JPS61215641A - Vinyl chloride polymer composition - Google Patents

Abstract

PURPOSE:To provide a vinyl chloride polymer having improved electrical insulating properties, by adding a maleic anhydride adduct of a diene oligomer to a vinyl chloride polymer. CONSTITUTION:A polymer compsn. is obtd. by adding 10-50,000ppm of a maleic anhydride adduct of a diene oligomer to a vinyl chloride polymer. Examples of the vinyl chloride polymers are homopolymers, copolymers and graft copolymers mainly composed of vinyl chloride. The maleic anhydride adduct of a diene oligomer is obtd. by adding maleic anhydride to a 1,2-type or 1,4-type butadiene oligomer by the ene reaction or a radical addition reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a vinyl chloride polymer composition (hereinafter abbreviated as PVC) having improved electrical insulation properties.

[Conventional technology]

PvC originally has electrical insulating properties, that is, volume resistivity (hereinafter referred to as V
It is a plastic with a large ion (abbreviated as R) and is used as an electrical insulating material, but it contains trace amounts of metal ions and relatively ionization tendency during the purification process of vinyl chloride monomer, which is the raw material for PVO, and the manufacturing and processing processes of PVC. Contains compounds of metals with high
It is said that a decrease in R occurs.

It is extremely difficult to completely avoid the contamination of these metal ions, etc., which requires a great deal of cost and is virtually impossible.

In order to solve this problem, a method has conventionally been proposed in which Pva contains a substance that captures the above-mentioned metal ions and eliminates their conductivity.

For example, methods of adding clay or calcium carbonate are known, but these have the disadvantage of being less effective or deteriorating other properties of the product.

As methods for improving these, JP-A-56-81351 and JP-A-56-141356 disclose a method of adding carboxylic acids, and JP-A-56-159242 and JP-A-57-119944 disclose a method of adding carboxylic acids. discloses a method of adding vinyl ether or a copolymer of styrene and maleic anhydride, JP-A-57-179255 discloses a method of adding xanthan gum, JP-A-59-152942 discloses a method of adding polyvinylpyrrolidone, etc. ing.

[Problem that the invention seeks to solve]

However, when these methods are used, for example, the polymerization rate decreases, the action of the suspension stabilizer is adversely affected, the VR improvement effect varies, and a PVC composition with uniform properties cannot be obtained. There are many points that need improvement.

As a result of intensive research to eliminate these drawbacks, the present inventors have discovered that the VR of a PVC composition can be improved by adding a specific amount of a specific substance, and have completed the present invention.

[Means for solving problems]

That is, in the present invention, a maleic anhydride adduct of a diene oligomer is added to a vinyl chloride polymer in an amount of 10 to 5,000.
The present invention relates to a vinyl chloride-based polymer composition with excellent electrical insulation properties, characterized in that it contains 0 ppm.

[For production]

In the present invention, PVO refers to not only vinyl chloride homopolymer, but also ethylene, propylene, vinyl acetate, vinyl propionate, acrylic acid, acrylic esters, vinyl ethers, and various other known copolymerizable monomers. Including vinyl chloride copolymers and vinyl chloride-based graft copolymers, which are obtained by any of the known polymerization methods such as suspension polymerization, emulsion polymerization, bulk polymerization, and gas phase polymerization. can.

The maleic anhydride adduct of diene oligomer used in the present invention can be obtained, for example, by adding maleic anhydride to a 1.2-type or 1.4-type butadiene oligomer by an ene reaction or a radical addition reaction. .

Further, the molecular weight is not particularly limited in its range, but it is practically preferably about 500 to 5,000, and the acid value is preferably 100 or more.

pv of maleic anhydride adduct of this diene oligomer
The larger the amount added to a, the greater the VR improvement effect, but adding more than 50,000 ppm to PVOK is not practical because it has a large effect on other qualities, and if it is less than 10 ppm, almost no VR improvement effect is observed. I can't do it.

'X'V maleic anhydride adduct of diene oligomer
The timing of adding O may be before, during, during, or after the polymerization of 27G, or during the molding process, but adding it during the polymerization process is better than during the molding process because the same amount adds a larger V.
The effect of improving R can be obtained.

In addition, when adding this maleic anhydride adduct of diene oligomer during polymerization, there are no particular restrictions on the polymerization recipe, and dispersants, emulsifiers, initiators, etc. commonly used in suspension polymerization and emulsion polymerization can be used. I can do that.

For example, dispersants and emulsifiers include protective colloidal compounds such as partially saponified polyvinyl acetate, acrylic acid copolymers, cellulose derivatives, gelatin, starch, esters of higher fatty acids and polyhydric alcohols, polyhydric alcohols, etc. Anionic surfactants such as oxyethylene derivatives, metal salts of higher fatty acids, and metal salts of alkylbenzenesulfonic acids are used.

Benzoyl peroxide is used as a polymerization initiator.

Organic peroxides such as rau tetrayl peroxide, dioctyl peroxydicarbonate, and t-butyl peroxybivalate, azo compounds such as azobisisodimethylvaleronitrile, and persulfur brass salts such as potassium persulfate and ammonium persulfate. used.

Moreover, the polymerization temperature is carried out within the commonly used range of 30 to 80°C.

Furthermore, when molding PVO obtained by adding a maleic anhydride adduct of a diene oligomer during polymerization, or when molding a PVO obtained by adding a maleic anhydride adduct of a diene oligomer during the molding process, , plasticizers, stabilizers according to the usual methods.

Fillers, ultraviolet absorbers, colorants, pigments, lubricants, etc. can be mixed uniformly and molded using an extrusion molding machine, a calendar roll, an injection molding machine, etc.

〔effect〕

As explained above, an excellent vinyl chloride polymer composition can be obtained by the present invention.

〔Example〕

The present invention will be specifically explained below with reference to Examples.
This is not intended to limit the scope of the invention.

[Comparative Example 1] After charging 250 parts of pure water, 25 parts of partially saponified polyvinyl acetate (L), and 5 parts of 2.2'-azobis-2,4 dimethylvaleronitrile αO into a polymerization vessel with an internal volume of 1, the mixture was placed under reduced pressure. Then, 100 parts of vinyl chloride monomer was injected.

Next, the mixture was heated to 57° C. with stirring, and when the pressure inside the polymerization vessel decreased from the pressure in the steady state of the polymerization reaction to 2.9/d, recovery of unreacted monomers was started. The polymerization time at this time was 10 hours.

After collecting the unreacted monomers, the polymerization suspension was taken out from the polymerization vessel, dehydrated and dried, and the weight of the polymerization product was measured, and the polymerization conversion rate was about 85%.

For 100 parts of the product thus obtained, DO
50 parts of P and 5 parts of tribasic lead sulfate were mixed, kneaded for 10 minutes with rolls heated to 150°C, and then pressed for 5 minutes at 170°C to create a sheet with a thickness of about 1.0 mm. When the VB value was measured using a method similar to I-67231C, the values were as shown in Table 1.

[Example 1] 1. Add 250 parts of pure water to the same polymerization vessel as in Comparative Example 1.

Partially saponified polyvinyl acetate a, 25 parts t2.2t-azobis-2,4 dimethylvaleronitrile αos, parts,
Molecular weight 1100. After charging α005 parts of a maleic anhydride adduct of butadiene oligomer with an acid value of 110, 100 parts of vinyl chloride monomer was injected under reduced pressure.

Next, a polymerization reaction and dehydration and drying were performed using the same sandals as in Comparative Example 1. Polymerization conversion rate is approximately 85% in 10 hours of polymerization time.
Met.

When VR was measured using this product in the same manner as in Comparative Example 1, the values shown in Table 1 were obtained, indicating an improvement in VB.

[Comparative Example 2] A polymerization reaction was carried out in the same manner as in Comparative Example 1 except that the amount of maleic anhydride adduct of butadiene oligomer added was reduced to 08 parts (LOO) in the formulation of Example 1.

The polymerization conversion rate was about 85% at a polymerization time of 10 hours. V
The B value was as shown in Table 1, and almost no improvement in VR was observed.

[Example 2] Polymerization reaction was started in the same manner as Comparative Example 1, and 3
After the elapse of time, 3 parts of the maleic anhydride adduct Q, 0 of the butadiene oligomer used in Comparative Example 1 was added as a 5% by weight acetone solution.

Thereafter, a polymerization reaction was carried out in the same manner as in Comparative Example 1. The polymerization conversion rate was about 85% at a polymerization time of 10 hours.

The VB values were as shown in Table 1, and an improvement in VR was observed.

[Example 5] A polymerization reaction was carried out in the same manner as in Comparative Example 1, and immediately before recovering the unreacted monomers, a maleic anhydride adduct (105 parts of the butadiene oligomer used in Comparative Example 1 was added to 5% by weight). Added as an acetone solution.

After collecting unreacted monomers, the polymer suspension was taken out from the polymerization vessel, dehydrated and dried, and VR was measured in the same manner as in Comparative Example 1.

The polymerization conversion rate was about 85% at a polymerization time of 10 hours. V
The B value was as shown in Table 1, and an improvement in VR was observed.

[Example 4] For 100 parts of PVO obtained in Comparative Example 1, DOP5
0 parts, 5 parts of tribasic lead sulfate, and the maleic anhydride adduct of the butadiene oligomer used in Comparative Example 1 were added in the proportions shown in Table 2, mixed well, and heated to 150°C. After kneading for 10 minutes, press at 170°C for 5 minutes to obtain a mixture of about 1. A sheet having a thickness of Qss was prepared, and the VR value of this sheet was measured using a method similar to J.Eng. S-6723. The values shown in Table 2 were obtained, confirming the VR improvement effect.

Table-2

Claims (1)

[Claims] (1) A vinyl chloride polymer composition with excellent electrical insulation properties, which contains 10 to 50,000 ppm of a maleic anhydride adduct of a diene oligomer based on the vinyl chloride polymer.