JPS6036515A - Manufacture of vinyl chloride resin - Google Patents

Abstract

PURPOSE:To obtain the titled resin with good delustered appearance, by dissolving diallyl phthalate prepolymer in vinyl chloride monomer or its mixture with another monomer copolymerizable with it followed by graft copolymerization. CONSTITUTION:The objective resin can be obtained by dissolving (A) a diallyl phthalate prepolymer (pref. with an average molecular weight 4,000-30,000) in (B) vinyl chloride monomer or its mixture with another monomer copolymerizable with it (e.g., ethylene) (preferably with a weight ratio (A)/(B) of 0.5-20/ 99.5-80 followed by graft copolymerization, pref. in the presence of radical polymerization initiator (e.g., azobisisobutylonitrile) through aqueous suspension process.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel matte vinyl chloride resin by graft copolymerizing a diallyl phthalate polymer with a divinyl chloride monomer.

PVC resin is used for rigid applications such as hard plates, pipes, corrugated sheets, and irregularly shaped products, as well as for films, sheets, Shizu-1 flooring, hoses,
It is widely used for soft products such as footwear, but depending on the purpose of use, molded products with excellent texture and no gloss are produced.7')

Conventionally, various methods have been studied to obtain molded products with excellent matte properties. For example, methods of lowering the resin temperature during molding of ordinary vinyl chloride resin, methods of adding inorganic fillers such as calcium carbonate and colloidal silica, methods of adding resins such as acrylic resins, ethylene-vinyl acetate copolymers, etc. However, as described below, none of these methods yielded a satisfactory matting effect. For example, in the method of lowering the resin temperature during molding, the kneading and melting of the resin is not sufficient. Due to insufficient additive I, the desired mechanical properties of the molded product deteriorated and the surface matteness became uneven. The matting effect was insufficient, and even when a large amount was added, the expected good matting properties were not achieved.

On the other hand, Special Publication No. 35-7590, Special Publication No. 46-13
Copolymers of vinyl chloride monomers, single sialyl maleates, and sialyl fumarate monomers described in Japanese Patent Publication No. 38-1494, etc., and vinyl chloride monomers described in Japanese Patent Publication No. 38-1494. The copolymer of sialyl phthalate and sialyl phthalate monomer is a copolymer of monosoft vinyl chloride and a copolymerizable sialyl ester monomer, and can have a branched structure or a branched structure depending on the sialyl ester monomer concentration and polymerization conditions. It produces a framework structure that is insoluble in solvents, and the molded product has a somewhat better surface matte property than vinyl chloride homopolymer.

However, although copolymers with these sialyl ester monomers have a higher concentration of sialyl ester monomers, the matte properties of the molded products become better, but in order to improve the strength of the molded products, they cannot be used under high temperature conditions. When molded, the matteness of the molded product becomes uneven, impairing its aesthetic appearance, and the amount of solvent insoluble matter increases, resulting in extremely poor molding processability. It was restricted. These phenomena were common not only to sialyl ester monomers but also to monomers such as ethylene glycol dimethacrylate, triallyl trimellitate, and triallyl cyanurate.

Also, JP-A-56-79141, JP-A-57-1
Oligomers having at least two ethylenic double bonds in one molecule that are copolymerizable with vinyl chloride monomers, such as polyethylene glycol methacrylate), 1,2-polybutadiene, etc., and vinyl chloride described in Japanese Patent No. 0636 Copolymerization with monomers not only does not provide good egg oil properties under high-temperature molding conditions, but also produces fish eyes.

It had some drawbacks.

In order to improve the various drawbacks mentioned above, the present inventors have conducted intensive research and found that a sialyl phthalate prepolymer containing aromatic ester bonds in the main chain, which impairs heat resistance,
We have discovered a method for producing a matte vinyl chloride resin by graft copolymerizing vinyl chloride monomers or monomers copolymerizable with vinyl chloride monomers.

That is, in the present invention, after dissolving a zoallyl phthalate polymer vinyl in a mixture of a vinyl chloride monomer and a monomer copolymerizable with the vinyl chloride monomer, a lasocal polymerization initiator is added. This is a method for producing a matte vinyl chloride resin, which is characterized by graft copolymerization.

The present invention will be explained in more detail below.

The units constituting the zoallyl phthalate prepolymer used in the present invention are the same as those of ordinary sialyl heptathalate resin,
At least one monomer selected from sialyl orthophthalate and sialyl isophthalate may be used. In addition, zoallyl chlorendate can also be used in the same manner as sialyl phthalate. The prepolymer manufacturing method is described in Japanese Patent Publication No. 35-1
Well-known methods described in Japanese Patent Publication No. 6035, Japanese Patent Publication No. 38-10344, etc. may be used, and there are no particular limitations. The average molecular weight of the prepolymer is too small, but the high-concentration addition that is characteristic of using a prepolymer and the high-temperature matting properties are slightly inferior. Because the solubility of copolymerized monomers decreases and the polymerization system becomes non-uniform and unstable,
4,000-30. [100 is preferred.

In addition, in the present invention, the vinyl chloride monomer to be graft copolymerized with the sialyl phthalate prepolymer or the mourning group copolymerizable with the vinyl chloride monomer has a 0T ability to copolymerize with the vinyl chloride monomer. The bodies include α-olefins such as ethylene and propylene, vinyl esters such as vinyl acetate and vinyl stearate, methyl vinyl ether,
Vinyl ethers such as lauryl vinyl ether, acrylics such as methyl acrylate and methyl methacrylate)
Q, and esters of methacrylic acid, amides such as methacrylamide and acrylonitrile, nitriles, styrenes such as styrene and α-methylstyrene, and small amounts of polyfunctional monomers such as sialyl phthalate and ethylene glycol dimethacrylate. It contains a small amount of oligo 1- such as polyethylene glycol dimethacrylate and 1,2-polybutadiene, and does not impair the solubility of the sialyl phthalate prepolymer, which is the backbone polymer. There is no problem in using them together if they are available.

The ratio of the phthal(9) sialyl prepolymer to the vinyl chloride monomer or a monomer copolymerizable therewith is preferably 0.5 to 2 U to 99.5 to 80 by electroplating.

The production method of the present invention involves dissolving the sialyl phthalate prepolymer, the above-mentioned vinyl chloride monomer, or a mixture with a copolymerizable monomer such as vinyl chloride monomer, followed by radical polymerization. It is characterized by the action of an initiator, and the polymerization method can be any of bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. Suspension polymerization is preferred because operations such as filtration and filtration are industrially easy. Hereinafter, the aqueous (water-based) (dark weight fK) will be explained in more detail.

As the suspension stabilizer, any substance that is normally used for suspension polymerization of vinyl chloride resin may be used, such as partially saponified polyvinyl alcohol, alkyl cellulose, fatty acid ester of polyethylene glycol, etc.

The method for dissolving the sialyl phthalate prepolymer is not particularly limited, but pure water, suspension stabilizer, sialyl phthalate prepolymer, etc. are charged into a superimposed can, and after degassing, vinyl chloride monomer is charged, 7 [) A good method is to dissolve the sialyl phthalate prepolymer by stirring at a temperature of approximately 1 to 2 hours.

Radical polymerization initiators include oil-soluble azo compounds such as isobutyronidrile, 2-ethylhexyl,
It is added after the sialyl heptatarate prepolymer is dissolved into a copolymerizable monomer such as vinyl chloride monomer or vinyl chloride jF suspension by using a oxidized oxide such as peroxycarbonate.

The addition method may be a pressure equalization method or a nitrogen mesogas injection method using a post-addition tank.

The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention should not be limited by these.

Example 1 In a stainless steel autoclave with an internal volume of 6007, a suspension stabilizer was added with a chlorination degree of 80 molar and an average concentration of 240.
Partially saponified polyvinyl albinol 54 (,!
i'l, average molecular weight 10000. After charging 2.4 (kl?) of sialyl 7-talate prepolymer with an iodine value of 0 and 18 D (kg) of pure water and evacuating it in an autoclave, 57.6 Ckg of vinyl chloride monomer was added.
'& was added and the sialyl phthalate prepolymer was suspended in one bath at 55°C for 2 hours with stirring. As a radical polymerization initiator, C-2-ethylhexyl silver oxyzocarbonate 15 (g)? The mixture was added and combined for about 12 hours at 55°C. Collect unreacted vinyl chloride monomer and make slurry? After dehydration and drying in a conventional manner, the yield was 51.0 (k
g). ≧゛IT− of the obtained vinyl chloride resin
Shown in the price list.

The matte vinyl chloride resin obtained by the production method of the present invention is
For hard molded products such as hard plates, pipes, corrugated sheets, and irregularly shaped products that require a good surface matte property, and for soft molded products such as films, drips, flooring materials, hoses, and high-grade electric wire coatings. You can use it. In particular, it can be preferably used in applications where surface matte properties are desired in coextrusion molded products with resins that require favorable molding conditions at high temperatures.

Examples 2 to 5, Comparative Example 1.2 A sialyl phthalate prepolymer having a predetermined average molecular weight was dissolved in a predetermined time to obtain a salt ffs vinyl resin in the same manner as in Example 1. (The iodine value of sialyl phthalate with an average molecular i specification of 7011 O is 85).

Comparative Example 6 The same procedure as in Example 1 was carried out except that the 1-wave phthalic sialyl prepolymer was not used.

Example 6 Same as in Example 1 except that vinyl chloride weight 56.4 to 9 and vinyl acetate monomer 1.2 (kg) were used instead of vinyl chloride monomer 57.6 (kq). It was fat plum.

Comparison 1+ll 4 The same procedure as in Example 1 was carried out except that sialyl phthalate monomer was used instead of the zoallyl phthalate prepolymer. Comparative Examples 5 to 6 Comparative Example 60 Polymer was added with sialyl phthalate 5×7 (Comparative Example 5), and 10 kl? (Comparative Example 6) Each was blended at the time of compounding.

The vinyl chloride resins obtained in Examples and Comparative Examples were measured as follows.

(11 THF-insoluble content) Weighed 2 (g) of vinyl chloride thread resin, 500 (mi)
THF, (tetrahydrofuran), in a glass beaker.
3 Added together with Ot, 91 and left at room temperature for about 60 hours, filtered through a filter, took out the unbathed portion, air-dried, weighed 11, W (,!91. THF insoluble content (%)
was calculated using the following formula.

THF insoluble matter (%l= -X100 vinyl chloride resin 50 (,91, DOP (C2
~ethylhexyl phthalate) 25 (, V+, barium, zinc fatty acid salt composite stabilizer 1.5t, 91 heavy calcium carbonate 10 (gl carbon black 0.5Fg+
Tri-blend beggar with a surface temperature of 1500 (or 180" (1), rolled into two rolls with a roll gap of 0.3, the powder is wrapped around the rolls in a sheet form and the force is 5.
After kneading for a minute, the mixture was taken out. The surface matteness of the rolled sheet taken out was evaluated by visual observation according to the following criteria.

・Good matting properties---○ ・Slightly uneven matting properties---△0 Glossy---x (2) Roll surface temperature of 150"C The fish eyes remaining per 100 square square surface area of the roll sheet mixed and stretched for about 5 minutes were counted and evaluated based on the following criteria.

・Less than 201 solids---〇020~1000 pieces-111-△01[]More than 00 pieces----x According to the table, zoarylph fururate is 0 and 7) Comparison without adding vrimer Example 3 and Comparative Example 5.6, which is a blend of zoallyl phthalate derepolymer, is 150'01180
'O Both matte properties were poor at 7+;

In addition, Comparative Example 1.2, in which the diallyl phthalate prepolymer had insufficient melt edge, had many fish eyes.

In Example 4, which is a copolymer with sialyl phthalate monomer, a roll sheet could not be formed.

On the other hand, Examples 1 to 6 according to the present invention all have 1
Excellent matting properties at 50°C and 180°C, with few fish eyes.

Patent Applicant Denki Kagaku Kogyo Co., Ltd. Procedural Amendment ■, Indication of Case Patent Application No. 145204 of 1982 Title of Invention Process for Manufacturing Vinyl Chloride Resin 3, Person Making Amendment Relationship to Case Patent Applicant Address [Yurakucho, Chiyoda-ku, Tokyo] No. 4 I Name (329) Denki Kagaku Kogyo Co., Ltd. Column 5 of the detailed description of the invention in the specification, Contents of the amendment■) "Azopiiso" on page 8, line 7 is corrected as ``Abbis Iso-1.''

3) Diallyl 1-phthalate” on page 10, lines 4-5 [
Diallyl phthalate prepolymer” is corrected.

4) Page 10, lines 18-20 [Polymer 5 of Comparative Example 3 (
2.5Fg+ (Comparative Example 5) and 5(gl (Comparative Example 6)) were blended with Hgl and diallyl phthalate prepolymer having an average molecular weight of 7000 at the time of evaluation of matteness and finocia, respectively.'' is corrected.

5) 1-* (Blend■,
Weight part)" is deleted.

6) On page 12, line 5, "rTHF, (tetrahydrofuran)" is corrected to "r'THF (tetrahydrofuran)."

7) Correct "150°" in line 5 of page 12 to "150°C".

8) Add the following sentence after the second line of page 13.

[In addition, in Comparative Example 5.6, the polymer 50 of Comparative Example 3 (
2.5 (g) and 5 (g) of diallyl phthalate prepolymer with an average molecular weight of 7000 and the same formulation as gl.
(g) Blended. ] 9) Correct "Comparative Example, 1.2" on page 13, line 19 to "Comparative Example 1.2."

Claims (3)

[Claims] (1) Vinyl chloride with excellent matte properties, which is characterized by dissolving a sialyl phthalate prepolymer in a monopolymer of vinyl chloride or a mixture of a monopolymerizable monomer with vinyl chloride and then graft copolymerizing the prepolymer. Method for producing resin. (2) The method for producing a vinyl chloride resin with excellent oiliness according to claim 1, wherein the graft copolymerization is aqueous suspension polymerization in the presence of a radical polymerization initiator. (3) The method for producing a vinyl chloride resin with excellent matte properties according to claim 1, wherein the sialyl phthalate prepolymer has an average molecular weight of 400'0 to 30,000.