JPS5968360A - Polymer alloy - Google Patents

Abstract

PURPOSE:To provide a polymer alloy having high breaking strengths, well suited for hoses or belts, by reacting carboxylated polyvinyl chloride, carboxylated nitrile rubber, and (hydro)oxides of Group II or III metals. CONSTITUTION:Carboxylated polyvinyl chloride (A) such as vinyl chloride/alpha,beta- unsatd. carboxylic acid copolymers, carboxylated nitrile rubber (B) such as conjugated diene/acrylonitrile/alpha,beta-unsatd. carboxylic acid copolymer, and about 0.5-30pts.wt. based on 100pts.wt. total amt. of components A and B, oxide of Group II or III metal (e.g., magnesium or zinc oxide) or hydroxide thereof are mixed and reacted at a temp. above the softening point of the vinyl chloride polymer and about 180 deg.C or under, and, if necessary, reinforcing agents, fillers, plasticizers, etc. are incorporated with the reaction product to yield the intended polymer alloy.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polymer alloys with high fracture properties.

Traditionally, by combining and blending resin and rubber,
Many attempts have been made to improve the shortcomings of each.

However, these blend systems have a fatal drawback in that as the polymer composition approaches the middle between the two, the fracture properties deteriorate significantly, and therefore, there have been few polymer composition systems that can be put to practical use over a wide composition range.

One of the objects of the present invention is to provide polymer alloys with high fracture properties over a wide range of polymer compositions. Still another object is to provide a new polymer alloy having high fracture properties that could not be obtained using conventional polymer blend systems and polymer blend methods.

Namely, 1 Invention H, fAl carboxylated polyvinyl chloride, (B) carboxylated nitrile rubber, and (C) No.
An object of the present invention is to provide a polymer 7p with high fracture properties, which is obtained by reacting an oxide or hydroxide of a group metal or a group m metal.

PVC resin is blended with nitrile rubber or carboxylated nitrile rubber to increase flexibility.

Attempts have been made to improve impact fracture properties.

In the case of Sohara, high fracture properties 1-1 can be obtained with a wide range of polymer compositions such as the present invention σ), and the level of fracture strength is also significantly lower when compared with the present invention.

The effects of the present invention are first achieved by a combination of (A), (B), and (C).

The present invention will be explained in detail below.

The carboxylated polyvinyl chloride (Al component) used in the present invention is substantially a polymer of vinyl chloride and has a carboxyl group. For example, vinyl chloride to α,β-unsaturated carphone Acid co-merger, vinyl chloride to α, β to saturated carboxylic acid to plastic monomer copolymer, polyvinyl chloride or vinyl chloride-FP monomer copolymer to α.

There is one grafted with one cup of saturated carboxylic acid.

Examples of α,β-unsaturated carboxylic acids include anhydrides.

Examples of plastic monomers include vinyl acetate, vinylitine chloride, vinyl propionate, methyl acrylate, methyl methacrylate, and propylene. Of course, a carboxyl group may be introduced into a vinyl chloride polymer by an appropriate polymer reaction. Among them, vinyl chloride-(meth)acrylic acid-vinyl acetate co-5j combination is preferred.

Component (B) used in the present invention, carboxylated nitrile gono, is a copolymer of butadiene, isoprene bamboo conjugated diene, acrylate tolyo-d, and α,β-unsaturated carboxylic acid, or phtadiene or imprene conjugated diene. 7
α to copolymer of crylonitrile.

It is grafted with β-unsaturated carboxylic acid.

Here, examples of α,β-unfd pentahydrate carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, notraconic acid host, and anhydrides thereof. Of course, nitrile rubber that is carifoxylated by other polymer reactions may also be used. Carboxylation 2) l) Molecular conflict in rubber - tens of thousands, hundreds of thousands, or even more in some cases, so-called liquid rubber is not used because of its low strength. A copolymer of butadiene, acrylonitrile and (meth)acrylic acid is particularly preferred in that it provides a polymer alloy with high fracture properties. Carboxylated nitrile rubber usually has an acrylonitrile content of 20~
501i! 1%, α, β-unsaturated carboxylic acid 1-2
01 ft% is preferably used.

The oxide or hydroxide of the Group I or Group M Jincho of the component (0) reacts with the carboxyl group of the co-component (η) (B).
A) -(Al, (B) -(B) and/or tr
i (A) - (It brings about crosslinking etc. between the Bl components. Examples of these are magnesium, calcium, and strontium.

Examples include oxides or hydroxides of barium, zinc, and aluminum. Among them, magnesium oxide and zinc oxide are preferably used. (C) component is (Al component and (
B) Total amount of components: 05 to 30 parts by weight is usually used per 100 parts by weight. In particular, 25 to 20 weights are used in the device. (If the content of the C1 component is too small, a polymer 7p with high fracture properties cannot be obtained.

Moreover, if there are too many openings, workability will deteriorate, which is not preferable.

The polymer alloy of the present invention is prepared by reacting (A) (Bl) and (0) components.

The method is not particularly specified, but 1 For example (Ai a3)
A method in which both components are dissolved in a solvent, component (C) is added and mixed, and the solvent is removed to carry out the reaction. There are methods for conducting he, molding and reactions.

Although the reaction can be carried out at room temperature, it is generally not carried out at a temperature above the softening temperature of the vinyl chloride polymer and below 180°C. The reaction time is 9 minutes, depending on the temperature, and the cancellation takes about 1 to 30 minutes.

Polymer alloy ii of the present invention (Al(B) and (
Although there is no iZI with the C1 component, a first-order mechanism is presumed.

That is, (by the carboxyl group of the input ingredients and the carboxyl group of the component (B) reacting with the metal (hydr)oxide of the component (C) to form a gold salt.

(1) (A) component σ) Bonds between molecules (2+ (
B) Bonds between the molecules of the components (3) (Al (B) Bonds between the molecules of both components are occurring, and furthermore, these metal salts form some kind of ionic aggregate. It is thought that these factors work together to provide a large reinforcing effect.

Polymer 70 of the present invention is (Al (B) and (01
In addition to the three ingredients, reinforcing agents, fillers, plasticizers, stabilizers, anti-aging IV agents, antioxidants, ozone deterioration inhibitors, ultraviolet absorbers, colorants, etc., which are added to ordinary resins and rubbers, are added as needed. It is blended.

Because the polymer 70 of the present invention has high breaking properties, it has divine uses, such as belts and poses.

Tubes, pipes, vibration isolators, fenders t4. Rubber screen, compling material, bumper, low, r+, IQ.

These include the bottom, adhesive, paint, etc.

The present invention will be further explained in detail by giving examples below.

Real Kai 1f Series 1 to 3 In a kneader set at 100°C, force/l was applied. Polychlorinated polychlorinated chloride (Zeon 1 + 00 ), anti-aging agent MS-6 (+Crank N5-6 Inunai Shinko Kagaku Kogyo Co., Ltd. product), zinc stearate and calcium stearate were kneaded according to the formulation shown in Table 1 (expressed in 1 part by weight). The kneaded product was transferred onto a roll set at 70°C, and magnesium oxide was kneaded into it. Thereafter, the temperature was set at 160°C, and #L was allowed to react in the Teda mold for 10 minutes. Table IK shows the tensile fracture properties of the obtained polymer 70.

Even though the polymer composition is VCjk, it has destructive physical properties not found in conventional polymer friends ItCVi. For reference, a case in which magnesium oxide was removed in the same method as in Example 911 was used as a reference example. Non-Example 4 In the same method as in Example 2, zinc oxide was used instead of magnesium oxide. The obtained polymer alloy (-i
, breaking strength, 410 Kg/cv4. It exhibited high fracture properties with elongation at break of 0% and fracture energy of 720 K9 cm/d.

Reference Examples 4 to 6 The fracture properties of a conventionally known polymer system (lζ) are shown as reference examples.

Set to 130℃1. With a roll, polyvinyl chloride (Tenriki Hynyel S s 1110, a product of Uki Kagaku Kogyo & Co., Ltd.), nitrile rubber (TSRN231L), anti-aging agent MS-6. Zinc stearate, calcium stearate and stearic acid were kneaded. Kneaded material at 70℃
Zinc white, sulfur and accelerator MSA (
Contains Tsukusera MSA, Inunai Shinko Kagaku Kogyo Co., Ltd. products). Table 2 shows the number of blended parts.

Put the kneaded material into a mold set at 160°C.

The vulcanization reaction was carried out for 10 minutes. Table 2 shows the tensile fracture properties of these samples.

Table 2: As can be seen by comparing the physical properties in Tables 1 and 2, the breaking strength of this conventional polymer system and that of the present invention was found to be extremely high in physical property #-i of the present invention.

Claims (1)

[Scope of Claims] A high-destructibility product characterized by being obtained by reacting (11CAl carboxylated polyvinyl chloride ω) carboxylated nitrile rubber and (C) an oxide or hydroxide of a group II or group m metal. Physical polymer alloy.