin acid soap to distill low-boiling components and high-boiling components. The decolorized rosin acid of Gardner color number 3 obtained by removal was emulsified with 3 g of sodium hydroxide and 4800 g of distilled water, and polymerization was performed at 10 ° C. under a nitrogen atmosphere using potassium persulfate as an initiator. It was When the polymerization rate reached 70%, an emulsion of phenothiazine was added to terminate the polymerization. Then, unreacted monomers were removed by a conventional steam stripping method, and chloroprene polymer chips were obtained from the obtained latex by a conventional freeze-coagulation drying method. The color tone of the obtained polymer chips was inspected with a Z-Σ80 colorimetric color difference meter manufactured by Nippon Denshoku Industries Co., Ltd.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

Comparative Example A chloroprene polymer was obtained by carrying out polymerization in the same manner as in Example 1 except that disproportionated rosin acid having a Gardner color number of 10 (Londis R, manufactured by Arakawa Chemical Co., Ltd.) was used as an emulsifier. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 6, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

Example 1 Using a reactor having an internal volume of 10 liters, 4000 g of chloroprene monomer and 10 g of n-dodecyl mercaptan were distilled together with ordinary rosin acid soap to distill low-boiling components and high-boiling components. Lightened rosin acid 12 obtained by removal
The emulsion was emulsified with 0 g, 3 g of sodium hydroxide and 4800 g of distilled water, and polymerization was performed at 10 ° C. under a nitrogen atmosphere using potassium persulfate as an initiator. When the polymerization rate reached 70%, an emulsion of phenothiazine was added to terminate the polymerization. Then, unreacted monomers were removed by a conventional steam stripping method, and chloroprene polymer chips were obtained from the obtained latex by a conventional freeze-coagulation drying method. The obtained polymer chips are Z manufactured by Nippon Denshoku Industries Co., Ltd.
The color tone was examined with a Σ80 colorimeter.

Claims (2)

[Claims] 1. A chloroprene homopolymer, or a mixture of chloroprene and a mixture of chloroprene and a monomer copolymerizable with chloroprene in an alkaline aqueous emulsion to produce a chloroprene polymer, which is a light-colored product having a Gardner color number of 4 or less as an emulsifier. A method for producing a chloroprene polymer, which comprises using a rosin acid and / or a lightened rosin acid salt. 2. A mixture of diethylhydroxylamine and a phenolic antioxidant is added as a polymerization terminator,
The method for producing a chloroprene polymer according to claim 1, wherein the polymerization is stopped.