JPH10114802A - Production of chloroprene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing a scarecely colored chloroprene polymer suitable as a raw rubber for a solvent-type adhesive. SOLUTION: In producing a chloroprene polymer by subiecting chloroprene alone or its mixture with a monomer copolymerizable therewith to polymn. in an alkaline water-base emulsion, a light-colored rosin acid and/or a light- colored rosin acid salt having a Gardner color number of 4 or lower is used as the emulsifier and the polymn. is stopped by adding a mixture of diethylhydroxylamine and 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 less-colored chloroprene polymer which is suitably used particularly as an adhesive.

[0002]

2. Description of the Related Art Conventionally, a chloroprene polymer has been produced by polymerizing chloroprene alone or a mixture of chloroprene and a monomer copolymerizable with chloroprene in an alkaline aqueous emulsion.

In this case, the emulsifier may be, for example, an anionic emulsifier such as a rosinate, an alkyl fatty acid salt or an alkylbenzene sulfonate; a nonionic emulsifier such as an alkyl polyethylene glycol or polyvinyl alcohol; and a cationic emulsifier such as a quaternary ammonium salt. Etc. are used.

[0004] Among them, rosinate is known to have better strength during freeze-coagulation and drying after completion of polymerization than other emulsifiers, and not to cause excessive shrinkage and breakage when drying a film (Chemical Engineering). Progress, 43
(8), 391 (1947).).

[0005] For these reasons, in the production of chloroprene polymers, it is most common and preferred to use rosinate as an emulsifier.

[0008] Rosin acids are classified into gum rosin, wood rosin, tall oil rosin, and disproportionated rosin obtained by disproportionating them, depending on the production method. In the production of the chloroprene polymer, all rosin acids can be used, but when any rosin acid is used, the produced polymer is colored from yellow to brown.

In the production of a chloroprene polymer, if the polymerization rate is too high, a component insoluble in an organic solvent is generated and the physical properties of the obtained chloroprene polymer are impaired. Generally, the polymerization is terminated by adding a polymerization terminator.

As a polymerization terminator for terminating the polymerization, for example, phenothiazine, tetraethylthiuram disulfide and the like are used, and the coloring component contained therein may also cause the formed polymer to be colored.

[0009]

As described above, the chloroprene polymer produced by the conventional method is generally colored by the influence of the coloring components in the rosinate and the polymerization terminator. Have the following problems.

For example, a chloroprene polymer is used as a raw material rubber for a solvent-based adhesive. However, the coloring of the chloroprene polymer greatly affects the color tone of an adhesive produced using the chloroprene polymer. Adhesives made with colored chloroprene rubber are also colored. When various products are manufactured using such an adhesive, the adhesive layer is conspicuous because the adhesive is colored, and the appearance of the product is deteriorated.

For this reason, it is desired to reduce the color of the adhesive, and for that purpose, it is desired to suppress coloring of the chloroprene polymer as the raw rubber.

As a result of various studies for solving the above problems, the present invention has established a method for producing a chloroprene polymer with less coloring.

[0013]

That is, the present invention provides a method for producing a chloroprene polymer by polymerizing chloroprene alone or a mixture of chloroprene and a monomer copolymerizable with chloroprene in an alkaline aqueous emulsion. Polymerization is performed using a light-colored rosin acid and / or a light-colored rosinate having a Gardner color number of 4 or less as an emulsifier, and a mixture of diethylhydroxylamine and a phenolic antioxidant is added as a polymerization terminator to carry out polymerization. This is a method for producing a stopped chloroprene polymer.

In the present invention, the coloring of the chloroprene polymer is greatly improved only by using the lightened rosin acid and / or the lightened rosinate as the emulsifier. By using a polymerization terminator containing an inhibitor as a component, the effect is further enhanced, and a chloroprene polymer with less coloring can be obtained.

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

The monomer copolymerizable with chloroprene is not particularly limited. For example, 2,3-dichloro-1,3-
Butadiene, 1-chloro-1,3-butadiene, butadiene, isoprene, styrene, acrylonitrile, acrylic acid and its esters, methacrylic acid and its esters, and the like may be used. If necessary, two or more kinds may be used. Absent.

The molecular weight regulator is not particularly limited as long as it is 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 disulfide such as diisopropylxanthogen disulfide and diethylxanthogen disulfide and iodoform can be used.

As the emulsifier, a light-colored rosin acid and / or a light-colored rosinate are used. The light-colored rosin acid used here is one obtained by treating ordinary rosin acid by distillation, column chromatography, or the like to remove coloring components to make the Gardner color number 4.0 or less. Further, the light-colored rosinate is a salt of light-colored rosin acid, and examples thereof include alkali metal salts, alkaline earth metal salts, and ammonium salts.
Sodium salts and potassium salts are preferably used.

The amount of the light-colored rosin acid and / or the light-colored rosinate 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 a usual combination of rosin acid and / or rosin acid salt because the resulting product is colored. However, it is not preferable to use an emulsifier such as a fatty acid salt or an alkylbenzene sulfonate, or a condensation of naphthalenesulfonic acid and formaldehyde. The use of an anionic emulsion stabilizer such as a sodium salt of a product 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 in the polymerization of a general chloroprene polymer, but preferably the polymerization temperature is in the range of 0 to 55 ° C.

As the polymerization initiator, there can be used an organic or inorganic peroxide, such as benzoyl peroxide, potassium persulfate or ammonium persulfate, which is used in a usual emulsion polymerization method of chloroprene.

As the polymerization terminator, a commonly used terminator such as phenothiazine or tetraethylthiuram disulfide may be used. To obtain a higher pale color effect, a mixture of diethylhydroxylamine and a phenolic antioxidant is used. It is preferred to use.

Examples of the phenolic antioxidant used in the present invention include 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-methylphenol.
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'-butylidenebis (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.

As a method for isolating the polymer from the latex after completion of the polymerization, any commonly known method such as a freeze coagulation method, a salting out method, an extruder method and the like may be used. The freeze coagulation method is used.

In the case of using the freeze-coagulation method, the latex is coagulated after reducing the emulsifying power of the rosin acid by lowering the pH of the latex to near neutrality. It is common to use another emulsion stabilizer in combination.

As described above, in order to obtain a polymer by a freeze coagulation method, which is a well-known technique, Japanese Patent Application Laid-Open No. Sho 50-15868.
As described in Japanese Patent Publication No. 6 (1994), it is common to use a sulfate or sulfonate type anionic emulsion stabilizer used in the usual emulsion polymerization of chloroprene. Agents include alkyl sulfonates, alkyl sulfates, sulfonated and sulfated ethers, sulfonated alkyl esters of long chain aliphatic acids,
Alkali metal salts such as sulfonated glycol esters of long chain aliphatic acids, sulfonated N-alkylamides, alkylaryl sulfonates and alkyl sulfosuccinates are used. However, in the present invention, when using them, it is necessary to select and use a light-colored material that does not impair the effects of the present invention.

[0028]

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

Comparative Example 1 Using a reactor having an internal volume of 10 liters, 4,000 g of chloroprene monomer and 10 g of n-dodecylmercaptan were distilled together with ordinary rosin acid to remove low-boiling components and high-boiling components as coloring components. The emulsion was emulsified with 120 g of a light-colored rosin acid having a Gardner color number of 3, 3 g of sodium hydroxide, 16 g of Emal-10 needle (main component: sodium lauryl sulfate, manufactured by Kao Corporation) and 4800 g of distilled water,
Polymerization was carried out at 10 ° C. in a nitrogen atmosphere using potassium persulfate as an initiator. When the degree of polymerization reached 70%, an emulsion of phenothiazine was added to terminate the polymerization. Next, 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 chip was subjected to a color tone test using a Z- # 80 colorimeter manufactured by Nippon Denshoku Industries Co., Ltd.

Example 1 Diethylhydroxylamine and 4,4
Polymerization was carried out in the same manner as in Comparative Example 1 except that a mixture of 4′-thiobis (3-methyl-6-tert-butylphenol) was used.

Comparative Example 2 In place of Emar-10 needle, Nopco 38-C3
Polymerization was carried out in the same manner as in Comparative Example 1 except that 7 g (manufactured by San Nopco) was used.

Comparative Example 3 120 g of disproportionated rosin having a Gardner color number of 4 as an emulsifier
Polymerization was carried out in the same manner as in Comparative Example 1, except that Arakawa Chemical Co., Ltd .: Longis FR was used.

Comparative Example 4 Polymerization was carried out in the same manner as in Comparative Example 1, except that disproportionated rosin having Gardner color number of 10 (manufactured by Arakawa Chemical Co., Ltd .: Ron-Dose R) was used as an emulsifier to obtain a chloroprene polymer.

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

[0035]

[Table 1]

[0036]

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

Claims (1)

[Claims] 1. A 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, and a light color having a Gardner color number of 4 or less is used as an emulsifier. A method for producing a chloroprene polymer, comprising polymerizing using a rosin acid chloride and / or a light-colored rosin acid salt, and terminating the polymerization by adding a mixture of diethylhydroxylamine and a phenolic antioxidant.