JPS60255813A - Production of vinyl chloride resin - Google Patents

Abstract

PURPOSE:To obtain the titled resin excellent in impact resistance, weather resistance, and bending modulus, by graft-copolymerizing vinyl chloride with an acrylic copolymer comprising an alkyl (meth)acrylate having specified properties and a polyfunctional monomer. CONSTITUTION:An acrylic compolymer is prepared by copolymerizing 70- 99wt% alkyl (meth)acrylate which forms a homopolymer of a second-order transition temperature <=-10 deg.C (e.g., ethyl acrylate or lauryl methacryalte) with 30-1wt% polyfunctional monomer (e.g., ethylene glycol diacrylate or divinylbenzene). 99-70pts.wt. vinyl chloride is graft-copolymerized with 1-30pts. wt. obtained acrylic copolymer in the presence of a radical polymerization initiator (e.g., lauroyl peroxide), etc., to obtain the purpose vinyl chloride resin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing salt and vinyl resins, and more particularly, to a method for producing a vinyl salt and a vinyl resin, and more particularly, the present invention relates to a method for producing a vinyl salt and vinyl resin, and more particularly, an alkyl acrylate and/or an alkyl acrylate whose homopolymer has a secondary transition point of 110°C or less. Alternatively, the present invention relates to a method for producing a vinyl chloride resin having excellent impact resistance, weather resistance, and flexural modulus by graft copolymerizing vinyl chloride to a copolymer of alkyl methacrylate and a polyfunctional monomer.

[Conventional technology]

Vinyl chloride resin has excellent physical and mechanical properties, so it has many uses such as hard, semi-hard, and soft. However, when vinyl chloride homopolymer is used for hard materials, it has the disadvantage of poor impact resistance and weather resistance.

As a method to improve these drawbacks, there is a polymer blend of vinyl chloride homopolymer and various elastic bodies. According to this method, impact resistance can be improved, but
It has the disadvantage of reduced weather resistance and flexural modulus.

A vinyl chloride graft copolymer obtained by graft copolymerizing vinyl chloride onto an alkyl acrylate polymer is known (Japanese Patent Publication No. 39-17067), and this vinyl chloride graft copolymer has the impact resistance of a homopolymer. However, the flexural modulus is still insufficient.

As described above, each of the methods known to date has advantages and disadvantages, and therefore their applications are limited to some extent.

[Problem that the invention seeks to solve]

The first object of the present invention is to provide a method for producing a vinyl chloride resin having excellent impact resistance, weather resistance, and flexural modulus.

[Means for solving problems]

In order to achieve the above object, the present inventors have made extensive studies and found that an alkyl and/or alkyl methacrylate having a secondary transition point of a homopolymer of 110°C or less and a polyfunctional heptamer. By graft copolymerizing vinyl chloride to an acrylic copolymer of .

That is, in the present invention, the secondary transition point of the homopolymer is =lO
70-99% of alkyl acrylate and/or alkyl methacrylate and polyfunctional monomer 30%
-1% by weight of acrylic copolymer and 99 to 70 parts by weight of vinyl chloride is graft-copolymerized.It has excellent impact resistance, weather resistance, and flexural modulus. This is a method for producing vinyl chloride resin that has excellent properties.

The acrylic copolymer used in the present invention is a copolymer of alkyl acrylate and/or alkyl methacrylate and a polyfunctional heptamer. For improving impact resistance, it is necessary for the alkyl acrylate and/or alkyl methacrylate to have a secondary transition point of the polymer alone of 110°C or less. For example, ethyl acrylate, low propyl acrylate , in-butyl acrylate-1, n-butyl acrylate, n-hexyl acrylate, 2-ethyl hequinol acrylate, n-octyl acrylate, n-decyl acrylate, n-octyl methane lylate, n-decyl acrylate, n- Examples include 1゛decyl methacrylate and lauryl methacrylate.

The amount of alkyl acrylate and/or alkyl ivy acrylate used is preferably 99 to 70% by weight in the acrylic copolymer; if it is more than 99% by weight, no improvement in the flexural modulus can be expected, and if it is less than 70% by weight, This is undesirable as it reduces impact resistance.

In addition, the polyfunctional monomer is a monomer that can be copolymerized with alkyl acrylate and/or alkyl methacrylate and is present in the copolymer and is involved in crosslinking etc. in the graft copolymer, for example, Ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate-1-11,3-propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate ,
1. Acrylates or methacrylates of (poly)alkylene glycols such as 4-butylene glycol dimethacrylate, diallyl phthalate, diallyl maleate, diallyl phthalate, diarylbenzene, etc.V'
f and pillar center.

The amount of polyfunctional monomer used is preferably 1 to 30% by weight in the acrylic copolymer; if it is less than 1% by weight, no improvement in the flexural modulus can be expected, and if it exceeds 30% by weight, This is not preferred because impact resistance decreases.

The acrylic copolymer of alkyl acrylate and 7/or alkyl methacrylate and a polyfunctional monomer used in the present invention can be prepared using commonly known emulsifiers, dispersants, catalysts, etc. by polymerization methods such as emulsion polymerization, solution polymerization, and bulk polymerization. etc. can be obtained using It is desirable that emulsion polymerization be used for K to advantageously carry out the present invention.

To obtain a copolymer by a general emulsion polymerization method, for example, pure water, an anionic emulsifier, and a water-soluble polymerization catalyst are placed in a jacketed polymerization reactor, the air inside the can is removed, and then the alkyl acrylate is and/or alkyl methacrylate and a polyfunctional monomer are charged, and after emulsification, the inside of the can is filled with salmon.

The copolymerization reaction is carried out by heating. This copolymerization reaction is an exothermic reaction, and the internal temperature is controlled by a jacket as necessary. After the reaction is completed, unreacted heptamers are removed from the can to obtain an acrylic copolymer.

The method of charging into the polymerization reactor is not limited. Further, if necessary, a particle size adjusting agent for the acrylic copolymer, a decomposition promoter for the catalyst, etc. may be added to control the copolymerization reaction.

When used as a backbone polymer for graft copolymerization, the appropriate amount of the acrylic copolymer used is 1 to 30 parts by weight.

If the amount of the acrylic copolymer used is less than 1 part by weight, the impact resistance will not be sufficient, and if it exceeds 30 parts by weight, although the impact resistance will improve, the flexural modulus will decrease, which is not preferable.

Examples of the graft copolymerization method of the present invention include suspension polymerization, emulsion polymerization, solution polymerization, and solvent-free polymerization.
In order to carry out the present invention advantageously, it is desirable to employ a suspension polymerization method.

When carrying out the suspension polymerization method, the amount of water used is 1 to 5 times, preferably 1 to 3 times, the total amount of the acrylic copolymer and vinyl chloride hexamer.

To obtain a graft copolymer resin by a general suspension polymerization method, for example, pure water,
Add a suspension stabilizer such as hydroxypropyl methyl cellulose, a radical polymerization initiator, and if necessary a degree of polymerization reducer, add the acrylic copolymer and suspend it, then remove the air in the can, Next, vinyl chloride is charged together with other vinyl compounds as necessary.Then, the can is heated with a jacket to dissolve the acrylic copolymer in the vinyl chloride and start graft copolymerization. Polymerization is an exothermic reaction, and the internal temperature is controlled by a jacket as necessary. After the reaction, unreacted vinyl chloride is removed from the outside of the can to obtain a slurry of graft copolymer resin. The graft copolymer resin is obtained by dehydration and drying according to the method.The charging method to the polymerization reactor is not limited, but may include pure water, suspension stabilizer, acrylic copolymer, vinyl chloride, etc. Among the raw materials, a method of dissolving an acrylic copolymer in vinyl chloride and charging the same is also adopted.

During graft copolymerization, other monomers may be co-present as long as they do not reduce impact resistance, weather resistance, and flexural modulus (.

In carrying out the present invention, it is advantageous to carry out the graft copolymerization by a radical polymerization method, and the radical polymerization initiators used for this purpose include lauroyl peroxide, tert-butyl peroxy pivalate, diimpropyl peroxy Organic peroxides such as dicarbonate and dioctyl peroxydicarbonate, 2.2'
-Azobisinobutyronitrile, 2.2'-Azobis-
Examples include oil-soluble polymerization initiators such as azo compounds such as 2.4-dimethylvaleronitrile, and water-soluble polymerization initiators such as potassium persulfate and persulfate/ammonium.

The amount of these polymerization initiators used is preferably 0.005 to 1.0 parts by weight per 100 parts by weight of vinyl chloride.

Dispersants include methylcellulose, lurose, ethylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, polyvinyl alcohol and partially saponified products thereof, gelatin, polyvinylpyrrolidone, organic substances such as starch, magnesium carbonate, calcium carbonate, carnow phosphate, etc. These inorganic substances can be used alone or in combination.

The amount used is usually 0.01 to ]O parts by weight per 100 parts by weight of vinyl chloride.

Furthermore, the present invention replaces the chain transfer agent used in the conventional method of polymerizing vinyl monomers with vinyl chloride.
It may be added in an amount of 0001 to 10 parts by weight.

〔Effect of the invention〕

The graft copolymer resin obtained by the method of the present invention is:

Typical heat stabilizers, lubricants, processing aids, antioxidants, and fillers used in the molding process of PVC clothing.

By blending ultraviolet absorbers, pigments, etc., it can be subjected to normal molding processes, and its excellent properties such as impact resistance, weather resistance, and mechanical strength make it suitable for use in lining materials.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples. Note that the parts shown in the Examples are parts by weight.

Examples 1 to 4 Comparative Examples 1 to 7 Deionized water,
An acrylic copolymer having the composition shown in Table 1, a dispersant, and a polymerization initiator were charged, and after removing the air inside with a vacuum pump, vinyl chloride was charged and polymerization was carried out. In addition,
The polymerization recipe, polymerization temperature, time, etc. are shown in Table 1.

Thereafter, after removing vinyl chloride, the contents were filtered and dried to obtain a white powder. The average degree of polymerization of this powder and the amount of components other than vinyl chloride were measured. The results are shown in Table 1.

To 100 parts of the obtained graft copolymer resin, 2 parts of tribasic lead sulfate, 1 part of dibasic lead stearate, and 1 part of lead stearate were added.
5 parts were uniformly mixed, further kneaded for 5 minutes with a heated roll at 180°C, and pressed for 5 minutes at 180°C to make a sheet. Samples taken from this sheet were evaluated for Nyaruby impact strength, weather resistance, and bending properties. The elastic modulus was measured. These results are also shown in Table 1.

Comparative Example 8 Polymerization was carried out in the same manner as in Example 1 except that the acrylic copolymer was not used to obtain a vinyl chloride homopolymer.

To 100 parts of this homopolymer, 15 parts of acrylic impact agent (composition: 75% lobetyl acrylate, 20% methyl acrylate, 5% acrylyl), 2 parts of tribasic lead sulfate, 1 part of dibasic lead stearate. , 1.5 parts of lead stearate were mixed uniformly, a notebook was prepared in the same manner as in Example 1, and the material was measured.

The results are shown in Table 1.

Nyaruby impact strength was measured according to JISK-6745.

The flexural modulus was measured according to JISK-6740.

Weather resistance is determined by Carbon Arc Sun Yain Weatherometer (spray 12/60 minutes, black panel 63°C) K
The samples were irradiated for 200 hours and the discoloration was compared.

The above results show that the graft copolymer resin of the present invention has extremely excellent impact resistance and mechanical strength.

Claims (1)

[Claims] 1. 1 to 30% by weight of an acrylic copolymer consisting of 70 to 99% by weight of alkyl acrylate and/or alkyl methacrylate whose homopolymer has a secondary transition point of 110°C or less and 30 to 1% by weight of a polyfunctional monomer. Part K, a method for producing a vinyl chloride resin, comprising graft copolymerizing 99 to 70 parts by weight of vinyl chloride.