High-adhesiveness low-temperature-resistant chlorinated polyethylene composite material and preparation method thereof

Abstract

The invention belongs to the technical field of modified high polymer materials, and particularly discloses a high-adhesiveness low-temperature-resistant chlorinated polyethylene composite material and a preparation method thereof. The composite material is prepared from the following raw materials in parts by weight: 60-85 parts of chlorinated polyethylene, 5-15 parts of terpene resin, 10-25 parts of ethylene-butylene copolymer, 8-11 parts of a compound adhesive, 5-10 parts of a plasticizer, 3-6 parts of a stabilizer, 2-5 parts of a lubricant and 20-50 parts of a reinforcing agent. The chlorinated polyethylene, the terpene resin, the POE resin, the lubricant, the compound adhesive, the reinforcing agent and other components cooperate with one another to achieve synergistic interaction, the high-adhesiveness and low-temperature-resistant composite material is prepared, and an extruded product has better extrusion processing fluidity and high adhesiveness, is not prone to cracking in the construction and use process and is resistant to low temperature, and the service life of the product is prolonged. The preparation process is simple, vulcanization is not needed, and recovery is easy.

Description

Technical Field

[0001] The invention belongs to the technical field of modified polymer materials, and in particular relates to a high-adhesion, low-temperature-resistant 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] At present, steel wire wound medium pressure water pipes mainly include polyvinyl chloride composite (PVC) wound pipes and rubber wound pipes. Rubber wound pipes have the advantages of flame retardancy, wear resistance, high strength and good adhesion, but because they need to be vulcanized, the preparation process is complicated, and recycling is difficult, which can easily cause environmental pollution. PVC composite wound pipes have the advantages of flame retardancy, wear resistance, light weight, good toughness, and corrosion resistance, but PVC wound pipes need to add more plasticizers during the preparation process, and plasticizers are easy to precipitate, which is not environmentally friendly. Therefore, it is necessary to develop new high-performance composite materials for steel wire wound medium pressure water pipes. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a high-adhesion, low-temperature-resistant chlorinated polyethylene composite material for steel wire-wound medium-pressure water pipes and a preparation method thereof. By adding functional additives and compounding chlorinated polyethylene, terpene resin and POE resin, a high-strength ternary blended composite material can be obtained, which has good processing fluidity and high adhesion performance. The preparation process is simple, does not require vulcanization, and is easy to recycle.

[0005] In order to solve the above technical problems, the technical solution of the present invention is: High - adhesion low - temperature resistant chlorinated polyethylene composite material is composed of the following raw materials in parts by weight: 60 - 85 parts of chlorinated polyethylene, 5 - 15 parts of terpene resin, 10 - 25 parts of ethylene - butene copolymer (POE resin), 8 - 11 parts of compound adhesive, 5 - 10 parts of plasticizer, 3 - 6 parts of stabilizer, 2 - 5 parts of lubricant and 20 - 50 parts of reinforcing agent.

[0006] In order to improve the adhesion of the ternary blend composite material of chlorinated polyethylene, terpene resin and POE resin to the winding steel wire, the compound adhesive is adopted. The compound adhesive is composed of adhesive, GLR - 20 resin (resorcinol - formaldehyde resin) and epoxy resin in a weight ratio of 0.9 - 1.1:1:1.2 - 1.4. Among them, the adhesive can effectively improve the viscosity of the composite material surface, so that the material has better bonding force with the winding steel wire. At the same time, it also has a lubricating effect, reducing the decomposition caused by excessive frictional heat due to too strong shear. The adhesive can be one or a combination of two or more of hexamethoxymethylmelamine - type methylene donors RA, RA - 65, EA, RE, RFD, RZ, RH in any proportion. RA and RA - 65 have better adhesion, so the adhesive is more preferably RA and RA - 65. GLR - 20 resin is a modified resorcinol - formaldehyde resin. As a methylene acceptor adhesive, it does not contain free formaldehyde. When used in combination with the methylene donor, it can effectively play the role of bonding with the skeleton material. Epoxy resin is suitable as a surfactant, which can improve the bonding ability of the composite material and also improve brittleness. After compounding, the three cooperate synergistically to significantly improve the surface viscosity of the material and further improve the bonding force of the material. Epoxy resin is mainly composed of bisphenol A propane, and its epoxy value index is 0.48 - 0.54 mol / 100g, with good bonding strength and chemical resistance, and is preferably epoxy resin E - 51.

[0007] Preferably, the chlorine content of the chlorinated polyethylene is 30 - 40%, and the melting enthalpy ≤ 15 J / g (DSC method).

[0008] The terpene resin is a thermoplastic block copolymer, with excellent compatibility, weather resistance and tackifying effect. The terpene resin is preferably TR105, TP1105 or T80 type. Among them, when the TR105 type of terpene resin is used in the preparation of the composite material, the adhesion is better, and it is easier to be compatible with chlorinated polyethylene. The strength of the prepared composite material is relatively high. Therefore, the terpene resin is more preferably TR105 type.

[0009] Preferably, the melt index of the ethylene-butene copolymer (POE resin) is 0.8-2.5 g / 10min (190 °C / 2.16 kg), and the melting temperature is 34-45 °C. The POE resin can be selected from types 7467, 7256 or 8440. Among them, when preparing the composite material, the 7467-type POE resin has better processing fluidity and is easier to be compatible with chlorinated polyethylene, and the strength and hardness of the prepared composite material are relatively high. Therefore, the POE resin is more preferably of type 7467.

[0010] The plasticizer can improve the softness of the composite material during the processing, reduce the melt viscosity of the composite material, improve the fluidity, and lower the glass transition temperature. Preferably, the plasticizer is one or a combination of two or more of dioctyl terephthalate (DOTP), trichloroethyl phosphate (TCEP), chlorinated paraffin, and diisooctyl sebacate (DOS) in any proportion. Since dioctyl terephthalate (DOTP) is a main plasticizer with excellent performance and better cold resistance, the plasticizer is more preferably dioctyl terephthalate (DOTP).

[0011] Preferably, the stabilizer is one or a combination of two or more of calcium-zinc composite stabilizer, lead salt stabilizer, calcium stearate, lead stearate, and rare earth composite stabilizer. During the production and processing process, the addition amount of the stabilizer needs to be controlled well. If the addition amount of the stabilizer is too small, the heat resistance stability during the mixing, processing, and product use processes will be very poor, and the composite material is likely to decompose; if the addition amount of the stabilizer is too large, the stabilizer in the composite material will precipitate.

[0012] Preferably, the lubricant is one or a combination of two or more of oxidized polyethylene wax, paraffin wax, stearic acid, and polyethylene wax. During the production and processing process, the addition amount of the lubricant needs to be controlled well. If the amount of the lubricant is too low, it will affect the fluidity during the processing; if the amount is too high, it will affect the mechanical properties and flame retardancy of the composite material.

[0013] Preferably, the reinforcing agent is one or a combination of two or more of calcium carbonate, talcum powder, and calcium sulfate whiskers. Due to the high whiteness, small particle size, large sedimentation volume, strong stability, and high covering power of light calcium carbonate, calcium carbonate plays a role of skeleton in plastic products, can improve the dimensional stability, hardness, and rigidity of plastics, and at the same time improve the surface gloss and flatness of the products. In addition, the price of light calcium carbonate is relatively low, which can reduce the formulation cost. Therefore, the reinforcing agent is more preferably light calcium carbonate.

[0014] The preparation method of the high-adhesion low-temperature chlorinated polyethylene composite material includes the following steps: S1. Weigh each raw material according to the weight parts; S2. Put chlorinated polyethylene, terpene resin, compound adhesive, stabilizer, lubricant and reinforcing agent into a mixer and stir at high speed to obtain Material 1; When the temperature of Material 1 reaches 80 - 85 °C, add plasticizer and continue to stir at high speed to obtain Material 2; When the temperature of Material 2 reaches 98 - 100 °C, add ethylene - butene copolymer and stir at low speed to obtain Material 3; When the temperature of Material 3 reaches 110 - 120 °C, introduce Material 3 into a cold mixer for cooling. When the temperature drops to 40 - 45 °C, take it out to obtain a powdery composite material; S3. Extrude and pelletize the powdery composite material. The processing temperature for extrusion and pelletization is 110 - 160 °C, and the screw speed is 300 - 400 rpm. After the pellets are fully cooled, granular composite materials are obtained.

[0015] The present invention has at least the following beneficial effects: (1) Terpene resin is added to the high - adhesion low - temperature resistant chlorinated polyethylene composite material provided by the present invention. The obtained composite material has better adhesion performance and strength. Due to the excellent compatibility, weather resistance and tackifying effect of terpene resin, its compatibility with chlorinated polyethylene is improved, further improving the processability, adhesion performance and strength of the composite material, and increasing the adhesion force with the wound steel wire.

[0016] (2) POE resin is added to the high - adhesion low - temperature resistant chlorinated polyethylene composite material provided by the present invention. It has a relatively high melt index and is compounded with terpene resin, which can effectively improve the fluidity during the processing of the composite material, and is beneficial to reducing the frictional heat of the extruded product. POE also has good tensile properties and tensile strength, ensuring the durability and stability of the product.

[0017] (3) The high - adhesion low - temperature resistant chlorinated polyethylene composite material provided by the present invention adopts the compounding method of chlorinated polyethylene, terpene resin and POE resin. Compared with the existing rubber materials, the composite material has excellent impact resistance and low - temperature toughness, good corrosion resistance, high strength and good adhesion. Moreover, the preparation process is simple, does not require vulcanization, is easy to recycle, and has low or no environmental pollution.

[0018] (4) The high - adhesion low - temperature resistant chlorinated polyethylene composite material provided by the present invention adopts the method of blending compound adhesive and terpene resin, which cooperate with each other synergistically, can effectively improve the surface adhesion of the material, thereby improving the adhesion force between the composite material and the wound steel wire, and enhancing the burst pressure of the medium - pressure pipe.

[0019] (5) The composite material of the present invention can use the same extrusion equipment as that in PVC production, which is easy to realize industrial production. Moreover, the products such as medium-pressure pipes wound with steel wires extruded have excellent low-temperature toughness, good tensile properties, high adhesion, long service life, and are environmentally friendly and harmless.

[0020] (6) The preparation method of the present invention uses batch raw materials and industrial equipment, has strong generality, is easy to scale up production. The obtained high-adhesion low-temperature-resistant chlorinated polyethylene composite material with excellent performance meets the requirements of high-performance materials and has good industrial application prospects. Specific Embodiments

[0021] The present invention will be further specifically described below in conjunction with embodiments. In the following detailed description, only some exemplary embodiments of the present invention are described by way of illustration. Undoubtedly, those of ordinary skill in the art can recognize that the described embodiments can be modified in various different 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 used to limit the protection scope of the claims.

[0022] Example 1 The high-adhesion low-temperature-resistant chlorinated polyethylene composite material is composed of the following raw materials in parts by weight: 72 parts of chlorinated polyethylene, 7 parts of terpene resin, 21 parts of POE resin, 2.5 parts of adhesive RA, 2.5 parts of GLR-20 resin, 3.2 parts of epoxy resin, 5 parts of DOTP, 3 parts of DOS, 4 parts of calcium-zinc composite stabilizer, 2 parts of paraffin, 0.5 part of stearic acid, 0.8 part of polyethylene wax, and 40 parts of light calcium carbonate; Among them: the chlorine content of the chlorinated polyethylene is 36.1%, the melting enthalpy is 0.4 J / g, the Shore hardness is 57A, the tensile strength is 10.2 Mpa, and the elongation at break is 711%; The melt index of the POE resin is 1.2 g / 10 min (190 °C / 2.16 kg).

[0023] Weigh according to the stated parts by weight. Pour chlorinated polyethylene, terpene resin, binder RA, GLR-20 resin, epoxy resin, calcium-zinc composite stabilizer, paraffin wax, stearic acid, polyethylene wax and light calcium carbonate into a high-speed mixer. Start the mixer and stir at high speed (1500 - 3000 revolutions per minute). When the material temperature reaches 85°C, add DOTP and DOS, and continue to stir at high speed. When the material temperature reaches 100°C, add POE resin and stir at low speed (500 - 1000 revolutions per minute). When the material temperature reaches 110°C, the mixing time is 14 minutes. Discharge the material into a cold mixer. In the cold mixer, cool the material to 40 - 45°C, and then discharge the material to obtain a mixed material. Extrude and pelletize the obtained mixed material with a parallel twin-screw extruder. The processing temperature for extrusion and pelletization is 110 - 160°C, and the screw speed is 300 - 400 rpm. After the pellets are fully cooled, granular composite materials are obtained.

[0024] Example 2 A high-adhesion and low-temperature-resistant chlorinated polyethylene composite material is composed of the following raw materials in parts by weight: 65 parts of chlorinated polyethylene, 10 parts of terpene resin, 25 parts of POE resin, 2.8 parts of binder EA, 2.5 parts of GLR-20 resin, 3.0 parts of epoxy resin, 5.5 parts of DOTP, 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 and 35 parts of light calcium carbonate; Among them: the chlorine content of the chlorinated polyethylene is 36.1%, the melting enthalpy is 0.4 J / g, the Shore hardness is 57A, the tensile strength is 10.2 Mpa, and the elongation at break is 711% (the chlorinated polyethylene is the same raw material as in Example 1); The melt index of the POE resin is 1.2 g / 10 min (190°C / 2.16 kg) (the POE resin is the same raw material as in Example 1).

[0025] Weigh according to the stated parts by weight. Pour chlorinated polyethylene, terpene resin, binder EA, GLR-20 resin, epoxy resin, calcium-zinc composite stabilizer, paraffin wax, stearic acid, polyethylene wax and light calcium carbonate into a high-speed mixer. Start the mixer and stir at high speed (1500 - 3000 revolutions per minute). When the material temperature reaches 80°C, add DOTP, and continue to stir at high speed. When the material temperature reaches 100°C, add POE resin and stir at low speed (500 - 1000 revolutions per minute). When the material temperature reaches 110°C, the mixing time is 15 minutes. Discharge the material into a cold mixer. In the cold mixer, cool the material to 40 - 45°C, and then discharge the material to obtain a mixed material. Extrude and pelletize the obtained mixed material with a parallel twin-screw extruder. The processing temperature for extrusion and pelletization is 110 - 160°C, and the screw speed is 300 - 400 rpm. After the pellets are fully cooled, granular composite materials are obtained.

[0026] Example 3 High - adhesion low - temperature resistant chlorinated polyethylene composite material, which is composed of the following raw materials in parts by weight: 68 parts of chlorinated polyethylene, 14 parts of terpene resin, 18 parts of POE resin, 2.3 parts of binder RA, 2.8 parts of GLR - 20 resin, 3.6 parts of epoxy resin, 7 parts of DOTP, 3.5 parts of rare - earth composite stabilizer, 2 parts of paraffin wax, 1.2 parts of stearic acid, 1 part of polyethylene wax and 45 parts of light calcium carbonate; Among them: the chlorine content of chlorinated polyethylene is 36.1%, the melting enthalpy is 0.4 J / g, the Shore hardness is 57A, the tensile strength is 10.2 Mpa, and the elongation at break is 711% (the same raw material of chlorinated polyethylene as in Example 1); The melt index of POE resin is 1.2 g / 10 min (190℃ / 2.16 kg) (the same raw material of POE resin as in Example 1).

[0027] Weigh according to the said parts by weight. Pour chlorinated polyethylene, terpene resin, binder RA, GLR - 20 resin, epoxy resin, rare - earth composite stabilizer, paraffin wax, stearic acid, polyethylene wax and light calcium carbonate into a high - speed mixer. Start the mixer and stir at high speed (1500 - 3000 revolutions per minute). When the material temperature reaches 83℃, add DOTP. Continue to stir at high speed. When the material temperature reaches 100℃, add POE resin and stir at low speed (500 - 1000 revolutions per minute). When the material temperature reaches 110℃, the mixing time is 16 min. Discharge the material into a cold mixer. In the cold mixer, the material is cooled to 40 - 45℃, then discharge the material to obtain a mixed material. Use a parallel twin - screw extruder to extrude and pelletize the obtained mixed material. The processing temperature for extrusion and pelletization is 110 - 160℃, the screw speed is 300 - 400 rpm. After the pellets are fully cooled, granular composite materials are obtained.

[0028] Example 4 The difference between this example and Example 1 is that the indexes of chlorinated polyethylene and POE raw materials are different.

[0029] High - adhesion low - temperature resistant chlorinated polyethylene composite material, which is composed of the following raw materials in parts by weight: 72 parts of chlorinated polyethylene, 7 parts of terpene resin, 21 parts of POE resin, 2.5 parts of binder RA, 2.5 parts of GLR - 20 resin, 3.2 parts of epoxy resin, 5 parts of DOTP, 3 parts of DOS, 4 parts of calcium - zinc composite stabilizer, 2 parts of paraffin wax, 0.5 parts of stearic acid, 0.8 parts of polyethylene wax and 40 parts of light calcium carbonate; Among them: the chlorine content of chlorinated polyethylene is 40.4%, the melting enthalpy is 3.8 J / g, the Shore hardness is 58A, the tensile strength is 8.3 Mpa, and the elongation at break is 643%; The melt index of POE resin is 1.8 g / 10 min (190℃ / 2.16 kg).

[0030] Weigh the components according to the specified parts by weight. Pour chlorinated polyethylene, terpene resin, binder RA, GLR-20 resin, epoxy resin, calcium-zinc composite stabilizer, paraffin wax, stearic acid, polyethylene wax and light calcium carbonate into a high-speed mixer. Start the mixer and stir at high speed (1500 - 3000 revolutions per minute). When the material temperature reaches 85°C, add DOTP and DOS, and continue high-speed stirring. When the material temperature reaches 100°C, add POE resin and stir at low speed (500 - 1000 revolutions per minute). When the material temperature reaches 110°C, mix for 14 minutes, discharge the material into a cold mixer, and cool the material in the cold mixer to 40 - 45°C, then discharge the material to obtain a mixed material. Extrude and pelletize the obtained mixed material using a parallel twin-screw extruder. The processing temperature for extrusion and pelletization is 110 - 160°C, and the screw speed is 300 - 400 rpm. After the pellets are fully cooled, granular composite materials are obtained.

[0031] Example 5 The difference between this example and Example 2 lies in the different performance parameters of the chlorinated polyethylene and POE raw materials.

[0032] A high-adhesion and low-temperature-resistant chlorinated polyethylene composite material is composed of the following raw materials in parts by weight: 65 parts of chlorinated polyethylene, 10 parts of terpene resin, 25 parts of POE resin, 2.8 parts of binder EA, 2.5 parts of GLR-20 resin, 3.0 parts of epoxy resin, 5.5 parts of DOTP, 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 and 35 parts of light calcium carbonate; Among them: the chlorine content of the chlorinated polyethylene is 40.4%, the melting enthalpy is 3.8 J / g, the Shore hardness is 58A, the tensile strength is 8.3 Mpa, and the elongation at break is 643% (the chlorinated polyethylene is the same raw material as in Example 4); The melt index of the POE resin is 1.8 g / 10 min (190°C / 2.16 kg) (the POE resin is the same raw material as in Example 4).

[0033] Weigh the ingredients according to the stated parts by weight. Pour chlorinated polyethylene, terpene resin, binder EA, GLR-20 resin, epoxy resin, calcium-zinc composite stabilizer, paraffin wax, stearic acid, polyethylene wax, and light calcium carbonate into a high-speed mixer. Start the mixer and stir at high speed (1500 - 3000 revolutions per minute). When the material temperature reaches 80°C, add DOTP. Continue to stir at high speed. When the material temperature reaches 100°C, add POE resin and stir at low speed (500 - 1000 revolutions per minute). When the material temperature reaches 110°C, mix for 15 minutes, then discharge the material into a cold mixer. In the cold mixer, cool the material to 40 - 45°C, then discharge the material to obtain a mixed material. Extrude and pelletize the obtained mixed material using a parallel twin-screw extruder. The processing temperature for extrusion and pelletization is 110 - 160°C, and the screw speed is 300 - 400 rpm. After the pellets are fully cooled, a granular composite material is obtained.

[0034] Comparative Example 1 Compared with Example 2, this comparative example only removes the terpene resin, and the others are the same.

[0035] The chlorinated polyethylene composite material is composed of the following raw materials in parts by weight: 65 parts of chlorinated polyethylene, 25 parts of POE resin, 2.8 parts of binder EA, 2.5 parts of GLR-20 resin, 3.0 parts of epoxy resin, 5.5 parts of DOTP, 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, and 35 parts of light calcium carbonate; Among them: The chlorine content of chlorinated polyethylene is 36.1%, the melting enthalpy is 0.4 J / g, the Shore hardness is 57A, the tensile strength is 10.2 Mpa, and the elongation at break is 711%; The melt index of POE resin is 1.2 g / 10 min (190°C / 2.16 kg).

[0036] Weigh the ingredients according to the stated parts by weight. Pour chlorinated polyethylene, binder EA, GLR-20 resin, epoxy resin, calcium-zinc composite stabilizer, paraffin wax, stearic acid, polyethylene wax, and light calcium carbonate into a high-speed mixer. Start the mixer and stir at high speed (1500 - 3000 revolutions per minute). When the material temperature reaches 80°C, add DOTP. Continue to stir at high speed. When the material temperature reaches 100°C, add POE resin and stir at low speed (500 - 1000 revolutions per minute). When the material temperature reaches 110°C, mix for 15 minutes, then discharge the material into a cold mixer. In the cold mixer, cool the material to 40 - 45°C, then discharge the material to obtain a mixed material. Extrude and pelletize the obtained mixed material using a parallel twin-screw extruder. The processing temperature for extrusion and pelletization is 110 - 160°C, and the screw speed is 300 - 400 rpm. After the pellets are fully cooled, a granular composite material is obtained.

[0037] Comparative Example 2 Compared with Example 1, the adhesives added in this comparative example were not compounded.

[0038] The chlorinated polyethylene composite material is composed of the following raw materials in parts by weight: 72 parts of chlorinated polyethylene, 7 parts of terpene resin, 21 parts of POE resin, 2.5 parts of adhesive RA, 5 parts of DOTP, 3 parts of DOS, 4 parts of calcium-zinc composite stabilizer, 2 parts of paraffin wax, 0.5 part of stearic acid, 0.8 part of polyethylene wax, and 40 parts of light calcium carbonate; Among them: the chlorine content of the chlorinated polyethylene is 36.1%, the melting enthalpy is 0.4 J / g, the Shore hardness is 57A, the tensile strength is 10.2 Mpa, and the elongation at break is 711%; The melt index of the POE resin is 1.2 g / 10 min (190 °C / 2.16 kg).

[0039] Weigh according to the above parts by weight. Pour the chlorinated polyethylene, terpene resin, adhesive RA, calcium-zinc composite stabilizer, paraffin wax, stearic acid, polyethylene wax, and light calcium carbonate into a high-speed mixer. Start the mixer and stir at a high speed (1500 - 3000 revolutions per minute). When the material temperature reaches 85 °C, add DOTP and DOS, and continue to stir at a high speed. When the material temperature reaches 100 °C, add the POE resin and stir at a low speed (500 - 1000 revolutions per minute). When the material temperature reaches 110 °C, the mixing time is 14 minutes. Discharge the material into a cold mixer. In the cold mixer, cool the material to 40 - 45 °C, discharge the material, and obtain a mixed material. Extrude and pelletize the obtained mixed material with a parallel twin-screw extruder. The processing temperature for extrusion and pelletization is 110 - 160 °C, the screw speed is 300 - 400 rpm. After the pellets are fully cooled, granular composite materials are obtained.

[0040] Comparative Example 3 Compared with Example 1, the difference is only the performance parameters (low chlorine content) of the chlorinated polyethylene.

[0041] The chlorinated polyethylene composite material is composed of the following raw materials in parts by weight: 72 parts of chlorinated polyethylene, 7 parts of terpene resin, 21 parts of POE resin, 2.5 parts of adhesive RA, 2.5 parts of GLR-20 resin, 3.2 parts of epoxy resin, 5 parts of DOTP, 3 parts of DOS, 4 parts of calcium-zinc composite stabilizer, 2 parts of paraffin wax, 0.5 part of stearic acid, 0.8 part of polyethylene wax, and 40 parts of light calcium carbonate; Among them: the chlorine content of the chlorinated polyethylene is 26.1%, the melting enthalpy is 0.4 J / g, the Shore hardness is 55A, the tensile strength is 8.2 Mpa, and the elongation at break is 689%; The melt index of the POE resin is 1.2 g / 10 min (190 °C / 2.16 kg).

[0042] Weigh the components according to the specified parts by weight. Pour chlorinated polyethylene, terpene resin, binder RA, GLR-20 resin, epoxy resin, calcium-zinc composite stabilizer, paraffin wax, stearic acid, polyethylene wax, and light calcium carbonate into a high-speed mixer. Start the mixer and stir at a high speed (1500 - 3000 revolutions per minute). When the material temperature reaches 85°C, add DOTP and DOS, and continue high-speed stirring. When the material temperature reaches 100°C, add POE resin and stir at a low speed (500 - 1000 revolutions per minute). When the material temperature reaches 110°C, mix for 14 minutes, then discharge the material into a cold mixer. In the cold mixer, cool the material to 40 - 45°C, and then discharge the material to obtain a mixed material. Extrude and pelletize the obtained mixed material using a parallel twin-screw extruder. The processing temperature for extrusion and pelletization is 110 - 160°C, and the screw speed is 300 - 400 rpm. After the pellets are fully cooled, granular composite materials are obtained.

[0043] To verify the performance of the composite materials, the granular composite materials prepared in Examples 1 - 5 and Comparative Examples 1 - 3 were respectively used to extrude and form wire-wound pipes. The extrusion temperature was 120 - 180°C, and pipe products were obtained after cooling. The performance test results of each composite material and product are shown in Table 1.

[0044] Table 1 Performance Test Results As can be seen from Table 1, the composite materials prepared by the present invention have good tensile strength and elongation at break, good low-temperature resistance, low melt viscosity, good processing fluidity, high adhesion, and excellent adhesion performance with the wound steel wire.

[0045] By comparing Example 2 with Comparative Example 1, it can be seen that after removing the terpene resin in the combined material of the present invention, although a compound binder is added, the adhesion strength of the composite material still decreases, affecting its adhesion performance with the steel wire. This shows that the terpene resin and the compound binder play a synergistic role in the adhesion of the composite material.

[0046] By comparing Example 1 with Comparative Example 2, it can be seen that due to the absence of the compound binder, the adhesion performance of the composite material decreases significantly. By comparing Example 1 with Comparative Example 3, it can be seen that when the chlorine content of chlorinated polyethylene is less than 30%, the tensile strength and adhesion performance of the composite material also decrease. Through experiments, it is proved that when the chlorine content of chlorinated polyethylene is 30 - 40% and the melting enthalpy ≤ 15 J / g, the performance of the composite material can be maintained at the best.

[0047] The high-adhesion low-temperature-resistant 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 extruded plastic pipe products such as medium-pressure water pipes that need to be adhered to winding steel wires, and has better extrusion processing fluidity, adhesiveness, tensile properties and low-temperature resistance, and can increase the bursting pressure of the pipes. Its preparation process is simple, does not require vulcanization, is easy to recycle, has a low degree of environmental pollution, is easy to scale up production, and has good industrial application prospects.

[0048] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. A high-adhesion, low-temperature-resistant chlorinated polyethylene composite material, characterized in that: The invention is composed of the following raw materials in parts by weight: 60-85 parts of chlorinated polyethylene, 5-15 parts of terpene resin, 10-25 parts of ethylene-butene copolymer, 8-11 parts of compound adhesive, 5-10 parts of plasticizer, 3-6 parts of stabilizer, 2-5 parts of lubricant and 20-50 parts of reinforcing agent; The compound adhesive is composed of an adhesive, a GLR-20 resin and an epoxy resin in a weight ratio of 0.9 to 1.1:1:1.2 to 1.

4.

2. The high-adhesion low-temperature-resistant chlorinated polyethylene composite material according to claim 1, characterized in that: The chlorine content of the chlorinated polyethylene is 30-40%, and the melting enthalpy is ≤15 J / g.

3. The high-adhesion low-temperature-resistant chlorinated polyethylene composite material according to claim 1, characterized in that: The terpene resin is any one of TR105, TP1105 or T80.

4. The high-adhesion low-temperature-resistant 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.

5. The high-adhesion low-temperature-resistant chlorinated polyethylene composite material according to claim 1, characterized in that: The adhesive is one of the adhesives RA, RA-65, EA, RE, RFD, RZ, and RH, or a combination of two or more of them in any proportion.

6. The high-adhesion low-temperature-resistant chlorinated polyethylene composite material according to claim 1, characterized in that: The plasticizer is one of dioctyl terephthalate, trichloroethyl phosphate, chlorinated paraffin, and diisooctyl sebacate, or a combination of two or more of them in any proportion.

7. The high-adhesion low-temperature-resistant 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.

8. The high-adhesion low-temperature-resistant 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.

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

10. The method for preparing the high-adhesion low-temperature-resistant chlorinated polyethylene composite material according to any one of claims 1 to 9, comprising the following steps: S1. Weigh each raw material by weight; S2, putting chlorinated polyethylene, terpene resin, compound adhesive, stabilizer, lubricant 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 stirred 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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