Environment-friendly polyvinyl chloride wire and cable material as well as preparation method and application thereof

Abstract

The invention discloses an environment-friendly polyvinyl chloride wire and cable material as well as a preparation method and application thereof, and relates to the technical field of polyvinyl chloride cable sheath materials, the environment-friendly polyvinyl chloride wire and cable material comprises the following components in parts by weight: 70-85 parts of modified polyvinyl chloride, 5-12 parts of polyisoprene containing a UPy unit at the tail end, 10-20 parts of a filler and 12-18 parts of an auxiliary agent. On one hand, polyvinyl chloride is subjected to freezing-microwave plasma synergistic circulation treatment, the processability, mechanical properties and the like of a polyvinyl chloride base material are improved, meanwhile, a proper amount of polyisoprene which has a self-complementary quadruple hydrogen-bond interaction and contains a UPy unit at the tail end is introduced, and all the components have a synergistic effect; the obtained polyvinyl chloride wire and cable material has excellent high and low temperature resistance, and meets the service requirements in different environments; components containing arsenic, mercury, lead and other heavy metal elements are not added into the product, and the product meets the European Union ROHS environmental protection standard.

Description

Technical Field

[0001] The invention relates to the technical field of polyvinyl chloride cable sheath materials, and in particular to an environmentally friendly polyvinyl chloride wire and cable material and a preparation method and application thereof. Background Art

[0002] Wires and cables, as the core carriers of modern power transmission and signal transmission, the selection of their sheath materials has a vital impact on the overall performance, service life and safety of wires and cables. Polyvinyl chloride (PVC), with its excellent physical and mechanical properties, outstanding chemical corrosion resistance and economical and practical characteristics, has long occupied a dominant position in the field of wire and cable sheath materials. However, with the rapid advancement of science and technology and the increasing global environmental awareness, the limitations of traditional PVC wire and cable materials in terms of environmental protection, high and low temperature resistance, etc. have gradually emerged, becoming a major bottleneck restricting its sustainable development.

[0003] In terms of environmental protection, traditional PVC wire and cable materials may release substances that are harmful to the environment during production, processing, use and waste treatment, thereby polluting the ecological environment and posing a potential threat to human health. More seriously, some PVC wire and cable materials may also contain heavy metal elements such as arsenic, mercury and lead. These heavy metals are difficult to degrade in nature, are bioaccumulative and toxic, and pose a long-term and serious threat to the ecological environment and human health. With the continuous improvement of global environmental protection requirements, the research and development of environmentally friendly wire and cable materials has become an inevitable trend in the development of the industry and an important measure to respond to global environmental protection calls. For example, the EU ROHS (Restriction of Hazardous Substances) environmental protection standard, as an important policy aimed at strictly restricting the use of certain hazardous substances in electronic and electrical equipment, has had a profound impact on the wire and cable industry. The ROHS standard clearly stipulates the maximum limits of hazardous substances such as lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyls (PBBs), and polybrominated diphenyl ethers (PBDEs) in electronic and electrical equipment, and requires that the content of these hazardous substances in the product shall not exceed the specified limit. At the same time, the ROHS standard is constantly being updated and improved, gradually including more harmful substances in the restricted scope to further protect the ecological environment and human health. Products that meet the ROHS standard mean that their impact on the environment is minimized throughout their life cycle, from production, use to waste disposal, and the risks to human health are also effectively controlled.

[0004] In terms of high and low temperature resistance, the performance of traditional PVC wire and cable materials is also worrying. In high temperature environments, PVC materials have poor thermal stability and are prone to thermal decomposition, producing harmful gases. At the same time, their mechanical properties will also drop significantly, and their strength and toughness will be weakened, causing wire and cable sheaths to crack and deform easily, seriously affecting the safe and reliable operation of wires and cables. In high-cold environments, PVC materials will become hard and brittle, and their flexibility and impact resistance will be greatly reduced, increasing the risk of damage to wires and cables during transportation, installation and use. In addition, special heating measures are required to process PVC materials in low temperature environments, which not only increases production costs, but also increases processing difficulty and reduces production efficiency.

[0005] Therefore, in view of the many shortcomings of traditional PVC wire and cable materials in terms of environmental protection and high and low temperature resistance, it is particularly urgent to develop a polyvinyl chloride wire and cable material that is both environmentally friendly and has good high and low temperature resistance. Summary of the invention

[0006] In order to solve the above problems, the present invention provides an environmentally friendly polyvinyl chloride wire and cable material and a preparation method and application thereof.

[0007] In a first aspect, the present invention provides an environmentally friendly polyvinyl chloride wire and cable material, which comprises the following components in parts by weight: 70-85 parts of modified polyvinyl chloride, 5-12 parts of polyisoprene containing UPy units at the end, 10-20 parts of fillers and 12-18 parts of additives; The modified polyvinyl chloride is obtained by subjecting polyvinyl chloride to cryogenic-microwave plasma synergistic cycle treatment.

[0008] Furthermore, the environmentally friendly polyvinyl chloride wire and cable material comprises the following components in parts by weight: 78.5 parts of modified polyvinyl chloride, 9 parts of polyisoprene containing UPy units at the end, 14 parts of filler and 15 parts of additives.

[0009] Furthermore, if Figure 1 As shown, the preparation method of the modified polyvinyl chloride comprises the following process: S1: freezing the polyvinyl chloride at -35°C to -25°C for 1 to 2 hours, and then returning the polyvinyl chloride to room temperature to obtain a first polyvinyl chloride; S2: subjecting the first polyvinyl chloride to microwave plasma treatment for 20 to 40 seconds at a microwave power of 380 to 450 W and in an open atmosphere working mode to obtain a second polyvinyl chloride; S3: The second polyvinyl chloride is subjected to a cyclic treatment in accordance with the steps S1 and S2 for 4 to 8 times to obtain the modified polyvinyl chloride.

[0010] Furthermore, the temperature of the freezing treatment is -30°C, and the microwave power of the microwave plasma treatment is 425W.

[0011] Furthermore, the method for preparing the polyisoprene containing a UPy unit at the end comprises the following process: After degassing the dry flask, 40 mL of isoprene and 11 mL of sec-butyl lithium were injected and reacted at 40° C. for 2 hours, and then 30 mL of propylene oxide was injected into the flask and the reaction was continued at 40° C. for 5 hours, and finally 15 mL of degassed methanol was injected to terminate the reaction, and then the reaction solution was poured into 15 mL of isopropanol for precipitation to obtain hydroxy-terminated polyisoprene; 30 g of hexamethylene diisocyanate was added to a flask, and then 30 g of the hydroxy-terminated polyisoprene was added, and the obtained first mixture was stirred at room temperature under a nitrogen atmosphere for 3.5 hours to obtain a polyisoprene containing NCO at the end; 40 g of the polyisoprene containing NCO at the terminal and 20 g of 6-methylisocytosine were added to a flask and the obtained second mixture was stirred at room temperature under a nitrogen atmosphere for 40 minutes, and then heated to 60° C. and maintained for 4 hours to obtain the polyisoprene containing UPy units at the terminal.

[0012] Furthermore, the filler includes silica modified by an imidazole-functional silane coupling agent, and the preparation method of the silica modified by an imidazole-functional silane coupling agent includes the following process: The imidazole functional silane coupling agent, tetraethyl orthosilicate and solvent are stirred and mixed in a weight ratio of (2.0-2.3): (6.5-7.0): (15-20) to obtain a third mixture; The third mixture is stirred at a temperature of 62-68° C. for 5-6 hours, then heated to 95-100° C. and stirred for 1.5-2 hours, and finally dried at 80-85° C. for 14-16 hours, crushed, and passed through a 300-400 mesh sieve to obtain the imidazole functional group silane coupling agent modified silica; Wherein, the solvent is composed of ethanol and water in a volume ratio of (3-5):1, and the imidazole functional group silane coupling agent includes 1-(3-(trimethoxysilyl)propyl)-1H-imidazole.

[0013] Furthermore, the auxiliary agent includes a plasticizer, an antioxidant and a lubricant in a weight ratio of (19-23): (0.5-1.0): (1-2).

[0014] Further, the plasticizer includes at least one of dioctyl sebacate and dioctyl azelate, the antioxidant includes at least one of antioxidant 1010 and antioxidant 168, and the lubricant includes at least one of stearic acid and polyethylene wax.

[0015] In a second aspect, based on the same inventive concept, the present invention provides a method for preparing the environmentally friendly polyvinyl chloride wire and cable material as described in any one of the first aspects, such as Figure 2 As shown, the preparation method comprises the following steps: The modified polyvinyl chloride, the polyisoprene containing a UPy unit at the end and the auxiliary agent are stirred and mixed at a temperature of 110 to 120° C. for 20 to 30 minutes to obtain a fourth mixture; After the fourth mixture is cooled to 80-90° C., fillers are added and stirring is continued for 30-60 minutes to obtain a fifth mixture; The mixture is added into a twin-screw extruder for melt extrusion and granulation at a temperature of 170-185° C. to obtain the environmentally friendly polyvinyl chloride wire and cable material.

[0016] In the third aspect, based on the same inventive concept, the present invention provides an application of the environmentally friendly polyvinyl chloride wire and cable material as described in any one of the first aspect or the environmentally friendly polyvinyl chloride wire and cable material prepared by the preparation method of the environmentally friendly polyvinyl chloride wire and cable material as described in any one of the second aspect in the preparation of high and low temperature resistant cables, the high and low temperature resistant cable comprising a conductor and an insulating material coated on the conductor, the insulating material being the environmentally friendly polyvinyl chloride wire and cable material as described in any one of the first aspect or the environmentally friendly polyvinyl chloride wire and cable material prepared by the preparation method of the environmentally friendly polyvinyl chloride wire and cable material as described in any one of the second aspect.

[0017] The above technical solution provided by the embodiment of the present invention has at least the following advantages compared with the prior art: The embodiment of the present invention provides an environmentally friendly polyvinyl chloride wire and cable material, a preparation method and application thereof. On the one hand, the present invention improves the processability and mechanical properties of the polyvinyl chloride material by subjecting the polyvinyl chloride to a cryo-microwave plasma synergistic cycle treatment, and at the same time introduces an appropriate amount of polyisoprene containing a terminal UPy unit with a self-complementary quadruple hydrogen bond effect. The components synergize to enhance the effectiveness, so that the obtained polyvinyl chloride wire and cable material has excellent high and low temperature resistance and meets the service requirements in different environments; and the product does not contain components containing heavy metal elements such as arsenic, mercury, and lead, and meets the EU ROHS environmental protection standards. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and, together with the description, serve to explain the principles of the invention.

[0019] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0020] Figure 1 The present invention provides a schematic flow chart of a method for preparing modified polyvinyl chloride in an environmentally friendly polyvinyl chloride wire and cable material according to an embodiment of the present invention.

[0021] Figure 2 A schematic flow chart of a method for preparing an environmentally friendly polyvinyl chloride wire and cable material provided in an embodiment of the present invention. DETAILED DESCRIPTION

[0022] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0024] In a first aspect, the present invention provides an environmentally friendly polyvinyl chloride wire and cable material, which comprises the following components in parts by weight: 70-85 parts of modified polyvinyl chloride, 5-12 parts of polyisoprene containing UPy units at the end, 10-20 parts of fillers and 12-18 parts of additives; The modified polyvinyl chloride is obtained by subjecting polyvinyl chloride to cryogenic-microwave plasma synergistic cycle treatment.

[0025] The embodiment of the present invention provides an environmentally friendly polyvinyl chloride wire and cable material. On the one hand, the present invention improves the processability and mechanical properties of the polyvinyl chloride material by subjecting the polyvinyl chloride to a cryo-microwave plasma synergistic cycle treatment, and at the same time introduces an appropriate amount of polyisoprene containing a terminal UPy unit with a self-complementary quadruple hydrogen bond effect. The components synergize to enhance the effectiveness, so that the obtained polyvinyl chloride wire and cable material has excellent high and low temperature resistance and meets the service requirements in different environments. Moreover, no components containing heavy metal elements such as arsenic, mercury, and lead are added to the product, which complies with the EU ROHS environmental protection standard.

[0026] The polyvinyl chloride in the present invention can be prepared by the preparation method disclosed in the prior art or directly adopt a commercial product. Specifically, polyvinyl chloride with a polymerization degree between 2200 and 3100, such as the product model of Hangzhou Dianhua New Materials Co., Ltd., polyvinyl chloride DH-2500, is selected in the embodiments and comparative examples of the present invention.

[0027] In some specific embodiments, the environmentally friendly polyvinyl chloride wire and cable material includes the following components in parts by weight: 78.5 parts of modified polyvinyl chloride, 9 parts of polyisoprene containing UPy units at the end, 14 parts of filler and 15 parts of additives.

[0028] In some specific embodiments, Figure 1 As shown, the preparation method of the modified polyvinyl chloride comprises the following process: S1: freezing the polyvinyl chloride at -35°C to -25°C for 1 to 2 hours, and then returning the polyvinyl chloride to room temperature to obtain a first polyvinyl chloride; S2: subjecting the first polyvinyl chloride to microwave plasma treatment for 20 to 40 seconds at a microwave power of 380 to 450 W and in an open atmosphere working mode to obtain a second polyvinyl chloride; S3: The second polyvinyl chloride is subjected to a cyclic treatment in accordance with the steps S1 and S2 for 4 to 8 times to obtain the modified polyvinyl chloride.

[0029] In some specific embodiments, the temperature of the freezing treatment is -30°C, and the microwave power of the microwave plasma treatment is 425W.

[0030] In some specific embodiments, the polyisoprene containing UPy units at the end of the present invention refers to a polymer in which a polyisoprene molecular chain is grafted with UPy (ureidopyrimidone, a functional group capable of forming multiple hydrogen bonds) units, which can be prepared according to the method described in Example 2 of the prior art (patent application number: 201410453519.5, all relevant contents described in the patent document are introduced into this patent), and the preparation method includes the following process: After degassing the dry flask, 40 mL of isoprene and 11 mL of sec-butyl lithium were injected and reacted at 40° C. for 2 hours, and then 30 mL of propylene oxide was injected into the flask and the reaction was continued at 40° C. for 5 hours, and finally 15 mL of degassed methanol was injected to terminate the reaction, and then the reaction solution was poured into 15 mL of isopropanol for precipitation to obtain hydroxy-terminated polyisoprene; 30 g of hexamethylene diisocyanate was added to a flask, and then 30 g of the hydroxy-terminated polyisoprene was added, and the obtained first mixture was stirred at room temperature under a nitrogen atmosphere for 3.5 hours to obtain a polyisoprene containing NCO at the end; 40 g of the polyisoprene containing NCO at the terminal and 20 g of 6-methylisocytosine were added to a flask and the obtained second mixture was stirred at room temperature under a nitrogen atmosphere for 40 minutes, and then heated to 60° C. and maintained for 4 hours to obtain the polyisoprene containing UPy units at the terminal.

[0031] In some specific embodiments, the filler includes silica modified by an imidazole-functional silane coupling agent, and the preparation method of the silica modified by an imidazole-functional silane coupling agent includes the following process: The imidazole functional silane coupling agent, tetraethyl orthosilicate and solvent are stirred and mixed in a weight ratio of (2.0-2.3): (6.5-7.0): (15-20) to obtain a third mixture; The third mixture is stirred at a temperature of 62-68° C. for 5-6 hours, then heated to 95-100° C. and stirred for 1.5-2 hours, and finally dried at 80-85° C. for 14-16 hours, crushed, and passed through a 300-400 mesh sieve to obtain the imidazole functional group silane coupling agent modified silica; Wherein, the solvent is composed of ethanol and water in a volume ratio of (3-5):1, and the imidazole functional group silane coupling agent includes 1-(3-(trimethoxysilyl)propyl)-1H-imidazole.

[0032] In some specific embodiments, the auxiliary agent includes a plasticizer, an antioxidant and a lubricant in a weight ratio of (19-23): (0.5-1.0): (1-2).

[0033] In some specific embodiments, the plasticizer includes at least one of dioctyl sebacate and dioctyl azelate, the antioxidant includes at least one of antioxidant 1010 and antioxidant 168, and the lubricant includes at least one of stearic acid and polyethylene wax.

[0034] In a second aspect, based on the same inventive concept, the present invention provides a method for preparing the environmentally friendly polyvinyl chloride wire and cable material as described in any one of the first aspects, such as Figure 2 As shown, the preparation method comprises the following steps: The modified polyvinyl chloride, the polyisoprene containing a UPy unit at the end and the auxiliary agent are stirred and mixed at a temperature of 110 to 120° C. for 20 to 30 minutes to obtain a fourth mixture; After the fourth mixture is cooled to 80-90° C., fillers are added and stirring is continued for 30-60 minutes to obtain a fifth mixture; The mixture is added into a twin-screw extruder for melt extrusion and granulation at a temperature of 170-185° C. to obtain the environmentally friendly polyvinyl chloride wire and cable material.

[0035] The method for preparing the environmentally friendly polyvinyl chloride wire and cable material provided by the embodiment of the present invention is simple to operate, does not require additional specific equipment, and is suitable for industrial mass production.

[0036] In the third aspect, based on the same inventive concept, the present invention provides an application of the environmentally friendly polyvinyl chloride wire and cable material as described in any one of the first aspect or the environmentally friendly polyvinyl chloride wire and cable material prepared by the preparation method of the environmentally friendly polyvinyl chloride wire and cable material as described in any one of the second aspect in the preparation of high and low temperature resistant cables, the high and low temperature resistant cable comprising a conductor and an insulating material coated on the conductor, the insulating material being the environmentally friendly polyvinyl chloride wire and cable material as described in any one of the first aspect or the environmentally friendly polyvinyl chloride wire and cable material prepared by the preparation method of the environmentally friendly polyvinyl chloride wire and cable material as described in any one of the second aspect.

[0037] It should be noted that the component raw materials involved in the environmentally friendly polyvinyl chloride wire and cable material and its preparation method and application provided by the embodiments of the present invention, unless otherwise specified or specified, can directly adopt commercially available products or adopt existing public preparation methods to make their own products; at the same time, the steps and parameters involved, unless otherwise specified or specified, can be carried out according to the preparation process steps and parameters of polyvinyl chloride cable sheath materials disclosed in the prior art or directly carried out using existing equipment according to the instruction manual, and the present invention document will not repeat them one by one.

[0038] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are intended only to illustrate the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples that do not specify specific conditions are usually measured according to national standards. If there is no corresponding national standard, then the conditions recommended by the manufacturer are followed.

[0039] Example 1 This example provides an environmentally friendly polyvinyl chloride wire and cable material, which includes the following components in parts by weight: 78.5 parts of modified polyvinyl chloride, 9 parts of polyisoprene containing UPy units at the end, 14 parts of filler and 15 parts of additives; The modified polyvinyl chloride is obtained by subjecting polyvinyl chloride to a cryogenic-microwave plasma synergistic cycle treatment. The preparation method of the modified polyvinyl chloride comprises the following steps: S1: subjecting the polyvinyl chloride to a cryogenic treatment at -30°C for 1.5 hours, and then recovering to room temperature to obtain a first polyvinyl chloride; S2: subjecting the first polyvinyl chloride to a microwave plasma treatment for 30 seconds under the conditions of a microwave power of 425W and an open-air working mode to obtain a second polyvinyl chloride; S3: subjecting the second polyvinyl chloride to a cycle treatment for 6 times in sequence according to the S1 step and the S2 step to obtain the modified polyvinyl chloride; The preparation method of the polyisoprene containing UPy units at the end comprises the following steps: after degassing a dry flask, 40 mL of isoprene and 11 mL of sec-butyl lithium are injected into the flask and reacted at 40° C. for 2 hours, then 30 mL of propylene oxide is injected into the flask and the reaction is continued at 40° C. for 5 hours, and finally 15 mL of degassed methanol is injected to terminate the reaction, and then the reaction solution is poured into 15 mL of isopropanol for precipitation to obtain terminal hydroxyl polyisoprene; 30 g of hexamethylene diisocyanate is added into the flask, and then 30 g of the terminal hydroxyl polyisoprene is added and the obtained first mixture is stirred at room temperature and nitrogen atmosphere for 3.5 hours to obtain terminal NCO-containing polyisoprene; 40 g of the terminal NCO-containing polyisoprene and 20 g of 6-methylisocytosine are added into the flask and the obtained second mixture is stirred at room temperature and nitrogen atmosphere for 40 minutes, and then the temperature is raised to 60° C. and maintained for 4 hours to obtain the terminal UPy-containing polyisoprene; The filler includes silica modified by an imidazole-functional silane coupling agent. The preparation method of the silica modified by the imidazole-functional silane coupling agent includes the following steps: the imidazole-functional silane coupling agent, tetraethyl orthosilicate and a solvent are stirred and mixed in a weight ratio of 2.1:6.8:18 to obtain a third mixture; the third mixture is stirred for 5.5 hours at a temperature of 65° C., then heated to 98° C. and stirred for 2 hours, and finally dried at 83° C. for 15 hours, crushed, and passed through a 350-mesh sieve to obtain the silica modified by the imidazole-functional silane coupling agent; wherein the solvent is composed of ethanol and water in a volume ratio of 4:1, and the imidazole-functional silane coupling agent is 1-(3-(trimethoxysilyl)propyl)-1H-imidazole; The auxiliary agent is a plasticizer, an antioxidant and a lubricant in a weight ratio of 22:0.8:1.5, wherein the plasticizer is dioctyl sebacate, the antioxidant is antioxidant 1010, and the lubricant is stearic acid.

[0040] The preparation method of the above-mentioned environmentally friendly polyvinyl chloride wire and cable material comprises the following steps: Step (1): stirring and mixing the modified polyvinyl chloride, the polyisoprene containing a UPy unit at the end and the auxiliary agent at a temperature of 115° C. for 25 minutes to obtain a fourth mixture; Step (2): After the fourth mixture is cooled to 85° C., filler is added and stirring is continued for 45 minutes to obtain a fifth mixture; Step (3): adding the mixture into a twin-screw extruder for melt extrusion and granulation at a temperature of 180° C. to obtain the environmentally friendly polyvinyl chloride wire and cable material.

[0041] Example 2 This example provides an environmentally friendly polyvinyl chloride wire and cable material, which includes the following components in parts by weight: 70 parts of modified polyvinyl chloride, 5 parts of polyisoprene containing UPy units at the end, 10 parts of filler and 12 parts of additives; The modified polyvinyl chloride is obtained by subjecting polyvinyl chloride to a cryogenic-microwave plasma synergistic cycle treatment. The preparation method of the modified polyvinyl chloride comprises the following steps: S1: subjecting the polyvinyl chloride to a cryogenic treatment at -35°C for 1 hour, and then recovering to room temperature to obtain a first polyvinyl chloride; S2: subjecting the first polyvinyl chloride to a microwave plasma treatment for 40 seconds under the conditions of a microwave power of 380W and an atmospheric open working mode to obtain a second polyvinyl chloride; S3: subjecting the second polyvinyl chloride to a cycle treatment for 4 times in sequence according to the S1 step and the S2 step to obtain the modified polyvinyl chloride; The preparation method of the polyisoprene containing UPy units at the end is the same as that in Example 1; The filler includes silica modified by an imidazole-functional silane coupling agent. The preparation method of the silica modified by the imidazole-functional silane coupling agent includes the following steps: the imidazole-functional silane coupling agent, tetraethyl orthosilicate and a solvent are stirred and mixed in a weight ratio of 2.0:6.5:15 to obtain a third mixture; the third mixture is stirred at 62° C. for 6 hours, then heated to 100° C. and stirred for 1.5 hours, and finally dried at 80° C. for 16 hours, crushed, and passed through a 300-mesh sieve to obtain the silica modified by the imidazole-functional silane coupling agent; wherein the solvent is composed of ethanol and water in a volume ratio of 3:1, and the imidazole-functional silane coupling agent is 1-(3-(trimethoxysilyl)propyl)-1H-imidazole; The auxiliary agent is composed of a plasticizer, an antioxidant and a lubricant in a weight ratio of 19:0.5:1, the plasticizer is dioctyl azelate, the antioxidant is antioxidant 168, and the lubricant is polyethylene wax.

[0042] The preparation method of the above-mentioned environmentally friendly polyvinyl chloride wire and cable material comprises the following steps: Step (1): stirring and mixing the modified polyvinyl chloride, the polyisoprene containing a UPy unit at the end and the auxiliary agent at 110° C. for 30 minutes to obtain a fourth mixture; Step (2): After the fourth mixture is cooled to 90° C., filler is added and stirring is continued for 30 minutes to obtain a fifth mixture; Step (3): adding the mixture into a twin-screw extruder for melt extrusion and granulation at a temperature of 170° C. to obtain the environmentally friendly polyvinyl chloride wire and cable material.

[0043] Example 3 This example provides an environmentally friendly polyvinyl chloride wire and cable material, which includes the following components in parts by weight: 85 parts of modified polyvinyl chloride, 12 parts of polyisoprene containing UPy units at the end, 20 parts of filler and 18 parts of additives; The modified polyvinyl chloride is obtained by subjecting polyvinyl chloride to a cryogenic-microwave plasma synergistic cycle treatment. The preparation method of the modified polyvinyl chloride comprises the following steps: S1: subjecting polyvinyl chloride to a cryogenic treatment at -25°C for 2 hours, and then recovering to room temperature to obtain a first polyvinyl chloride; S2: subjecting the first polyvinyl chloride to a microwave plasma treatment for 20 seconds under the conditions of a microwave power of 450W and an atmospheric open working mode to obtain a second polyvinyl chloride; S3: subjecting the second polyvinyl chloride to a cycle treatment of 8 times in sequence according to the S1 step and the S2 step to obtain the modified polyvinyl chloride; The preparation method of the polyisoprene containing UPy units at the end is the same as that in Example 1; The filler includes silica modified by an imidazole-functional silane coupling agent. The preparation method of the silica modified by the imidazole-functional silane coupling agent includes the following steps: the imidazole-functional silane coupling agent, tetraethyl orthosilicate and a solvent are stirred and mixed in a weight ratio of 2.3:7.0:20 to obtain a third mixture; the third mixture is stirred at 68° C. for 5 hours, then heated to 95° C. and stirred for 2 hours, and finally dried at 85° C. for 14 hours, crushed, and passed through a 400-mesh sieve to obtain the silica modified by the imidazole-functional silane coupling agent; wherein the solvent is composed of ethanol and water in a volume ratio of 5:1, and the imidazole-functional silane coupling agent is 1-(3-(trimethoxysilyl)propyl)-1H-imidazole; The auxiliary agent is composed of a plasticizer, an antioxidant and a lubricant in a weight ratio of 23:1.0:2, wherein the plasticizer is dioctyl azelate, the antioxidant is antioxidant 168, and the lubricant is polyethylene wax.

[0044] The preparation method of the above-mentioned environmentally friendly polyvinyl chloride wire and cable material comprises the following steps: Step (1): stirring and mixing the modified polyvinyl chloride, the polyisoprene containing a UPy unit at the end and the auxiliary agent at 120° C. for 20 minutes to obtain a fourth mixture; Step (2): After the fourth mixture is cooled to 80° C., filler is added and stirring is continued for 60 minutes to obtain a fifth mixture; Step (3): adding the mixture into a twin-screw extruder for melt extrusion and granulation at a temperature of 185° C. to obtain the environmentally friendly polyvinyl chloride wire and cable material.

[0045] Comparative Example 1 This example provides an environmentally friendly polyvinyl chloride wire and cable material and a preparation method thereof. The only difference from Example 1 is that the modified polyvinyl chloride is replaced by unmodified polyvinyl chloride (i.e., no cryo-microwave plasma synergistic cycle treatment is performed), and the polyisoprene containing a UPy unit at the end is replaced by the terminal hydroxyl polyisoprene obtained in Example 1; the remaining steps and parameters are the same.

[0046] Comparative Example 2 This example provides an environmentally friendly polyvinyl chloride wire and cable material and a preparation method thereof, which is different from Example 1 only in that the polyisoprene containing a UPy unit at the end is replaced by the terminal hydroxyl polyisoprene obtained in Example 1; the remaining steps and parameters are the same.

[0047] Comparative Example 3 This example provides an environmentally friendly polyvinyl chloride wire and cable material and a preparation method thereof. The only difference from Example 1 is that the modified polyvinyl chloride is replaced by unmodified polyvinyl chloride (i.e., no cryo-microwave plasma synergistic cycle treatment is performed); the remaining steps and parameters are the same.

[0048] Comparative Example 4 This example provides an environmentally friendly polyvinyl chloride wire and cable material and a preparation method thereof. The only difference from Example 1 is that the preparation method of modified polyvinyl chloride is adjusted as follows: S1: Under the conditions of a microwave power of 425 W and an open working mode to the atmosphere, polyvinyl chloride is subjected to microwave plasma treatment for 30 seconds to obtain a first polyvinyl chloride; S2: the first polyvinyl chloride is treated 6 times according to the step S1 to obtain the modified polyvinyl chloride (i.e., the polyvinyl chloride is modified only by microwave plasma); the remaining steps and parameters are the same.

[0049] Test Example 1 In this example, the mechanical properties and low temperature resistance of the environmentally friendly polyvinyl chloride wire and cable materials obtained in the above-mentioned Examples 1 to 3 and Comparative Examples 1 to 4 were tested.

[0050] The test performance index parameters and standards are as follows: 1) Mechanical properties: The elongation at break (%) test was carried out according to GB / T508-2008 standard.

[0051] 2) Low temperature resistance test: refer to GB / T2843-2008 standard for low temperature impact strength (KJ / m 2 )test.

[0052] The test results are shown in Table 1.

[0053] Table 1 It can be seen from Table 1 that, compared with Comparative Examples 1 to 4, the environmentally friendly polyvinyl chloride wire and cable materials provided by Examples 1 to 3 of the present invention have better mechanical properties and low temperature resistance, and through the combination of specific modified polyvinyl chloride and polyisoprene containing UPy units at the end, the two show significant positive synergistic effect.

[0054] Test Example 2 Based on the mechanical property test in the above test example 1, this example further tests the high temperature resistance of the environmentally friendly polyvinyl chloride wire and cable materials obtained in the above examples 1 to 3.

[0055] Test method: After the test sample was heat aged at 150°C for 240 hours, the elongation at break (%) was tested again, and the elongation at break retention rate after heat aging treatment (%, i.e., the degree to which the elongation at break was maintained relative to the initial elongation at break) was calculated according to the test standard and results of the elongation at break in Test Example 1.

[0056] The test results are shown in Table 2.

[0057] Table 2 It can be seen from Table 2 that after heat aging for 240 hours at 150° C., the elongation at break retention rate of the environmentally friendly polyvinyl chloride wire and cable materials provided by Examples 1 to 3 of the present invention is excellent, and can reach up to 91.1%.

[0058] In summary, the embodiments of the present invention provide an environmentally friendly polyvinyl chloride wire and cable material, a preparation method and application thereof. On the one hand, the present invention improves the processability and mechanical properties of the polyvinyl chloride material by subjecting the polyvinyl chloride to a cryo-microwave plasma synergistic cycle treatment, and at the same time introduces an appropriate amount of polyisoprene containing a terminal UPy unit with a self-complementary quadruple hydrogen bond effect. The components synergize to enhance the effectiveness, so that the obtained polyvinyl chloride wire and cable material has excellent high and low temperature resistance and meets the service requirements under different environments; and no components containing heavy metal elements such as arsenic, mercury and lead are added to the product, which complies with the EU ROHS environmental protection standards.

[0059] Various embodiments of the present invention may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be understood as a rigid limitation on the scope of the present invention; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numerical values ​​within the range. For example, the range description from 1 to 6 should be considered to have specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which are applicable regardless of the range. In addition, whenever a numerical range is indicated herein, it is intended to include any cited number (fractional or integer) within the indicated range.

[0060] The foregoing is merely a specific embodiment of the present invention, which enables those skilled in the art to understand or implement the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features claimed herein.

Claims

1. An environmentally friendly polyvinyl chloride wire and cable material, characterized in that: The environmentally friendly polyvinyl chloride wire and cable material comprises the following components in parts by weight: 70-85 parts of modified polyvinyl chloride, 5-12 parts of polyisoprene containing UPy units at the end, 10-20 parts of fillers and 12-18 parts of additives; The modified polyvinyl chloride is obtained by subjecting polyvinyl chloride to cryogenic-microwave plasma synergistic cycle treatment.

2. The environmentally friendly polyvinyl chloride wire and cable material according to claim 1, characterized in that: The environmentally friendly polyvinyl chloride wire and cable material comprises the following components in parts by weight: 78.5 parts of modified polyvinyl chloride, 9 parts of polyisoprene containing UPy units at the end, 14 parts of filler and 15 parts of additives.

3. The environmentally friendly polyvinyl chloride wire and cable material according to claim 1, characterized in that: Preparation method of modified polyvinyl chloride The process includes: S1: freezing the polyvinyl chloride at -35°C to -25°C for 1 to 2 hours, and then returning the polyvinyl chloride to room temperature to obtain a first polyvinyl chloride; S2: subjecting the first polyvinyl chloride to microwave plasma treatment for 20 to 40 seconds at a microwave power of 380 to 450 W and in an open atmosphere working mode to obtain a second polyvinyl chloride; S3: The second polyvinyl chloride is subjected to a cyclic treatment in accordance with the steps S1 and S2 for 4 to 8 times to obtain the modified polyvinyl chloride.

4. The environmentally friendly polyvinyl chloride wire and cable material according to claim 3, characterized in that: The temperature of the freezing treatment is -30°C, and the microwave power of the microwave plasma treatment is 425W.

5. The environmentally friendly polyvinyl chloride wire and cable material according to any one of claims 1 to 4, characterized in that: The method for preparing the polyisoprene containing a UPy unit at the end comprises the following steps: After degassing the dry flask, 40 mL of isoprene and 11 mL of sec-butyl lithium were injected and reacted at 40° C. for 2 hours, and then 30 mL of propylene oxide was injected into the flask and the reaction was continued at 40° C. for 5 hours, and finally 15 mL of degassed methanol was injected to terminate the reaction, and then the reaction solution was poured into 15 mL of isopropanol for precipitation to obtain terminal hydroxyl polyisoprene; 30 g of hexamethylene diisocyanate was added to a flask, and then 30 g of the hydroxy-terminated polyisoprene was added, and the obtained first mixture was stirred at room temperature under a nitrogen atmosphere for 3.5 hours to obtain a polyisoprene containing NCO at the end; 40 g of the polyisoprene containing NCO at the terminal and 20 g of 6-methylisocytosine were added to a flask and the obtained second mixture was stirred at room temperature under a nitrogen atmosphere for 40 minutes, and then heated to 60° C. and maintained for 4 hours to obtain the polyisoprene containing UPy units at the terminal.

6. The environmentally friendly polyvinyl chloride wire and cable material according to any one of claims 1 to 4, characterized in that: The filler comprises silica modified by an imidazole functional group silane coupling agent, and a preparation method of the silica modified by an imidazole functional group silane coupling agent The process includes: The imidazole functional silane coupling agent, tetraethyl orthosilicate and solvent are stirred and mixed in a weight ratio of (2.0-2.3): (6.5-7.0): (15-20) to obtain a third mixture; The third mixture is stirred at a temperature of 62-68° C. for 5-6 hours, then heated to 95-100° C. and stirred for 1.5-2 hours, and finally dried at 80-85° C. for 14-16 hours, crushed, and passed through a 300-400 mesh sieve to obtain the imidazole functional group silane coupling agent modified silica; Wherein, the solvent is composed of ethanol and water in a volume ratio of (3-5):1, and the imidazole functional group silane coupling agent includes 1-(3-(trimethoxysilyl)propyl)-1H-imidazole.

7. The environmentally friendly polyvinyl chloride wire and cable material according to any one of claims 1 to 4, characterized in that: The auxiliary agent includes a plasticizer, an antioxidant and a lubricant in a weight ratio of (19-23): (0.5-1.0): (1-2).

8. The environmentally friendly polyvinyl chloride wire and cable material according to claim 7, characterized in that: The plasticizer includes at least one of dioctyl sebacate and dioctyl azelate, the antioxidant includes at least one of antioxidant 1010 and antioxidant 168, and the lubricant includes at least one of stearic acid and polyethylene wax.

9. A method for preparing the environment-friendly polyvinyl chloride wire and cable material according to any one of claims 1 to 8, characterized in that: The preparation method comprises the following steps: The modified polyvinyl chloride, the polyisoprene containing a UPy unit at the end and the auxiliary agent are stirred and mixed at a temperature of 110 to 120° C. for 20 to 30 minutes to obtain a fourth mixture; After the fourth mixture is cooled to 80-90° C., fillers are added and stirring is continued for 30-60 minutes to obtain a fifth mixture; The mixture is added into a twin-screw extruder for melt extrusion and granulation at a temperature of 170-185° C. to obtain the environmentally friendly polyvinyl chloride wire and cable material.

10. Use of the environment-friendly polyvinyl chloride wire and cable material according to any one of claims 1 to 8 or the environment-friendly polyvinyl chloride wire and cable material prepared by the preparation method of the environment-friendly polyvinyl chloride wire and cable material according to claim 9 in preparing a high and low temperature resistant cable, characterized in that: The high and low temperature resistant cable comprises a conductor and an insulating material coated on the conductor, wherein the insulating material is the environmentally friendly polyvinyl chloride wire and cable material as described in any one of claims 1 to 8 or the environmentally friendly polyvinyl chloride wire and cable material prepared by the preparation method of the environmentally friendly polyvinyl chloride wire and cable material as described in claim 9.

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