High-adhesion, low-temperature-resistant 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-adhesion, low-temperature-resistant 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 85 parts of chlorinated polyethylene, 5 to 15 parts of terpene resin, 10 to 25 parts of ethylene-butene copolymer, 8 to 11 parts of compound adhesive, 5 to 10 parts of plasticizer, 3 to 6 parts of stabilizer, 2 to 5 parts of lubricant and 20 to 50 parts of reinforcing agent. The present invention prepares a high-adhesion, low-temperature-resistant composite material by the mutual coordination and synergistic effect of components such as chlorinated polyethylene, terpene resin, POE resin and lubricant, compound adhesive and reinforcing agent. The extruded product has better extrusion processing fluidity and high adhesion, is not easy to crack and is low-temperature resistant during construction and use, has a simple preparation process, 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 particularly 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 with excellent resistance to heat, oxygen, ozone, acids, alkalis, and chemicals. CPE contains chlorine, making it inherently flame-retardant and drip-resistant. It is non-toxic, odorless, and free of heavy metals and PAHs (carcinogenic polycyclic aromatic hydrocarbons), fully complying with environmental requirements. Its high filling capacity allows it to be manufactured into products meeting a variety of performance requirements. CPE resin exhibits a range of excellent properties. It serves as an excellent impact modifier for polyvinyl chloride (PVC) plastics and is a well-rounded elastomer with a wide range of applications, including cables, wires, hoses, tapes, rubber and plastic products, sealants, flame-retardant conveyor belts, waterproof membranes, tent films, floor coverings, and various profiles. CPE can also be blended with polypropylene, high- and low-pressure polyethylene, and ABS to improve the flame retardancy, impact resistance, aging resistance, and printability of these plastics.

[0003] Currently, steel-wire wound medium-pressure water pipes primarily include polyvinyl chloride (PVC) composite pipes and rubber-based pipes. Rubber-based pipes offer advantages such as flame retardancy, abrasion resistance, high strength, and good adhesion. However, due to the need for vulcanization, the manufacturing process is complex, recycling is difficult, and they can easily cause environmental pollution. PVC composite pipes offer advantages such as flame retardancy, abrasion resistance, light weight, good toughness, and corrosion resistance. However, the manufacturing process requires the addition of a high amount of plasticizers, which are prone to precipitation and are environmentally unfriendly. Therefore, there is a need 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 adopting a compounding method of 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:

[0006] The high-adhesion and 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.

[0007] To improve the adhesion of a ternary composite material of chlorinated polyethylene, terpene resin, and POE resin to the winding steel wire, a composite adhesive is used. The composite adhesive consists 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. The adhesive effectively improves the surface viscosity of the composite material, thereby enhancing adhesion to the winding steel wire. It also provides lubrication, reducing decomposition caused by excessive frictional heat due to excessive shear. The adhesive can be one or a combination of two or more of the hexamethoxymethylmelamine methylene donors RA, RA-65, EA, RE, RFD, RZ, and RH in any proportion. RA and RA-65 exhibit better adhesion, making them more preferred. GLR-20 resin is a modified resorcinol formaldehyde resin. As a methylene acceptor adhesive, it contains no free formaldehyde. When used in combination with a methylene donor, it effectively bonds to the framework material. Epoxy resin is suitable as a surfactant, improving the bonding ability of composite materials and reducing brittleness. After compounding, the synergistic effect of the three can significantly improve the surface viscosity of the material, further enhancing its adhesion. The epoxy resin is primarily composed of diphenol propane, with an epoxy value of 0.48 to 0.54 mol / 100g, exhibiting good bonding strength and chemical resistance. Epoxy resin E-51 is preferred.

[0008] Preferably, the chlorine content of the chlorinated polyethylene is 30-40%, and the melting enthalpy is ≤15 J / g (DSC method).

[0009] The terpene resin is a thermoplastic block copolymer with excellent compatibility, weather resistance, and tackifying properties. The terpene resin is preferably TR105, TP1105, or T80. TR105 offers better adhesion and compatibility with chlorinated polyethylene when preparing composite materials, resulting in relatively high strength composite materials. Therefore, TR105 is a more preferred terpene resin.

[0010] Preferably, the ethylene-butene copolymer (POE resin) has a melt index of 0.8-2.5 g / 10 min (190°C / 2.16 kg) and a melting temperature of 34-45°C. POE resins of type 7467, 7256, or 8440 can be used. POE resin type 7467 offers better processing fluidity and compatibility with chlorinated polyethylene when preparing composite materials. The resulting composite materials exhibit relatively high strength and hardness. Therefore, type 7467 is the more preferred POE resin.

[0011] Plasticizers can improve the flexibility of composite materials during processing, reduce their melt viscosity, enhance their fluidity, and lower their glass transition temperature. Preferably, the plasticizer is one or a combination of two or more of the following in any proportion: dioctyl terephthalate (DOTP), trichloroethyl phosphate (TCEP), chlorinated paraffin, or diisooctyl sebacate (DOS). Since DOTP is a high-performance primary plasticizer with improved cold resistance, it is more preferably used as the plasticizer.

[0012] Preferably, the stabilizer is one or a combination of two or more of the group consisting of a calcium-zinc composite stabilizer, a lead salt stabilizer, calcium stearate, lead stearate, and a rare earth composite stabilizer in any proportion. During production and processing, the amount of stabilizer added must be carefully controlled. Too little stabilizer can lead to poor heat stability during mixing, processing, and product use, and the composite material can easily decompose. Too much stabilizer can cause the stabilizer to precipitate from the composite material.

[0013] Preferably, 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. During the production process, the amount of lubricant added needs to be carefully controlled. Too little lubricant can affect fluidity during processing, while too much can affect the mechanical and flame retardant properties of the composite material.

[0014] Preferably, the reinforcing agent is one or a combination of two or more of calcium carbonate, talc, or calcium sulfate whiskers in any proportion. Light calcium carbonate, due to its high whiteness, small particle size, large sedimentation volume, strong stability, and high coverage, plays a skeletal role in plastic products, improving their dimensional stability, hardness, and rigidity, while also enhancing the surface gloss and smoothness of the finished product. Furthermore, light calcium carbonate is relatively inexpensive, which can reduce formulation costs. Therefore, light calcium carbonate is a more preferred reinforcing agent.

[0015] The preparation method of the high-adhesion low-temperature resistant chlorinated polyethylene composite material comprises the following steps:

[0016] S1. Weigh each raw material by weight;

[0017] S2, placing chlorinated polyethylene, terpene resin, compound adhesive, stabilizer, lubricant and reinforcing agent into a mixer and stirring at high speed to obtain material 1;

[0018] When the temperature of the material 1 reaches 80-85°C, a plasticizer is added and the high-speed stirring is continued to obtain the material 2;

[0019] When the temperature of the second material reaches 98-100° C., ethylene-butene copolymer is added and stirred at a low speed to obtain a third material;

[0020] When the temperature of the material 3 reaches 110-120°C, the material 3 is introduced into a cold mixer for cooling. When the temperature drops to 40-45°C, the material is taken out to obtain a powdered composite material.

[0021] S3. Extruding and granulating the powdery composite material. The processing temperature of the extrusion and granulation is 110-160° C., the screw speed is 300-400 rpm, and the pellets are fully cooled to obtain a granular composite material.

[0022] The present invention has at least the following beneficial effects:

[0023] (1) The high-adhesion, low-temperature-resistant chlorinated polyethylene composite material provided by the present invention is added with a terpene resin, and the resulting composite material has better adhesion and strength. Since the terpene resin has excellent compatibility, weather resistance and viscosity-increasing effect, its compatibility with chlorinated polyethylene is improved, and the processability, adhesion and strength of the composite material are further improved, and the adhesion to the winding steel wire is improved.

[0024] (2) The POE resin added to the high-adhesion, low-temperature-resistant chlorinated polyethylene composite material provided by the present invention has a high melt index. When compounded with the terpene resin, it can effectively improve the fluidity of the composite material during processing, which is beneficial to reducing the friction heat of the extruded product. POE also has good tensile properties and tensile strength, ensuring the durability and stability of the product.

[0025] (3) The high-adhesion, low-temperature-resistant chlorinated polyethylene composite material provided by the present invention is compounded with chlorinated polyethylene, terpene resin and POE resin, so that the composite material has excellent impact resistance and low-temperature toughness, good corrosion resistance, high strength and good adhesion 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.

[0026] (4) The high-adhesion, low-temperature-resistant chlorinated polyethylene composite material provided by the present invention adopts a blending method of a compound adhesive and a terpene resin, which cooperates with each other to enhance the synergistic effect, and can effectively improve the surface adhesion of the material, thereby improving the adhesion between the composite material and the winding steel wire, and enhancing the bursting pressure of the medium-pressure pipe.

[0027] (5) The composite material of the present invention can be produced using the same extrusion equipment as PVC, and is easy to realize industrial production. The extruded steel wire wound medium pressure pipe and other products have excellent low temperature toughness, good tensile properties, high adhesion, long service life, and are environmentally friendly.

[0028] (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 high-performance, high-adhesion, low-temperature-resistant chlorinated polyethylene composite material meets the requirements of high-performance materials and has good prospects for industrial application. DETAILED DESCRIPTION

[0029] The present invention will be further described in detail below with reference to the embodiments. In the following detailed description, certain exemplary embodiments of the present invention are described only by way of illustration. It is understood that those skilled in the art will recognize that the described embodiments may be modified in various ways without departing from the spirit and scope of the present invention. Therefore, the descriptions in the embodiments are illustrative in nature and are not intended to limit the scope of the claims.

[0030] Example 1

[0031] A 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 RA adhesive, 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;

[0032] 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 is 711%;

[0033] The melt index of POE resin is (190°C / 2.16kg) 1.2g / 10min.

[0034] The chlorinated polyethylene, terpene resin, adhesive RA, GLR-20 resin, epoxy resin, calcium zinc composite stabilizer, paraffin wax, stearic acid, polyethylene wax, and light calcium carbonate were weighed according to the stated weight ratios and poured into a high-speed mixer. The mixer was started and stirred at high speed (1500-3000 rpm). When the material temperature reached 85°C, DOTP and DOS were added. High-speed stirring was continued. When the material temperature reached 100°C, POE resin was added and stirred at low speed (500-1000 rpm). When the material temperature reached 110°C, the mixing time was 14 minutes, and the material was discharged into a cold mixer. The material was cooled to 40-45°C in the cold mixer and discharged to obtain a mixed material. The obtained mixed material was extruded and granulated using a parallel twin-screw extruder granulator at a processing temperature of 110-160°C and a screw speed of 300-400 rpm. After the pellets were fully cooled, a granular composite material was obtained.

[0035] Example 2

[0036] A high-adhesion, 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 EA adhesive, 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;

[0037] The chlorinated polyethylene has a chlorine content of 36.1%, a melting enthalpy of 0.4 J / g, a Shore hardness of 57A, a tensile strength of 10.2 MPa, and an elongation of 711% (the raw material is the same as that of the chlorinated polyethylene in Example 1);

[0038] 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).

[0039] The chlorinated polyethylene, terpene resin, adhesive EA, GLR-20 resin, epoxy resin, calcium zinc composite stabilizer, paraffin wax, stearic acid, polyethylene wax, and light calcium carbonate were weighed according to the aforementioned weight ratios and poured into a high-speed mixer. The mixer was started and stirred at high speed (1500-3000 rpm). When the material temperature reached 80°C, DOTP was added and continued stirring at high speed. When the material temperature reached 100°C, POE resin was added and stirred at low speed (500-1000 rpm). When the material temperature reached 110°C, the mixing time was 15 minutes and the material was discharged into a cold mixer. The material was cooled to 40-45°C in the cold mixer and discharged to obtain a mixed material. The obtained mixed material was extruded and granulated using a parallel twin-screw extruder granulator at a processing temperature of 110-160°C and a screw speed of 300-400 rpm. After the pellets were fully cooled, a granular composite material was obtained.

[0040] Example 3

[0041] A high-adhesion, low-temperature-resistant chlorinated polyethylene composite material 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 RA adhesive, 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;

[0042] The chlorinated polyethylene has a chlorine content of 36.1%, a melting enthalpy of 0.4 J / g, a Shore hardness of 57A, a tensile strength of 10.2 MPa, and an elongation of 711% (the raw material is the same as that of the chlorinated polyethylene in Example 1);

[0043] 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).

[0044] The chlorinated polyethylene, terpene resin, adhesive RA, GLR-20 resin, epoxy resin, rare earth composite stabilizer, paraffin wax, stearic acid, polyethylene wax, and light calcium carbonate were weighed according to the stated weight ratios and poured into a high-speed mixer. The mixer was started and stirred at high speed (1500-3000 rpm). When the material temperature reached 83°C, DOTP was added and stirred at high speed again. When the material temperature reached 100°C, POE resin was added and stirred at low speed (500-1000 rpm). When the material temperature reached 110°C, the mixing time was 16 minutes and the material was discharged into a cold mixer. The material was cooled to 40-45°C in the cold mixer and discharged to obtain a mixed material. The obtained mixed material was extruded and granulated using a parallel twin-screw extruder granulator at a processing temperature of 110-160°C and a screw speed of 300-400 rpm. After the pellets were fully cooled, a granular composite material was obtained.

[0045] Example 4

[0046] This embodiment differs from embodiment 1 in that the indicators of the chlorinated polyethylene and POE raw materials are different.

[0047] A 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 RA adhesive, 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;

[0048] 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 is 643%;

[0049] The melt index of POE resin is (190°C / 2.16kg) 1.8g / 10min.

[0050] The chlorinated polyethylene, terpene resin, adhesive RA, GLR-20 resin, epoxy resin, calcium zinc composite stabilizer, paraffin wax, stearic acid, polyethylene wax, and light calcium carbonate were weighed according to the stated weight ratios and poured into a high-speed mixer. The mixer was started and stirred at high speed (1500-3000 rpm). When the material temperature reached 85°C, DOTP and DOS were added. High-speed stirring was continued. When the material temperature reached 100°C, POE resin was added and stirred at low speed (500-1000 rpm). When the material temperature reached 110°C, the mixing time was 14 minutes, and the material was discharged into a cold mixer. The material was cooled to 40-45°C in the cold mixer and discharged to obtain a mixed material. The obtained mixed material was extruded and granulated using a parallel twin-screw extruder granulator at a processing temperature of 110-160°C and a screw speed of 300-400 rpm. After the pellets were fully cooled, a granular composite material was obtained.

[0051] Example 5

[0052] This embodiment differs from embodiment 2 in that the performance parameters of the chlorinated polyethylene and POE raw materials are different.

[0053] A high-adhesion, 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 EA adhesive, 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;

[0054] The chlorinated polyethylene has a chlorine content of 40.4%, a melting enthalpy of 3.8 J / g, a Shore hardness of 58A, a tensile strength of 8.3 MPa, and an elongation of 643% (the raw material is the same as that of the chlorinated polyethylene 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] The chlorinated polyethylene, terpene resin, adhesive EA, GLR-20 resin, epoxy resin, calcium zinc composite stabilizer, paraffin wax, stearic acid, polyethylene wax, and light calcium carbonate were weighed according to the aforementioned weight ratios and poured into a high-speed mixer. The mixer was started and stirred at high speed (1500-3000 rpm). When the material temperature reached 80°C, DOTP was added and continued stirring at high speed. When the material temperature reached 100°C, POE resin was added and stirred at low speed (500-1000 rpm). When the material temperature reached 110°C, the mixing time was 15 minutes and the material was discharged into a cold mixer. The material was cooled to 40-45°C in the cold mixer and discharged to obtain a mixed material. The obtained mixed material was extruded and granulated using a parallel twin-screw extruder granulator at a processing temperature of 110-160°C and a screw speed of 300-400 rpm. After the pellets were fully cooled, a granular composite material was obtained.

[0057] Comparative Example 1

[0058] Compared with Example 2, this comparative example only removes the terpene resin, and the rest are the same.

[0059] A 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 EA adhesive, 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;

[0060] 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 is 711%;

[0061] The melt index of POE resin is (190°C / 2.16kg) 1.2g / 10min.

[0062] The chlorinated polyethylene, EA adhesive, GLR-20 resin, epoxy resin, calcium-zinc composite stabilizer, paraffin wax, stearic acid, polyethylene wax, and light calcium carbonate were weighed according to the stated weight ratios and poured into a high-speed mixer. The mixer was started and stirred at high speed (1500-3000 rpm). When the material temperature reached 80°C, DOTP was added and continued stirring at high speed. When the material temperature reached 100°C, POE resin was added and stirred at low speed (500-1000 rpm). When the material temperature reached 110°C, the mixing time was 15 minutes and the material was discharged into a cold mixer. The material was cooled to 40-45°C in the cold mixer and discharged to obtain a mixed material. The obtained mixed material was extruded and granulated using a parallel twin-screw extruder granulator at a processing temperature of 110-160°C and a screw speed of 300-400 rpm. After the pellets were fully cooled, a granular composite material was obtained.

[0063] Comparative Example 2

[0064] Compared with Example 1, the added adhesive in this comparative example was not compounded.

[0065] A 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 RA adhesive, 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;

[0066] 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 is 711%;

[0067] The melt index of POE resin is (190°C / 2.16kg) 1.2g / 10min.

[0068] The chlorinated polyethylene, terpene resin, adhesive RA, calcium-zinc composite stabilizer, paraffin wax, stearic acid, polyethylene wax, and light calcium carbonate were weighed according to the stated weight ratios and poured into a high-speed mixer. The mixer was started and stirred at high speed (1500-3000 rpm). When the material temperature reached 85°C, DOTP and DOS were added. High-speed stirring was continued. When the material temperature reached 100°C, POE resin was added and stirred at low speed (500-1000 rpm). When the material temperature reached 110°C, the mixing time was 14 minutes, and the material was discharged into a cold mixer. The material was cooled to 40-45°C in the cold mixer and discharged to obtain a mixed material. The obtained mixed material was extruded and granulated using a parallel twin-screw extruder granulator at a processing temperature of 110-160°C and a screw speed of 300-400 rpm. After the pellets were fully cooled, a granular composite material was obtained.

[0069] Comparative Example 3

[0070] The only difference between this comparative example and Example 1 is the performance parameters of the chlorinated polyethylene (low chlorine content).

[0071] A 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 RA adhesive, 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;

[0072] Among them: the chlorine content of 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 is 689%;

[0073] The melt index of POE resin is (190°C / 2.16kg) 1.2g / 10min.

[0074] The chlorinated polyethylene, terpene resin, adhesive RA, GLR-20 resin, epoxy resin, calcium zinc composite stabilizer, paraffin wax, stearic acid, polyethylene wax, and light calcium carbonate were weighed according to the stated weight ratios and poured into a high-speed mixer. The mixer was started and stirred at high speed (1500-3000 rpm). When the material temperature reached 85°C, DOTP and DOS were added. High-speed stirring was continued. When the material temperature reached 100°C, POE resin was added and stirred at low speed (500-1000 rpm). When the material temperature reached 110°C, the mixing time was 14 minutes, and the material was discharged into a cold mixer. The material was cooled to 40-45°C in the cold mixer and discharged to obtain a mixed material. The obtained mixed material was extruded and granulated using a parallel twin-screw extruder granulator at a processing temperature of 110-160°C and a screw speed of 300-400 rpm. After the pellets were fully cooled, a granular composite material was obtained.

[0075] In order to verify the performance of the composite materials, the granular composite materials prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were extruded into steel wire pipes. The extrusion temperature was 120 to 180° C., and the pipe products were obtained after cooling. The performance test results of each composite material and product are shown in Table 1.

[0076] Table 1 Performance test results

[0077]

[0078] As can be seen from Table 1, the composite material prepared by the present invention has good tensile strength and elongation at break, good low temperature resistance, low melt viscosity, good processing fluidity, high adhesion, and excellent adhesion to the winding steel wire.

[0079] By comparing Example 2 with Comparative Example 1, it can be seen that after the terpene resin in the composite material of the present invention is removed, although the compound adhesive is added, the bonding strength of the composite material still decreases, affecting its bonding performance with the steel wire, indicating that the terpene resin and the compound adhesive have a synergistic effect on the bonding performance of the composite material.

[0080] Comparison of Example 1 with Comparative Example 2 shows that the absence of a composite adhesive significantly reduces the composite's adhesive properties. Comparison of Example 1 with Comparative Example 3 shows that when the chlorine content of the chlorinated polyethylene is less than 30%, the composite's tensile strength and adhesive properties also decline. Experimental results indicate that optimal composite properties are achieved when the chlorine content of the chlorinated polyethylene is between 30% and 40% and the melting enthalpy is ≤15 J / g.

[0081] The high-adhesion, low-temperature-resistant chlorinated polyethylene composite material of the present invention is granular and primarily white in color. Other colors are also available based on user or production needs. It can be used in extruded plastic pipes, such as medium-pressure water pipes, that require bonding with wound steel wire. It exhibits improved extrusion processing fluidity, adhesion, tensile strength, and low-temperature resistance, and can increase the pipe's burst pressure. Its preparation process is simple, requiring no vulcanization, making it easily recyclable, with minimal environmental pollution, and amenable to large-scale production, promising promising industrial applications.

[0082] The above embodiments are preferred implementations of the present invention, but the implementations 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 considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. Highly adhesive and 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 composite adhesive is composed of adhesive, GLR-20 resin and epoxy resin in a weight ratio of 0.9-1.1:1:1.2-1.4; The adhesive is one of the adhesives RA, RA-65, EA, RE, RFD, RZ, RH or a combination of two or more in any proportion. The chlorine content of the chlorinated polyethylene is 30-40%, and the melting enthalpy is ≤15 J / g.

2. 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.

3. The high-adhesion, low-temperature-resistant chlorinated polyethylene composite material according to claim 1, wherein: The melt index of the ethylene-butene copolymer is 0.8 to 2.5 g / 10 min.

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

5. The high-adhesion, low-temperature-resistant chlorinated polyethylene composite material according to claim 1, wherein: The stabilizer is one or a combination of two or more of a calcium zinc composite stabilizer, a lead salt stabilizer, calcium stearate, and a rare earth composite stabilizer in any proportion.

6. The high-adhesion, low-temperature-resistant chlorinated polyethylene composite material according to claim 1, wherein: 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-adhesion, low-temperature-resistant chlorinated polyethylene composite material according to claim 1, wherein: The reinforcing agent is one of calcium carbonate, talc or calcium sulfate whiskers, or a combination of two or more of them in any proportion.

8. The method for preparing the high-adhesion, low-temperature-resistant chlorinated polyethylene composite material according to any one of claims 1 to 7, comprising the following steps: S1. Weigh each raw material by weight; S2, placing 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 second material reaches 98-100° C., ethylene-butene copolymer is added and stirred to obtain the third material; When the temperature of the material 3 reaches 110-120°C, the material 3 is introduced into a cold mixer for cooling. When the temperature drops to 40-45°C, the material is taken out to obtain a powdered composite material. S3. Extruding and granulating the powdery composite material. The processing temperature of the extrusion and granulation is 110-160° C., the screw speed is 300-400 rpm, and the pellets are fully cooled to obtain a granular composite material.

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