WO2018209825A1

WO2018209825A1 - Maleic anhydride grafted poe cable material and preparation method therefor

Info

Publication number: WO2018209825A1
Application number: PCT/CN2017/096545
Authority: WO
Inventors: 袁森; 袁柳淑; 吴航; 贺盟; 柏爱华; 唐家烨
Original assignee: 盐城申源塑胶有限公司
Priority date: 2017-05-16
Filing date: 2017-08-09
Publication date: 2018-11-22
Also published as: KR20200007105A; CN107057179A

Abstract

A maleic anhydride grafted POE cable material, comprising the following materials in parts by weight: 60-86 parts of POE, 55-65 parts of maleic anhydride, 1-3 parts of a co-crosslinking agent, 5-9 parts of an enhancer, 3-7 parts of amorphous silica fiber, 1-3 parts of a coupling agent, 10-14 parts of antimony trioxide, 12-20 parts of melamine, and 3-9 parts of an antioxidant. The co-crosslinking agent is one or more of triallyl isocyanurate, trimethylol propane trimethacrylate, and trihydroxymethylpropyl trimethylacrylate. Addition of the amorphous silica fiber facilitates to improve tenacity and weather fastness of the cable material. The cable has a flexural strength as high as 18.5 MPa and an elongation at break as high as 200%, and thus will not crack in low temperature (-40°C) impact or during low temperature (-40°C) bending.

Description

Maleic acid grafted POE cable material and preparation method thereof

Technical field

The invention relates to the field of cable materials, in particular to a maleic acid grafted POE cable material and a preparation method thereof.

Background technique

Plastics for wire and cable insulation and sheathing are commonly known as cable materials, including rubber, plastic, nylon and other varieties. Wire and cable in the transmission of electrical energy due to aging, self-heating or external fires will burn, as the quality and performance requirements of the cable in various fields are getting higher and higher, wire and cable need to improve its flame retardancy, by adding halogen-containing resistance The flammable agent and halogen-containing wire and cable release a large amount of smoke and hydrogen halide gas during the combustion process, which is easy to suffocate and cause corrosion to equipment and equipment. At present, the development direction of cables and other fields at home and abroad is low-smoke, low-halogen and halogen-free flame retardant materials.

The invention patent "201510197415.7""a high flame retardant low smoke zero halogen cable material and a preparation method thereof" discloses a high flame retardant low smoke zero halogen cable material and a preparation method thereof, wherein the high flame retardant low smoke halogen free The cable material, in terms of mass percentage, the composition components and the respective contents are: ethylene-vinyl acetate copolymer 12-22%, polyethylene 5-10%, maleic anhydride grafted polyethylene 5-10%, inorganic filler 40 ~50%, self-made composite flame retardant 15-20%, anti-oxidation aid 1~3%, the sum of the mass percentages of each component is 100%, the advantage is that the self-made composite flame retardant can improve the carbon formation performance of the cable material And self-extinguishing performance, the prepared cable material is made into 1.5mm ² single-core wire through UL's VW-1 burning test, the insulation electrical properties of the cable material are guaranteed, and the white appearance of the cable material can be made into various colors required by customers. However, its strength is not high and its service life is short.

At present, most of the production of halogen-free low-smoke flame-retardant cable materials is to add a large amount of magnesium hydroxide or aluminum hydroxide to the polyolefin substrate to achieve the purpose of flame retardancy, but adding a large amount of inorganic materials, physical and mechanical properties of the cable material and The processing performance is deteriorated, and its weather resistance, oil resistance and low temperature resistance are not good.

Summary of the invention

In order to solve the above problems, the present invention discloses a maleic acid grafted POE cable material and a preparation method thereof.

In order to achieve the above object, the present invention provides the following technical solutions:

A maleic acid grafted POE cable material comprising the following parts by weight: 60-86 parts of POE, 55-65 parts of maleic acid, 1-3 parts of co-crosslinking agent, 5-9 parts of reinforcing agent, no 3-7 parts of stereotyped silica fibers, 1-3 parts of coupling agent, 10-14 parts of antimony trioxide, 12-20 parts of melamine, 3-9 parts of antioxidant, and the triene C. One or more of a polyisocyanate, trimethylolpropane trimethacrylate or trimethylolpropane trimethacrylate.

Preferably, the reinforcing agent comprises: 10-16 parts of a butadiene rubber resin, 6-12 parts of magnesium oxide, 7-11 parts of silica, and 2-4 parts of graphene.

Preferably, the amorphous silica fiber has an average particle diameter of 20 nm and a specific surface area of 180 m ² /g.

Preferably, the coupling agent is one or more of propyltrimethoxysilane, phenyltrimethoxysilane, tetraisobutyl titanate or stearic acid.

Preferably, the antioxidant is L-ascorbyl palmitate and benzotriazole, and the weight ratio of L-ascorbyl palmitate to benzotriazole is 2:1.

A method for preparing a maleic acid grafted POE cable material comprises the following steps:

S1: mixing POE and maleic acid with a mixer for 1-3 hours, adding a co-crosslinking agent, and kneading for 3-6 hours;

S2: placing the amorphous silica fiber into a crusher, grinding for 30-60 minutes, adding a coupling agent to continue to crush for 1-2 hours;

S3: mixing the obtained products of S1 and S2, placing them in a co-rotating twin-screw extruder, adding a reinforcing agent, antimony trioxide, melamine and an antioxidant, and extruding at a processing temperature of 200-260 ° C;

S4: The S3 product was subjected to granulation and then packaged.

Preferably, the kneader in S1 is a two-roll kneader, and the kneading roll temperature of the kneader is 45 °C.

Preferably, the screw of the co-rotating twin-screw extruder is tapered, and the screw has an aspect ratio of 22 or more.

The invention has the beneficial effects that the invention adds the amorphous silica fiber, which is beneficial to improving the toughness of the cable material and enhancing the weather resistance thereof; the cable of the invention does not crack at low temperature (-40 ° C) impact, at low temperature ( -40 ° C) does not crack when bent; the invention is granulated by extrusion in a co-rotating twin-screw extruder, and the prepared cable material is halogen-free, has good physical properties and processing properties, and has a long service life.

detailed description

The technical solutions provided by the present invention are described in detail below with reference to the specific embodiments, and the following detailed description is only to illustrate the invention and not to limit the scope of the invention.

The amorphous silica fibers used in the examples of the present invention have an average particle diameter of 20 nm and a specific surface area of 180 m ² /g.

Example 1

S1: 60 parts of POE and 55 parts of maleic acid were kneaded in a two-roll kneader for 1 hour, the temperature of the kneading roll was 45 ° C, and 1 part of a co-crosslinking agent, triallyl isocyanurate, was added. Mixing for 3 hours;

S2: 3 parts of amorphous silica fiber was placed in a crusher, ground for 30 min, 1 part of propyltrimethoxysilane coupling agent was added, and the crushing was continued for 1 h;

S3: mixing the obtained products of S1 and S2 into a co-rotating twin-screw extruder with a screw taper, the length-to-diameter ratio of the screw is 22 or more, and then adding 5 parts of reinforcing agent, 10-14 parts of trioxide锑, 12-20 parts of melamine and 3-9 parts of antioxidant, the antioxidant is L-ascorbyl palmitate and benzotriazole in a weight ratio of 2:1, the reinforcing agent comprises 10 parts of butadiene rubber resin, magnesium oxide 6 parts, 7 parts of silica, 2 parts of graphene, extruded at a processing temperature of 200 ° C;

S4: The S3 product was subjected to granulation and then packaged.

Example 2

S1: 86 parts of POE and 65 parts of maleic acid were kneaded in a two-roll kneader for 3 hours, the temperature of the kneading roll was 45 ° C, and 3 parts of a crosslinking agent trimethylolpropane trimethacrylate was added. Mixing for 6 hours;

S2: Put 7 parts of amorphous silica fiber into the crusher, grind for 60min, add 3 parts of phenyltrimethoxysilane coupling agent, continued to break for 2h;

S3: mixing the obtained products of S1 and S2 into a co-rotating twin-screw extruder with a screw taper, the length-to-diameter ratio of the screw is 22 or more, and then adding 9 parts of reinforcing agent, 14 parts of antimony trioxide, 20 A portion of melamine and 9 parts of antioxidant, the antioxidant is 2:1 by weight of L-ascorbyl palmitate and benzotriazole, the reinforcing agent comprises 16 parts of butadiene rubber resin, 12 parts of magnesium oxide, and silica 11 Parts, 4 parts of graphene, extruded at a processing temperature of 260 ° C;

S4: The S3 product was subjected to granulation and then packaged.

Example 3

S1: 73 parts of POE and 60 parts of maleic acid were kneaded in a two-roll kneader for 2 hours, the temperature of the kneading roll was 45 ° C, and 2 parts of trimethylolpropane trimethacrylate co-crosslinking agent was added. Mixing for 4.5 hours;

S2: 5 parts of amorphous silica fiber was placed in a crusher, ground for 45 min, 2 parts of tetraisobutyl titanate coupling agent was added, and the crushing was continued for 1.5 h;

S3: mixing the obtained products of S1 and S2 into a co-rotating twin-screw extruder with a screw taper, the length-to-diameter ratio of the screw is 22 or more, and then adding 7 parts of reinforcing agent, 12 parts of antimony trioxide, 16 A portion of melamine and 6 parts of antioxidant, the antioxidant is L-ascorbyl palmitate and benzotriazole in a weight ratio of 2:1, and the reinforcing agent comprises 13 parts of a butadiene rubber resin, 9 parts of magnesium oxide, and 9 parts of silica. Parts, 3 parts of graphene, extruded at a processing temperature of 230 ° C;

S4: The S3 product was subjected to granulation and then packaged.

Example 4

S1: 63 parts of POE and 57 parts of maleic acid were kneaded in a two-roll mill for 1 hour, the temperature of the mixing roll was 45 ° C, and 2 parts of the triallyl isocyanurate and trimethyl group were added. Trimethylolpropane acrylate crosslinker, kneaded for 4 hours;

S2: 4 parts of amorphous silica fiber was placed in a crusher, ground for 350 min, 2 parts of stearic acid coupling agent was added, and the crushing was continued for 1 h;

S3: Mixing the obtained products of S1 and S2 into a co-rotating twin-screw extruder with a screw taper, the length-to-diameter ratio of the screw is 22 or more, and then adding 6 parts of reinforcing agent, 11 parts of antimony trioxide, 13 A portion of melamine and 4 parts of antioxidant, the antioxidant is 2:1 by weight of L-ascorbyl palmitate and benzotriazole, the reinforcing agent comprises 11 parts of butadiene rubber resin, 7 parts of magnesium oxide, and silica 8 Parts, 3 parts of graphene, extruded at a processing temperature of 210 ° C;

S4: The S3 product was subjected to granulation and then packaged.

Example 5

S1: 84 parts of POE and 63 parts of maleic acid were kneaded in a two-roll mixer for 2 hours, the temperature of the mixing roll was 45 ° C, and 3 parts of the triallyl isocyanurate and the trishydroxyl was added. a cross-linking agent of propane trimethacrylate, kneaded for 5 hours;

S2: 6 parts of amorphous silica fiber was placed in a crusher, ground for 50 min, 2 parts of tetraisobutyl titanate and stearic acid coupling agent were added, and the crushing was continued for 2 hours;

S3: mixing the obtained products of S1 and S2 into a co-rotating twin-screw extrusion with a screw taper In the machine, the aspect ratio of the screw is 22 or more, and then 8 parts of reinforcing agent, 13 parts of antimony trioxide, 18 parts of melamine and 8 parts of antioxidant are added. The antioxidant is L-ascorbyl palmitate in a weight ratio of 2:1. Ester and benzotriazole, the reinforcing agent comprises 15 parts of a butadiene rubber resin, 10 parts of magnesium oxide, 10 parts of silica, 4 parts of graphene, and extruded at a processing temperature of 250 ° C;

S4: The S3 product was subjected to granulation and then packaged.

Test 1

The samples of the examples 1-5 were tested for mechanical properties according to industry standards. The detailed experimental data is shown in Table 1:

Table 1 Experimental data record of mechanical properties of different samples

It can be seen from Table 1 that the maleic acid grafted POE cable material of the invention has good bending strength and elongation at break, and the bending strength is up to 18.5 MPa, and the elongation at break is up to 200%. It does not crack at low temperature (-40 ° C) impact, does not crack when bent at low temperature (-40 ° C), and has good flexibility.

The technical means disclosed in the solution of the present invention is not limited to the technical means disclosed in the above embodiments, and includes a technical solution composed of any combination of the above technical features. It should be noted that those skilled in the art will not deviate from the present invention. Under the premise of the principle, several improvements and retouchings can be made, and these improvements and retouchings are also considered as protection scope of the present invention.

Claims

A maleic acid grafted POE cable material characterized by comprising the following parts by weight: POE 60-86 parts, maleic acid 55-65 parts, co-crosslinking agent 1-3 parts, reinforcing agent 5- 9 parts, 3-7 parts of amorphous silica fiber, 1-3 parts of coupling agent, 10-14 parts of antimony trioxide, 12-20 parts of melamine, 3-9 parts of antioxidant, said co-crosslinking agent It is one or more of triallyl isocyanurate, trimethylolpropane trimethacrylate or trimethylolpropane trimethacrylate.
The maleic acid grafted POE cable material according to claim 1, wherein the reinforcing agent comprises: 10-16 parts of a butadiene rubber resin, 6-12 parts of magnesium oxide, and 7-11 parts of silicon dioxide. 2-4 parts of graphene.
The maleic acid grafted POE cable material according to claim 1, wherein the amorphous silica fiber has an average particle diameter of 20 nm and a specific surface area of 180 m 2 /g.
The maleic acid grafted POE cable material according to claim 1, wherein the coupling agent is propyltrimethoxysilane, phenyltrimethoxysilane, tetraisobutyl titanate or stearin. One or more of the acids.
The maleic acid grafted POE cable material according to claim 1, wherein said antioxidant is L-ascorbyl palmitate and benzotriazole, said L-ascorbyl palmitate and styrene-acrylic acid. The weight ratio of triazole is 2:1.
The method for preparing a maleic acid grafted POE cable material according to claim 5, comprising the steps of:

S1: mixing POE and maleic acid with a mixer for 1-3 hours, adding a co-crosslinking agent, and kneading for 3-6 hours;

S2: placing the amorphous silica fiber into a crusher, grinding for 30-60 minutes, adding a coupling agent to continue to crush for 1-2 hours;

S3: mixing the obtained products of S1 and S2, placing them in a co-rotating twin-screw extruder, adding a reinforcing agent, antimony trioxide, melamine and an antioxidant, and extruding at a processing temperature of 200-260 ° C;

S4: The S3 product was subjected to granulation and then packaged.
The method for preparing a maleic acid grafted POE cable material according to claim 6, wherein the kneading machine in the S1 is a two-roll kneader, and the kneading roller temperature of the kneading machine is 45 ° C.
The method for preparing a maleic acid grafted POE cable material according to claim 6, wherein the screw of the co-rotating twin-screw extruder is tapered, and the length-to-diameter ratio of the screw is 22 or more.