JPS58213044A - Polymer alloy having high breaking strength - Google Patents

Abstract

PURPOSE:To provide a polymer alloy having a wide polymer composition and high breaking strength, by reacting a polyamide resin, a carboxylated nitrile rubber and ZnO with heating. CONSTITUTION:A polymer alloy having high breaking strength is obtd. by reacting a polyamide resin such as nylon 6 or nylon 66, a carboxylated nitrile rubber (such as a copolymer of a conjugated diene such as butadiene or isoprene with a crylonitrile and an alpha,beta-unsaturated carboxylic acid such as methacrylic acid) and ZnO with heating. The polymer alloy has a wide polymer composition and high breaking strength which could not be obtd. by conventional polymer blends or polymer blending methods, and is suitable for use in belt, hose, pipe, vibration insulator, fender, solid tire, bumper, soling, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polymer 7pi having 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 a polymer 7p type having a wide range of polymer compositions and high fracture properties. Yet another object is to provide a novel polymer 70 with high fracture properties that could not be obtained with conventional polymer blend systems and polymer blend methods.

That is, one aspect of the present invention provides a polymer API with high fracture properties, which is obtained by subjecting a polyamide resin, carboxylated nitrile rubber, and zinc oxide to a heat reaction.

Attempts have been made to blend nitrile rubber or carboxylated nitrile rubber with polyamide resin to increase flexibility and improve the physical properties at impact. 1 in those cases
High fracture properties cannot be obtained with a wide range of polymer compositions as in the present invention, and the level of fracture strength is also significantly lower than in the present invention. The effects of the present invention are first achieved by a combination of polyamide resin, carboxylated nitrile rubber and zinc oxide.

The present invention will be explained in detail below.

The polyamide resin used in the present invention is generally called nylon, and contains a condensate of diamine and dicarboxylic acid, a polycondensate of W-7 minocarboxylic acid, a compound of lactams, and a combination of these compounds. Polymers, etc. Examples of these are nylon 6. Nylon 66, nylon 6101 nylon 611, nylon 61
2. Nylon7. knife 9. knife 11. Nylon 12. Nylon 6/6.10, nylon 6/12
．． Naipun6/6.6. Nylon 6/6.6
/6.10. Nylon 6/6.6/12. Nylon 6/
66/ 6.10/12. Nylon 6.6/1
2 and mixtures thereof.

The carboxylated nitrile rubber used in the present invention is
Conjugated dienes such as butadiene and isoprene.

It is a copolymer of acrylonitrile and α,β-unsaturated carboxylic acid, or a copolymer of butadiene or isoprene and 7-acrylonitrile, to which α,β-unsaturated carboxylic acid is grafted. Here α.

An example of a β-unsaturated carboxylic acid is acrylic acid.

Examples include methacrylic acid, maleic acid, fumaric acid, itaconic acid, rytonic acid, citraconic acid, etc., and their anhydrides. Of course, nitrile rubber carboxylated by other polymer reactions may also be used. The molecular weight of carboxylated nitrile rubber is several hundred thousand, and in some cases even higher.

So-called liquid rubbers are used because of their low strength, and copolymers of tadiene, 7-acrylonitrile, and (meth)acrylic acid are particularly preferred because they provide polymeric materials with high fracture properties. Carboxylated nitrile rubber usually has an acrylonitrile content of 20 to 50% by weight, α! β
-Unsaturated unsaturated carboxylic acids 1 to 0 Zinc oxides include zinc white, which is used as an ordinary rubber compounding agent. Depending on the GJ combination, activated zinc white 1 surface-treated zinc white. Zinc peroxide etc. are used.

The amount of zinc oxide used is usually 1 to 30 parts by weight per 100 parts by weight of the total amount of carboxylated nitrile rubber and polyamide resin.
Parts by weight. In particular, 25 to 20 parts by weight is preferably used. If the amount of zinc oxide is too small, polymer 71:Ia with high fracture properties cannot be obtained. or.

If l is too large, processability will deteriorate, which is not preferable.

The polymer 7p of the present invention is usually a polyamide resin at a temperature at or above the melting point of the polyamide resin.

Carboxylated nitrile rubber and zinc oxide required.

If so, it is manufactured by kneading and molding other ingredients. Generally, kneading and molding are carried out at a temperature of 130 to 500°C. Mixed wires and molding 4! l! #-i Depending on the polymer composition, general kneading machines and molding machines for resins and rubbers can be used. Polyamide resin, carboxylated nitrile rubber, and zinc oxide are heated and reacted to form polymer 7 of the present invention.
0i manufacturing. Generally, it is carried out using heating during cross-conducting and molding.2 The reaction time is determined by cross-conducting and molding temperature as well as the compounding composition.2 For example, at 170℃, the total reaction time is about 10 to 60 minutes. It is.

There are no particular restrictions on the addition side of each compounding component at the time of cross-wiring, but if carboxylated nitrile rubber and zinc oxide are cross-wired at a high temperature such that these two components react in the absence of polyamide resin, processability and final Care must be taken as the breakage properties of the product will be significantly impaired.

Polymer 7p of the present invention is obtained by subjecting three components, polyamide resin, carboxylated nitrile rubber, and zinc oxide, to a heating reaction.

Although the formation mechanism of such polymer 7pi has not yet been fully elucidated, a first-order mechanism is presumed.

That is, the carboxyl group at the terminal of the polyamide molecule and the carboxyl group of the hydroxycarpoxylated nitri-7t rubber react with zinc oxide to form a zinc salt.

(1) Bonds between polyamide molecules (2) Bonds between carboxylated nitrile rubber molecules (3) Bonds between polyamide molecules and carboxylated nitrile rubber molecules, etc., and furthermore, these zinc salts bond with each other. It is thought that they form ion aggregates.

It is thought that these factors work together to provide a large reinforcing effect.

Polymer 7P of the present invention is a reinforcing agent that can be blended into ordinary resins and rubbers in addition to the three components of polyamide resin, carboxylated nitrile rubber, and zinc oxide.

Filling agent. plasticizer, stabilizer, anti-aging agent, antioxidant,
Ozone deterioration inhibitors, ultraviolet absorbers, colorants, etc. are sometimes added.

Since the polymer 70 of the present invention has high fracture properties, it has various uses. For example, belts and hoses.

These include tubes, pipes, vibration isolators, fenders, rubber screens, coupling materials, solid tires, tire members, bumpers, rolls, shoe soles 1, etc.

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

Implementation fll 1 to 5 In a kneader set at 160°C, nylon 12 (Diamide N1901, a product of Daicel Corporation), carboxylated nitrile rubber (Nipole 1072, a product of Nippon Zeon Corporation), zinc white, and anti-aging agent RD (non-oxidizing agent) were added. Flex RD (product of Seiko Kagaku Co., Ltd.) and stearic acid were kneaded according to the formulation shown in Table 1 (expressed in parts by weight). The kneading time is 1.5 minutes. Then transfer to a mold set at 180℃.

A heating reaction was carried out for 60 minutes. Table IK shows the tensile fracture properties of the obtained polymer alloy. Both polymer compositions have high fracture properties not found in conventional polymer blends. For reference, a case in which zinc white was removed in the same manner as in the example is shown as a reference example.

Examples 4 to 6 Copolymerized nylon (Amilan 0Ml100O, manufactured by Toshi Co., Ltd.), carboxylated nitrile rubber (Nipole 1072), and zinc i in a kneader set at 1000°C.

Antioxidant RD and stearic acid were kneaded according to the formulation shown in Table 2. The kneading time is 2 minutes.

Thereafter, the mixture was transferred to a mold set at 170° C. and reacted by heating for 60 minutes to obtain a polymer alloy. Table 2 shows examples and reference examples conducted in the same manner except for zinc white.

(Table 1) (Table 2) As can be seen from the examples, the polymer API of the present invention achieves both high breaking strength and high breaking elongation that could not be achieved with conventional blends of resin and rubber. It is the material.

Claims (1)

[Claims] (1) Polyamide resin, carboxylated nitrile