A high-fluidity, scratch-resistant, flame-retardant, chlorinated polyethylene composite material and preparation method thereof

Abstract

The present invention belongs to the technical field of modified polymer materials, and specifically discloses a high-fluidity, scratch-resistant flame-retardant chlorinated polyethylene composite material and a preparation method thereof. The composite material is composed of the following raw materials in parts by weight: 60 to 80 parts of chlorinated polyethylene, 5 to 15 parts of acrylic copolymer polyvinyl chloride resin, 20 to 35 parts of ethylene-butene copolymer, 4 to 7 parts of compounded scratch-resistant agent, 2 to 4 parts of plasticizer, 3 to 6 parts of stabilizer, 3 to 6 parts of lubricant, 6 to 10 parts of flame retardant and 5 to 15 parts of reinforcing agent. The present invention obtains a high-fluidity, scratch-resistant composite material by the mutual coordination and synergistic effect of components such as high-chlorine-content chlorinated polyethylene, AGR resin, POE resin and lubricant, compounded scratch-resistant agent, and reinforcing agent. The extruded calendered product has better extrusion processing fluidity and scratch resistance. It is not easy to produce scratches and cracks on the surface during construction and use. Its preparation process is simple, does not require vulcanization, and is easy to recycle.

Description

Technical Field

[0001] The invention belongs to the technical field of modified polymer materials, and in particular relates to a high-fluidity, scratch-resistant, flame-retardant, chlorinated polyethylene composite material and a preparation method thereof. Background Art

[0002] Chlorinated polyethylene (CPE) is a saturated thermoplastic elastomer material with excellent resistance to heat oxygen aging, ozone aging, acid and alkali resistance and chemical resistance. Chlorinated polyethylene contains chlorine, which has excellent flame retardant properties, and has anti-drip properties. It is non-toxic and tasteless, does not contain heavy metals and PAHs (PAHs is a carcinogenic polycyclic aromatic hydrocarbons), fully meets environmental protection requirements, and has high filling performance. It can be made into products that meet various performance requirements. Chlorinated polyethylene resin has a series of excellent properties. It is an excellent impact modifier for polyvinyl chloride (PVC) plastics, and is also an elastomer material with good comprehensive performance. It has a very wide range of applications and has been widely used in cables, wires, hoses, tapes, rubber and plastic products, sealing materials, flame retardant conveyor belts, waterproof rolls, tent films, floor cloths and various special-shaped products; Chlorinated polyethylene can also be blended with polypropylene, high and low pressure polyethylene, ABS, etc. to improve the flame retardant properties, impact resistance, aging resistance and printing properties of these plastics.

[0003] However, CPE has high viscosity, high friction heat, poor fluidity, easy dehydrochlorination, and self-catalysis, which leads to its violent decomposition and degradation, thus affecting the various properties of the product. It also has problems such as low strength and poor scratch resistance, which affect its application range. Although CPE can be vulcanized to improve strength and scratch resistance, the preparation process is complicated because of the need for vulcanization, and it is difficult to recycle and easily causes environmental pollution.

[0004] The above existing technologies have some problems, so the research on high-flowability, scratch-resistant chlorinated polyethylene composite materials and preparation methods thereof is of great significance. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a high-fluidity, scratch-resistant, flame-retardant chlorinated polyethylene composite material and a preparation method thereof. By adding functional additives and compounding chlorinated polyethylene, AGR resin and POE resin, a high-strength ternary blended composite material can be obtained, which has good fluidity and scratch resistance. The preparation process is simple, does not require vulcanization, and is easy to recycle.

[0006] In order to solve the above technical problems, the technical solution of the present invention is:

[0007] A high-fluidity, scratch-resistant, flame-retardant chlorinated polyethylene composite material, comprising the following raw materials in parts by weight: 60-80 parts of chlorinated polyethylene, 5-15 parts of acrylic copolymer polyvinyl chloride resin (AGR resin), 20-35 parts of ethylene-butene copolymer (POE resin), 4-7 parts of compounded scratch-resistant agent, 2-4 parts of plasticizer, 3-6 parts of stabilizer, 3-6 parts of lubricant, 6-10 parts of flame retardant and 5-15 parts of reinforcing agent;

[0008] In order to improve the surface scratch resistance of the ternary blended composite material of chlorinated polyethylene, AGR resin and POE resin, a composite scratch resistant agent is used, and the composite scratch resistant agent is composed of a scratch resistant agent, basalt fiber chopped yarn and quartz sand in a weight ratio of 1-1.2:1:0.4-0.6. Among them, the scratch resistant agent can effectively reduce the friction coefficient of the composite surface and reduce the surface stress, so that the material has better scratch resistance, friction resistance and other properties, and also has a lubricating effect, reducing the decomposition caused by excessive friction heat caused by excessive shear. The scratch resistant agent can be one or more of polysiloxane, organic silicone grafted long-chain alkane, erucamide, stearyl erucamide, oleamide, ethylene bisoleamide or JYN999 (microcrystalline compound compounded with bio-based acid ester modifier) ​​in any proportion. Polysiloxane and aliphatic amides have better lubricity, so the scratch resistant agent is more preferably polysiloxane and erucamide. Basalt fiber chopped yarn and quartz sand are both hard, wear-resistant and chemically stable. After compounding with the scratch-resistant agent, the three can work together to significantly improve the surface strength of the material and further improve the scratch resistance of the material. The diameter of the basalt fiber chopped yarn is generally 5.5μm to 25μm, the length is 6mm to 100mm, and the surface is treated with a silane coupling agent; the quartz sand particle size is generally 1250 mesh.

[0009] Preferably, the chlorine content of the chlorinated polyethylene is 40-45%, and the melting enthalpy is ≤15 J / g (DSC method).

[0010] Preferably, the melt index of the ethylene-butene copolymer (POE resin) is 0.8-2.5 g / 10 min (190°C / 2.16 kg), and the melting temperature is 34-45°C. The POE resin can be selected from 7467, 7256 or 8440. Among them, the 7467 type POE resin has better processing fluidity when preparing composite materials, and is more easily compatible with chlorinated polyethylene. The strength and hardness of the composite materials are relatively high. Therefore, the POE resin is more preferably 7467 type.

[0011] Preferably, the scratch resistant agent is one or a combination of any proportion of two or more of polysiloxane, organic silicone grafted long-chain alkane, erucamide, stearyl erucamide, oleamide, ethylene bisoleamide, and JYN999 (microcrystalline compound combined with bio-based acid ester modified product).

[0012] The plasticizer can improve the flexibility of the composite material during processing, reduce the melt viscosity of the composite material, improve fluidity, and reduce the glass transition temperature. Preferably, the plasticizer is a combination of one or two or more of trichloroethyl phosphate, chlorinated paraffin, and dioctyl adipate in any proportion. Since trichloroethyl phosphate has better flame retardancy and cold resistance, the plasticizer is more preferably trichloroethyl phosphate.

[0013] Preferably, the stabilizer is one or a combination of any proportion of calcium zinc composite stabilizer, lead salt stabilizer, calcium stearate, lead stearate, and rare earth composite stabilizer. During the production and processing, the amount of stabilizer added needs to be controlled. If the amount of stabilizer added is too little, the heat resistance stability during mixing, processing, and product use will be very poor, and the composite material will be easily decomposed; if the amount of stabilizer added is too much, the stabilizer in the composite material will precipitate.

[0014] Preferably, the lubricant is one or a combination of any proportion of oxidized polyethylene wax, paraffin wax, stearic acid or polyethylene wax. During the production process, the amount of lubricant added needs to be controlled. If the amount of lubricant is too low, it will affect the fluidity during the processing, and if the amount is too high, it will affect the mechanical properties and flame retardant properties of the composite material.

[0015] Preferably, the flame retardant is one or a combination of any proportion of antimony trioxide, aluminum hydroxide or decabromodiphenyl ether. Since the flame retardant is an inorganic substance, the more it is added, the worse the fluidity during the production and processing, and the worse the anti-slip and friction resistance of the composite material. When the flame retardant is antimony trioxide, the amount of the flame retardant is the least and the flame retardant performance of the composite material can meet the requirements of the corresponding standards, and the oxygen index is ≥29%. Therefore, the flame retardant is more preferably antimony trioxide.

[0016] Preferably, the reinforcing agent is a combination of one or more of talcum powder, calcium carbonate or calcium sulfate whisker in any proportion. Since the crystal structure of talcum powder is layered, it is easy to split into scales. At the same time, talcum powder has good lubricity, which can improve the fluidity of composite materials during production and processing, and can improve the dimensional stability and hardness and rigidity of plastics. In addition, the price of talcum powder is low, which can reduce the formulation cost. Therefore, the reinforcing agent is more preferably talcum powder.

[0017] The method for preparing the high-fluidity, scratch-resistant, flame-retardant, chlorinated polyethylene composite material comprises the following steps:

[0018] S1. Weigh each raw material by weight;

[0019] S2, putting chlorinated polyethylene, acrylic copolymer polyvinyl chloride resin, compound anti-scratch agent, stabilizer, lubricant, flame retardant and reinforcing agent into a mixer and stirring at high speed to obtain material 1;

[0020] When the temperature of the material 1 reaches 80-85°C, a plasticizer is added and high-speed stirring is continued to obtain a material 2;

[0021] When the temperature of the material 2 reaches 98-100° C., ethylene-butene copolymer is added and stirred at a low speed to obtain material 3;

[0022] When the temperature of the material three reaches 110-120° C., the material three is introduced into a cold mixer for cooling, and when the temperature drops to 40-45° C., the material is taken out to obtain a powdery composite material;

[0023] S3, extruding and granulating the powdery composite material, wherein the processing temperature of the extrusion granulation is 110-160° C., the screw speed is 300-400 rpm, and after the pellets are fully cooled, a granular composite material is obtained.

[0024] The present invention has at least the following beneficial effects:

[0025] (1) The high-flowability, scratch-resistant, flame-retardant chlorinated polyethylene composite material provided by the present invention contains POE resin, which has a high melt index. When compounded with AGR resin, it can effectively improve the fluidity of the composite material during processing, which is beneficial for extruding wide-width waterproof rolls, tent films, floor cloths and other extrusion calendering products that require high fluidity. POE also has good tensile properties and tensile strength, ensuring the durability and stability of the product.

[0026] (2) AGR resin is added to the high-fluidity, scratch-resistant, flame-retardant chlorinated polyethylene composite material provided by the present invention. The composite material is resistant to low temperatures, has high impact resistance, good rigidity and good compatibility, making it easy to plasticize and process. The prepared composite material has better low-temperature toughness, friction resistance, scratch resistance and strength. Since AGR resin also has excellent flame retardant properties, the composite material can reduce the amount of flame retardant added, and further improve the fluidity, friction resistance and scratch resistance of the composite material while meeting the flame retardant performance standards.

[0027] (3) The high-flowability, scratch-resistant, flame-retardant chlorinated polyethylene composite material provided by the present invention is a compound of chlorinated polyethylene, AGR resin and POE resin, so that the composite material has excellent impact resistance and low-temperature toughness, good corrosion resistance, high strength and good compatibility compared with the rubber material in the prior art; and the preparation process is simple, does not require vulcanization, is easy to recycle, and has low or no environmental pollution.

[0028] (4) The high-flowability, scratch-resistant, flame-retardant, chlorinated polyethylene composite material provided by the present invention adopts a scratch-resistant agent compounded with basalt fiber chopped yarn and quartz sand, which can effectively reduce the surface friction coefficient of the material and improve the surface strength, thereby improving the scratch resistance of the composite material and preventing scratches.

[0029] (5) The composite material of the present invention can be produced using the same extrusion and calendering equipment as PVC, and can be easily industrialized. It can also extrude ultra-wide waterproof rolls, tent films, floor cloths, etc. It has excellent flame retardant properties, good anti-slip properties, scratch resistance, long service life, and is environmentally friendly.

[0030] (6) The preparation method of the present invention uses batch raw materials and industrial equipment, has strong versatility, and is easy to mass-produce. The obtained flame-retardant chlorinated polyethylene composite material with high fluidity and scratch resistance meets the requirements of high-performance materials and has a good prospect for industrial application. DETAILED DESCRIPTION

[0031] The present invention will be further specifically described below in conjunction with the embodiments. In the following detailed description, some exemplary embodiments of the present invention are described only by way of illustration. Needless to say, those of ordinary skill in the art will appreciate that the described embodiments may be modified in various ways without departing from the spirit and scope of the present invention. Therefore, the description in the embodiments is illustrative in nature and is not intended to limit the scope of protection of the claims.

[0032] Example 1

[0033] A high-fluidity, scratch-resistant, flame-retardant chlorinated polyethylene composite material, comprising the following raw materials in parts by weight: 68 parts of chlorinated polyethylene, 8 parts of AGR resin, 30 parts of POE resin, 2.2 parts of erucamide, 2 parts of basalt fiber chopped yarn, 1.2 parts of quartz sand, 3 parts of trichloroethyl phosphate, 4 parts of calcium-zinc composite stabilizer, 2 parts of paraffin wax, 1 part of stearic acid, 1 part of polyethylene wax, 6.8 parts of antimony trioxide and 11 parts of talc;

[0034] Among them: the chlorine content of chlorinated polyethylene is 40.8%, the melting enthalpy is 8.4J / g, the Shore hardness is 58A, the tensile strength is 9.2Mpa, and the elongation is 420%;

[0035] The melt index of POE resin is (190°C / 2.16kg) 1.2g / 10min.

[0036] Weigh the chlorinated polyethylene, AGR resin, erucic acid amide, basalt fiber chopped yarn, quartz sand, calcium zinc composite stabilizer, paraffin, stearic acid, polyethylene wax, antimony trioxide and talcum powder according to the weight proportion, start the mixer, stir at high speed (1500-3000 rpm), add trichloroethyl phosphate when the material temperature reaches 85°C, continue stirring at high speed, add POE resin when the material temperature reaches 100°C, stir at low speed (500-1000 rpm), when the material temperature reaches 110°C, the mixing time is 14min, discharge the material into a cold mixer, cool the material in the cold mixer to 40-45°C, discharge the material, and obtain a mixed material. The obtained mixed material is extruded and granulated by a parallel twin-screw extruder granulator, the processing temperature of the extrusion granulation is 110-160°C, the screw speed is 300-400rpm, and the granules are fully cooled to obtain a granular composite material.

[0037] Example 2

[0038] A high-fluidity, scratch-resistant, flame-retardant chlorinated polyethylene composite material, comprising the following raw materials in parts by weight: 62 parts of chlorinated polyethylene, 10 parts of AGR resin, 32 parts of POE resin, 2.8 parts of polysiloxane, 2.3 parts of basalt fiber chopped yarn, 1.4 parts of quartz sand, 3.8 parts of trichloroethyl phosphate, 4.2 parts of calcium zinc composite stabilizer, 1.5 parts of paraffin wax, 1.2 parts of stearic acid, 1 part of polyethylene wax, 6.5 parts of antimony trioxide and 9 parts of talc;

[0039] Wherein: the chlorine content of the chlorinated polyethylene is 40.8%, the melting enthalpy is 8.4 J / g, the Shore hardness is 58A, the tensile strength is 9.2 MPa, and the elongation is 420% (the chlorinated polyethylene is the same raw material as that in Example 1);

[0040] The melt index of the POE resin is (190°C / 2.16kg) 1.2g / 10min (the POE resin is the same raw material as that in Example 1).

[0041] Weigh the chlorinated polyethylene, AGR resin, polysiloxane, basalt fiber chopped yarn, quartz sand, calcium zinc composite stabilizer, paraffin, stearic acid, polyethylene wax, antimony trioxide and talcum powder according to the weight proportion, start the mixer, stir at high speed (1500-3000 rpm), add trichloroethyl phosphate when the material temperature reaches 80°C, continue stirring at high speed, add POE resin when the material temperature reaches 100°C, stir at low speed (500-1000 rpm), when the material temperature reaches 110°C, the mixing time is 15min, discharge the material into a cold mixer, cool the material in the cold mixer to 40-45°C, discharge the material, and obtain a mixed material. The obtained mixed material is extruded and granulated by a parallel twin-screw extruder granulator, the processing temperature of the extrusion granulation is 110-160°C, the screw speed is 300-400rpm, and the granules are fully cooled to obtain a granular composite material.

[0042] Example 3

[0043] A high-fluidity, scratch-resistant, flame-retardant chlorinated polyethylene composite material, composed of the following raw materials in parts by weight: 72 parts of chlorinated polyethylene, 13 parts of AGR resin, 25 parts of POE resin, 2.2 parts of erucamide, 1.7 parts of basalt fiber chopped yarn, 1 part of quartz sand, 2.8 parts of dioctyl adipate, 4 parts of rare earth composite stabilizer, 2 parts of paraffin wax, 1.2 parts of stearic acid, 1 part of polyethylene wax, 7.1 parts of decabromodiphenyl ether and 10 parts of talc;

[0044] Wherein: the chlorine content of the chlorinated polyethylene is 40.8%, the melting enthalpy is 8.4 J / g, the Shore hardness is 58A, the tensile strength is 9.2 MPa, and the elongation is 420% (the chlorinated polyethylene is the same raw material as that in Example 1);

[0045] The melt index of the POE resin is (190°C / 2.16kg) 1.2g / 10min (the POE resin is the same raw material as that in Example 1).

[0046] Weigh the chlorinated polyethylene, AGR resin, erucic acid amide, basalt fiber chopped yarn, quartz sand, rare earth composite stabilizer, paraffin, stearic acid, polyethylene wax, decabromodiphenyl ether and talcum powder according to the weight proportion, start the mixer, stir at high speed (1500-3000 rpm), add dioctyl adipate when the material temperature reaches 83°C, continue stirring at high speed, add POE resin when the material temperature reaches 100°C, stir at low speed (500-1000 rpm), when the material temperature reaches 110°C, the mixing time is 16min, discharge the material into a cold mixer, cool the material in the cold mixer to 40-45°C, discharge the material, and obtain a mixed material. The obtained mixed material is extruded and granulated by a parallel twin-screw extruder granulator, the processing temperature of the extrusion granulation is 110-160°C, the screw speed is 300-400rpm, and the granules are fully cooled to obtain a granular composite material.

[0047] Example 4

[0048] A high-fluidity, scratch-resistant, flame-retardant chlorinated polyethylene composite material, comprising the following raw materials in parts by weight: 68 parts of chlorinated polyethylene, 8 parts of AGR resin, 30 parts of POE resin, 2.2 parts of erucamide, 2 parts of basalt fiber chopped yarn, 1.2 parts of quartz sand, 3 parts of trichloroethyl phosphate, 4 parts of calcium-zinc composite stabilizer, 2 parts of paraffin wax, 1 part of stearic acid, 1 part of polyethylene wax, 6.8 parts of antimony trioxide and 11 parts of talc;

[0049] Among them: the chlorine content of chlorinated polyethylene is 44.5%, the melting enthalpy is 6.8J / g, the Shore hardness is 56A, the tensile strength is 8.9Mpa, and the elongation is 440%;

[0050] The melt index of POE resin is (190°C / 2.16kg) 1.8g / 10min.

[0051] Weigh the chlorinated polyethylene, AGR resin, erucic acid amide, basalt fiber chopped yarn, quartz sand, calcium zinc composite stabilizer, paraffin, stearic acid, polyethylene wax, antimony trioxide and talcum powder according to the weight proportion, start the mixer, stir at high speed (1500-3000 rpm), add trichloroethyl phosphate when the material temperature reaches 85°C, continue stirring at high speed, add POE resin when the material temperature reaches 100°C, stir at low speed (500-1000 rpm), when the material temperature reaches 110°C, the mixing time is 14min, discharge the material into a cold mixer, cool the material in the cold mixer to 40-45°C, discharge the material, and obtain a mixed material. The obtained mixed material is extruded and granulated by a parallel twin-screw extruder granulator, the processing temperature of the extrusion granulation is 110-160°C, the screw speed is 300-400rpm, and the granules are fully cooled to obtain a granular composite material.

[0052] Example 5

[0053] A high-fluidity, scratch-resistant, flame-retardant chlorinated polyethylene composite material, comprising the following raw materials in parts by weight: 62 parts of chlorinated polyethylene, 10 parts of AGR resin, 32 parts of POE resin, 2.8 parts of polysiloxane, 2.3 parts of basalt fiber chopped yarn, 1.4 parts of quartz sand, 3.8 parts of trichloroethyl phosphate, 4.2 parts of calcium zinc composite stabilizer, 1.5 parts of paraffin wax, 1.2 parts of stearic acid, 1 part of polyethylene wax, 6.5 parts of antimony trioxide and 9 parts of talc;

[0054] Wherein: the chlorine content of the chlorinated polyethylene is 44.5%, the melting enthalpy is 6.8 J / g, the Shore hardness is 56A, the tensile strength is 8.9 MPa, and the elongation is 440% (the chlorinated polyethylene is the same raw material as that in Example 4);

[0055] The melt index of the POE resin is (190°C / 2.16kg) 1.8g / 10min (the POE resin is the same raw material as that in Example 4).

[0056] Weigh the chlorinated polyethylene, AGR resin, polysiloxane, basalt fiber chopped yarn, quartz sand, calcium zinc composite stabilizer, paraffin, stearic acid, polyethylene wax, antimony trioxide and talcum powder according to the weight proportion, start the mixer, stir at high speed (1500-3000 rpm), add trichloroethyl phosphate when the material temperature reaches 80°C, continue stirring at high speed, add POE resin when the material temperature reaches 100°C, stir at low speed (500-1000 rpm), when the material temperature reaches 110°C, the mixing time is 15min, discharge the material into a cold mixer, cool the material in the cold mixer to 40-45°C, discharge the material, and obtain a mixed material. The obtained mixed material is extruded and granulated by a parallel twin-screw extruder granulator, the processing temperature of the extrusion granulation is 110-160°C, the screw speed is 300-400rpm, and the granules are fully cooled to obtain a granular composite material.

[0057] Comparative Example 1

[0058] A flame-retardant chlorinated polyethylene composite material, composed of the following raw materials in parts by weight: 68 parts of chlorinated polyethylene, 8 parts of polyvinyl chloride resin, 30 parts of POE resin, 2.2 parts of erucamide, 2 parts of basalt fiber chopped yarn, 1.2 parts of quartz sand, 3 parts of trichloroethyl phosphate, 4 parts of calcium zinc composite stabilizer, 2 parts of paraffin wax, 1 part of stearic acid, 1 part of polyethylene wax, 6.8 parts of antimony trioxide and 11 parts of talc;

[0059] Among them: the chlorine content of chlorinated polyethylene is 40.8%, the melting enthalpy is 8.4J / g, the Shore hardness is 58A, the tensile strength is 9.2Mpa, and the elongation is 420%;

[0060] The melt index of POE resin is (190°C / 2.16kg) 1.2g / 10min.

[0061] Weigh the chlorinated polyethylene, polyvinyl chloride resin, erucic acid amide, basalt fiber chopped yarn, quartz sand, calcium zinc composite stabilizer, paraffin, stearic acid, polyethylene wax, antimony trioxide and talcum powder according to the weight proportion, start the mixer, stir at high speed (1500-3000 rpm), add trichloroethyl phosphate when the material temperature reaches 85°C, continue stirring at high speed, add POE resin when the material temperature reaches 100°C, stir at low speed (500-1000 rpm), when the material temperature reaches 112°C, the mixing time is 15min, discharge the material into a cold mixer, cool the material in the cold mixer to 40-45°C, discharge the material, and obtain a mixed material. The obtained mixed material is extruded and granulated by a parallel twin-screw extruder granulator, the processing temperature of the extrusion granulation is 110-160°C, the screw speed is 300-400rpm, and the granules are fully cooled to obtain a granular composite material.

[0062] Comparative Example 2

[0063] A flame-retardant chlorinated polyethylene composite material, composed of the following raw materials in parts by weight: 62 parts of chlorinated polyethylene, 32 parts of POE resin, 2.8 parts of polysiloxane, 2.3 parts of basalt fiber chopped yarn, 1.4 parts of quartz sand, 3.8 parts of trichloroethyl phosphate, 4.2 parts of calcium zinc composite stabilizer, 1.5 parts of paraffin wax, 1.2 parts of stearic acid, 1 part of polyethylene wax, 6.5 parts of antimony trioxide and 9 parts of talc;

[0064] Among them: the chlorine content of chlorinated polyethylene is 40.8%, the melting enthalpy is 8.4J / g, the Shore hardness is 58A, the tensile strength is 9.2Mpa, and the elongation is 420%;

[0065] The melt index of POE resin is (190°C / 2.16kg) 1.2g / 10min.

[0066] Weigh the chlorinated polyethylene, polysiloxane, basalt fiber chopped yarn, quartz sand, calcium zinc composite stabilizer, paraffin, stearic acid, polyethylene wax, antimony trioxide and talcum powder according to the weight proportion, start the mixer, stir at high speed (1500-3000 rpm), add trichloroethyl phosphate when the material temperature reaches 82°C, continue stirring at high speed, add POE resin when the material temperature reaches 100°C, stir at low speed (500-1000 rpm), when the material temperature reaches 115°C, the mixing time is 16min, discharge the material into a cold mixer, cool the material in the cold mixer to 40-45°C, discharge the material, and obtain a mixed material. The obtained mixed material is extruded and granulated by a parallel twin-screw extruder granulator, the processing temperature of the extrusion granulation is 110-160°C, the screw speed is 300-400rpm, and the granules are fully cooled to obtain a granular composite material.

[0067] Comparative Example 3

[0068] A flame retardant chlorinated polyethylene composite material, composed of the following raw materials in parts by weight: 68 parts of chlorinated polyethylene, 8 parts of AGR resin, 30 parts of POE resin, 5.4 parts of erucamide, 3 parts of trichloroethyl phosphate, 4 parts of calcium zinc composite stabilizer, 2 parts of paraffin, 1 part of stearic acid, 1 part of polyethylene wax, 6.8 parts of antimony trioxide and 11 parts of talc;

[0069] Among them: the chlorine content of chlorinated polyethylene is 40.8%, the melting enthalpy is 8.4J / g, the Shore hardness is 58A, the tensile strength is 9.2Mpa, and the elongation is 420%;

[0070] The melt index of POE resin is (190°C / 2.16kg) 1.2g / 10min.

[0071] Weigh the chlorinated polyethylene, AGR resin, erucic acid amide, calcium zinc composite stabilizer, paraffin, stearic acid, polyethylene wax, antimony trioxide and talcum powder according to the weight proportion, start the mixer, stir at high speed (1500-3000 rpm), add trichloroethyl phosphate when the material temperature reaches 85°C, continue stirring at high speed, add POE resin when the material temperature reaches 100°C, stir at low speed (500-1000 rpm), when the material temperature reaches 110°C, the mixing time is 14min, discharge the material into a cold mixer, cool the material in the cold mixer to 40-45°C, discharge the material, and obtain a mixed material. The obtained mixed material is extruded and granulated by a parallel twin-screw extruder granulator, the processing temperature of the extrusion granulation is 110-160°C, the screw speed is 300-400rpm, and the granules are fully cooled to obtain a granular composite material.

[0072] Comparative Example 4

[0073] A flame-retardant chlorinated polyethylene composite material, composed of the following raw materials in parts by weight: 68 parts of chlorinated polyethylene, 8 parts of AGR resin, 30 parts of POE resin, 2.2 parts of erucamide, 2 parts of basalt fiber chopped yarn, 1.2 parts of quartz sand, 3 parts of trichloroethyl phosphate, 4 parts of calcium zinc composite stabilizer, 2 parts of paraffin wax, 1 part of stearic acid, 1 part of polyethylene wax, 6.8 parts of antimony trioxide and 11 parts of talc;

[0074] Among them: the chlorine content of chlorinated polyethylene is 34.8%, the melting enthalpy is 1.5J / g, the Shore hardness is 63A, the tensile strength is 7.8Mpa, and the elongation is 450%;

[0075] The melt index of POE resin is (190°C / 2.16kg) 1.2g / 10min.

[0076] Weigh the chlorinated polyethylene, AGR resin, erucic acid amide, basalt fiber chopped yarn, quartz sand, calcium zinc composite stabilizer, paraffin, stearic acid, polyethylene wax, antimony trioxide and talcum powder according to the weight proportion, start the mixer, stir at high speed (1500-3000 rpm), add trichloroethyl phosphate when the material temperature reaches 85°C, continue stirring at high speed, add POE resin when the material temperature reaches 100°C, stir at low speed (500-1000 rpm), when the material temperature reaches 110°C, the mixing time is 14min, discharge the material into a cold mixer, cool the material in the cold mixer to 40-45°C, discharge the material, and obtain a mixed material. The obtained mixed material is extruded and granulated by a parallel twin-screw extruder granulator, the processing temperature of the extrusion granulation is 110-160°C, the screw speed is 300-400rpm, and the granules are fully cooled to obtain a granular composite material.

[0077] In order to verify the performance of the composite materials, the granular composite materials obtained in Examples 1-5 and Comparative Examples 1-4 were extruded and calendered at a temperature of 120-180°C. Products were obtained after cooling. The performance test results of the composite materials and products are shown in Table 1.

[0078] Table 1 Performance test results

[0079]

[0080] As can be seen from Table 1, the composite material prepared by the present invention has good tensile strength and elongation at break, excellent flame retardancy, good low temperature resistance, strong wear resistance, low melt viscosity, good processing fluidity, and excellent scratch resistance.

[0081] By comparing Example 1 with Comparative Example 1, it can be seen that, under the condition that other conditions remain unchanged, when the AGR resin in the composite material of the present invention is replaced by polyvinyl chloride resin, the low-temperature brittleness of the product becomes worse, the melt viscosity increases, and the fluidity decreases; by comparing Example 2 with Comparative Example 2, it can be seen that after the AGR resin in the composite material of the present invention is removed, although the POE resin is added, the melt viscosity of the composite material is still large, the fluidity decreases, and its processing performance is affected, indicating that the AGR resin and the POE resin have a synergistic effect on the processing fluidity of the composite material.

[0082] By comparing Example 1 with Comparative Example 3, it can be seen that the scratch resistance of the composite material is significantly reduced due to the absence of the compound anti-scratch agent. By comparing Example 1 with Comparative Example 4, it can be seen that when the chlorine content of the chlorinated polyethylene is less than 40%, the tensile strength and scratch resistance of the composite material are also reduced. It has been proved through experiments that when the chlorine content of the chlorinated polyethylene is 40-45% and the melting enthalpy is ≤15 J / g, the various properties of the composite material can be maintained at the best.

[0083] The high-fluidity, scratch-resistant, flame-retardant, chlorinated polyethylene composite material of the present invention is granular, and its basic color is white. According to the needs of users or production, materials of other colors can also be provided. It can be used for extruding wide-width waterproof coiled materials, tent films, floor cloths and other extrusion calendering products that require high fluidity, has better extrusion processing fluidity, scratch resistance, flame retardancy, friction resistance and anti-skid properties, and is not easy to produce scratches and cracks on the surface during construction and use. It has a simple preparation process, does not require vulcanization, is easy to recycle, has a low degree of environmental pollution, is easy to mass produce, and has a good prospect for industrial application.

[0084] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A high-flowability, scratch-resistant, flame-retardant, chlorinated polyethylene composite material, characterized in that: The invention is composed of the following raw materials in parts by weight: 60-80 parts of chlorinated polyethylene, 5-15 parts of acrylic copolymer polyvinyl chloride resin, 20-35 parts of ethylene-butene copolymer, 4-7 parts of compound anti-scratch agent, 2-4 parts of plasticizer, 3-6 parts of stabilizer, 3-6 parts of lubricant, 6-10 parts of flame retardant and 5-15 parts of reinforcing agent; The composite anti-scratch agent is composed of an anti-scratch agent, basalt fiber chopped yarn and quartz sand in a weight ratio of 1-1.2:1:0.4-0.6; The chlorine content of the chlorinated polyethylene is 40-45%, and the melting enthalpy is ≤15 J / g.

2. The high-flowability, scratch-resistant, flame-retardant chlorinated polyethylene composite material according to claim 1, characterized in that: The melt index of the ethylene-butene copolymer is 0.8 to 2.5 g / 10 min.

3. The high-flowability, scratch-resistant, flame-retardant chlorinated polyethylene composite material according to claim 1, characterized in that: The scratch-resistant agent is one of polysiloxane, organic silicone grafted long-chain alkane, erucamide, stearyl erucamide, oleamide, and ethylene bisoleamide, or a combination of two or more of them in any proportion.

4. The high-flowability, scratch-resistant, flame-retardant chlorinated polyethylene composite material according to claim 1, characterized in that: The plasticizer is one of trichloroethyl phosphate, chlorinated paraffin, and dioctyl adipate, or a combination of two or more of them in any proportion.

5. The high-flowability, scratch-resistant, flame-retardant chlorinated polyethylene composite material according to claim 1, characterized in that: The stabilizer is one or a combination of any proportion of two or more of a calcium-zinc composite stabilizer, a lead salt stabilizer, calcium stearate, lead stearate, and a rare earth composite stabilizer.

6. The high-flowability, scratch-resistant, flame-retardant chlorinated polyethylene composite material according to claim 1, characterized in that: The lubricant is one or a combination of two or more of oxidized polyethylene wax, paraffin wax, stearic acid or polyethylene wax in any proportion.

7. The high-flowability, scratch-resistant, flame-retardant chlorinated polyethylene composite material according to claim 1, characterized in that: The flame retardant is one of antimony trioxide, aluminum hydroxide or decabromodiphenyl ether or a combination of two or more of them in any proportion.

8. The high-flowability, scratch-resistant, flame-retardant chlorinated polyethylene composite material according to claim 1, characterized in that: The reinforcing agent is one of talcum powder, calcium carbonate or calcium sulfate whisker, or a combination of two or more of them in any proportion.

9. A method for preparing the high-flowability, scratch-resistant, flame-retardant chlorinated polyethylene composite material according to any one of claims 1 to 8, characterized in that: The steps include: S1. Weigh each raw material by weight; S2, putting chlorinated polyethylene, acrylic copolymer polyvinyl chloride resin, compound anti-scratch agent, stabilizer, lubricant, flame retardant and reinforcing agent into a mixer and stirring to obtain material 1; When the temperature of the material 1 reaches 80-85°C, add the plasticizer and continue stirring to obtain the material 2; When the temperature of the material 2 reaches 98-100° C., ethylene-butene copolymer is added and stirring is continued to obtain material 3; When the temperature of the material three reaches 110-120° C., the material three is introduced into a cold mixer for cooling, and when the temperature drops to 40-45° C., the material is taken out to obtain a powdery composite material; S3, extruding and granulating the powdery composite material, wherein the processing temperature of the extrusion granulation is 110-160° C., the screw speed is 300-400 rpm, and after the pellets are fully cooled, a granular composite material is obtained.

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