The blends made of nitrile rubber (NBR) and polyvinyl chloride (PVC) blends are currently the main types of rubber and plastic used together. The main advantages of NBR/PVC blends are the combination of ozone resistance of PVC and oil resistance and crosslinkability of NBR, good physical and mechanical properties, and its main raw material PVC is rich in source and low in price, so it is widely used.
First, the application of NBR / PVC blends rubber is mainly used for oil pipe and fuel pipe outer plastic, wire and cable jacket, automotive waterproof strip, automotive seals, rubber rollers and rubber rings, automotive molded parts, microporous sponge, foam insulation Layers, soles, and protective coatings.
1. The hose NBR/PVC blends are widely used in rubber hoses, especially oil hoses and gas hoses. The Nanjing 7425 plant uses German Perbun-an NY/VC2870B rubber compound to produce fire-resistant oil hoses. The products have been officially produced. After the customer tests and uses, the general response is better. Pure rubber pipe extrusion molding, extrusion speed, surface smooth black products, good billet stiffness, expansion rate is small, easy to control the size. The rubber camp with braided layer needs to be dried after the woven rubber tube is finished, and the outer layer process is the same as the pure rubber tube extrusion process.
Zhejiang Haimen Rubber Factory and Yining Rubber Factory in Xinjiang used PVC modified NBR to produce textile hoses. The hose is divided into 3 types: YRC-9310 (for wool spinning), YRC-9311 (for cotton spinning) and YRC-9312 (for chemical fiber spinning). The machine has been tested in Yili Textile Factory with good results, especially in terms of wear resistance, aging resistance, life span and breakage rate.
Yizhong Zhongnan Rubber Group Co., Ltd. studied the formula and compounding process for the preparation of rubber hoses using NBR/PVC/CO ternary blends. The blends of Perbunan NT/VC 3470B and chlorohydrin rubber (CO) from Bayer AG were used. The developed oil-resistant hose is used for the accessories near the automobile engine. It is usually a special-shaped hose with a three-dimensional space size. When vulcanizing, the blank needs to be inserted into a shaped mandrel that meets the design requirements.
2, wire and cable NBR / PVC blends are widely used in wire and cable industry, in the field of submarine cables and other special cables can compete with EPDM / PP. There are 7000-8000 small and medium-sized cable factories in China, and the annual consumption of NBR/PVC is very large.
3, seals Seals are mainly automotive rubber seals and plastic window seals.
Automotive rubber seals are mainly used for parts of vehicles such as doors and windows, covers to create gaps, sealing, shock absorption, sound insulation, and decorative effects to prevent external sand, rain, dust, and other harmful substances from intruding into the car to enhance automotive parts. Working life and ride comfort. Automotive seals are the largest category of rubber used in cars except tires. The special materials for waterproof roof strips for automotive roofs are required to have sufficient resilience, hardness, oil resistance, weather resistance, and tightness. Moreover, in order to make the waterproof strips have a long-lasting rigidity, many metal pieces need to be lined, which requires the special materials to have good fluidity and mold filling properties, so as to ensure the simultaneous completion of the compounding in the extrusion process. The special waterproof material for automobile roofs developed by East China University of Science and Technology can be used in the production of Santana car roof weather strips. All performances have met the importation of Santana's Li top waterproof strips and can completely replace imported products. In addition to its use as roof weather strips, this special material can also be used as door trims, hood trims, fender trims and sill trims. Qingdao Institute of Chemical Technology carried out research on the use of powdered acrylonitrile-butadiene rubber modified high-degree-of-polymerization polyvinyl chloride (PVC) with a concealed structure to manufacture automobile weather strips. The pressed weather strips reached the LE608A index of Japanese imports. The Beijing Chemical Research Institute used the United States Good-Year company CHEMIGUMP83 to develop PVC window seals for plastic windows. The performance of the sealing strips can reach GB1200-89. This process can eliminate the need for cutting rubber, open mills, smelting processes and equipment. The process of direct blending, granulation, and extrusion seals. General profile production plants can produce without additional equipment.
4, rubber roller Cots are metal core, covered rubber, processed by a certain process. Due to the slight elastic deformation of the rubber layer of the roller surface, the product is subjected to a certain pressure, and at the same time it does not cause excessive shear stress and damage the product, so it has a very wide range of uses. For a long time, most rubber rollers use pure rubber as the outer core material of the metal core. Polyvinyl chloride (PVC) and nitrile rubber (NBR) blends combine the advantages of both PVC and NBR, with good resistance to oil, chemicals, and ozone. Compared with NBR rubber roller, the tensile strength, tear strength, abrasion resistance, solvent resistance and ozone cracking resistance of PVC/NRB blended and used roller are significantly improved. The adhesive roller made is especially suitable for the occasion where light-colored rubber rollers are required. This is because NBR/PVC has a high strength and can overcome the disadvantages of low-strength defects caused by the inability of carbon black to reinforce light-colored rubber products. At the same time, the NBR/PVC blender rubber roll is bright and colorful and can meet the latex glove linkage production line. , printing, printing and dyeing, textile and other industries. Nanjing Fidelity Rubber Application Technology Research Institute conducted a PVC/NBR/BR ternary blending process to prepare a light-colored rubber roller and studied the formula and process, and obtained a light-colored rubber roller with better overall performance.
Zhongnan Rubber Group Long March Parts Factory adopts NBR and emulsion method PVC to manufacture color printing rubber rollers. The products are oil-resistant, wear-resistant, hard to carry static electricity, the surface is easy to be ground and the ink printing performance is good. Yichang Xinhua Printing Co., Ltd. uses this roller to evaluate its performance: good elasticity, moderate hardness, rebound rate suitable for commercial speed printing, uniform ink transfer, small wear on printing plate, high printing rate, and oil resistance And the chemical resistance is better than the pure rubber type rubber roller; the glue residue phenomenon is not found in use, the radial movement is small, the appearance is smooth, the handle is good, and the processing precision is high. The performance meets the HG2287-92 standard. The printing roller made of the NBR/PVC blending glue is used by Lake Beijing Fengfeng Machinery Co., Ltd. in the supporting export printers. It has good oil resistance and wear resistance, uniform ink transfer, and is not easy to carry static electricity, improving the safety of the use environment. .
5. The shoe sole modified PVC is one of the most widely used kinds of sole material at home and abroad. The modifiers used are mainly NBR, polyurethane (PU), ethylene-vinyl acetate (EVA) containing the third polar component. Terpolymers (Elvaloy 741, 742 from DuPont). Compared with the latter two modifiers, NBR is more effective in improving the oil resistance, solvent resistance, flex crack resistance, and abrasion resistance of the substrate, and its lower price makes it a modified PVC sole material. High performance/price ratio varieties. It is worth mentioning that, since GoodYear and Polysar have successfully developed powder NBRs (Chemigun P83 and Krynac 1122), they can be used in advanced and efficient extrusion-injection processes to obtain pellets because of their convenient use and processing with PVC and additives. With the substrate, the PVC/NBR sole material has been rapidly developed at home and abroad in recent years. Sichuan United University studied domestically produced NBR powders and agglomerates for PVC modification, and used the injection molding method to manufacture the formulas and processing technology for leather shoe substrates. Based on the experimental research, the industrialization test produced a consistent performance CB4492-84. And QB1002-90 domestic modified PVC shoes with pellets and substrates. The trial production of pellets and substrates was tried by a number of plastics factories and shoe factories, which proved that it has good processing fluidity and thermal stability, high product yield, good appearance gloss, strong rubber feel, etc., and can be modified with the use of imports Similar products such as P83 and 741 are comparable. NBR/PVC can be used to produce imitation leather. Nanjing Plastics No. 9 Researched the blend ratio of non-vulcanized PVC/NBR blended imitation leather, anti-aging agent, old agent, mixing time and temperature to PVC/NBR leather. The effect of bottom physical and mechanical properties.
6. Sponge Foam At present, China's production of PVC flexible foam plastic still adopts the method of molding and secondary foaming, that is, the parison containing the foaming agent is first made by the method of molding, and then the parison is put into the oven and the parison is heated. The inner foaming agent releases gas to form a foam. This secondary foaming process is behind. Low production efficiency. After the NBR/PVC flexible foam, the parisons and parisons can be foamed and finished on a hydraulic press. This primary foaming process is more advanced than the secondary foaming process, and the production efficiency is improved. NBR/PVC foam products have excellent properties such as good elasticity, low density, small shrinkage deformation rate, etc., and have cushioning effect, and are widely used in sealing products, sporting goods, and shoe sole materials.
7. Others In addition, NBR/PVC can also be used for protective coatings and various accessories. Qingdao Chemical Engineering Institute has developed chemical fiber aprons with NBR/PVC and its performance has been significantly improved.
II. Development at home and abroad 1. Overview of foreign development As early as 1936, Konard theoretically stated that NBR/PVC blends have both ozone resistance, weather resistance, and cross-linkability of NBR. And oil resistance. With the in-depth study of the blending method. The emulsion coprecipitation method appears, and the research of NBR/PVC blends has attracted more and more attention. NBR/PVC blends are the first industrially produced rubber-plastic blends and are used in mechanical blends, emulsion blends, and solution blends. The blending ratios of foreign mechanical blended NBR/PVC thermoplastic elastomers are 70/30, 60/40, and 50/50, and representative products are Elastar of Japan Zeon Corporation and DenKa of Japan Electrochemical Corporation. DenKaLCS and Tempel of Pilltec, USA. The NBR/PVC representative product produced by the emulsion coprecipitation method is Bayer Perbunan NT/VC.
In 1985, Zeon Corporation first produced NBR/PVC alloys and thermoplastic elastomers by dynamic vulcanization and realized industrialization under the trade name of Elastar. The NBR/PVC blends produced by Zeon are produced at the Kawasaki plant. There are two production methods. One is mixed in the latex state and the other is dry mixing. The dry mixing technology has been exported to South Korea. Elastar has 10 grades of common grade, heat resistance, oil resistance and non-extraction. Among them, ES-3601 introduced in 1987 marks a new breakthrough in NBR/PVC blending technology. All products of Elastar can be molded by extrusion, injection, blow molding and other processing methods, featuring high elasticity, small permanent deformation, oil resistance, aging resistance, ozone resistance, and chemical resistance at high temperatures. The DenKa LCS introduced by DenKa in Japan is a PVC TPE modified with NBR. It has 12 grades and is superior in oil resistance, ozone resistance and sound absorption, and can partially replace EPDM.
Uniroyal Chemical Company of the United States produces OZO, OZO-HA, OZO-515, and X4 grades of NBR/PVC blends. OZO is used for special wire and cable sheathing, shoe soles, hoses, tapes, conveyors, sponges, and mechanical products. . There are two kinds of production methods. One is the use of PVC latex as raw material, the PVC latex in the latex blending process is added to the nitrile latex, coagulation - washing - extrusion dehydration - box drying - tablet cutting - packaging. The other is the use of PVC powder, the PVC powder is added to the agglomerate, the coagulation - washing - extrusion dehydration - mechanical drying - boiling drying - tablet cutting - packaging. Mechanical drying uses the special machinery of Uniroyal Chemical Company. NBR/PVC blends produced by Japan Synthetic Rubber Company (JSR) are dry-processed. The products are not produced at the Yokkaichi plant, but are produced at a subsidiary and the output is 2100-2400 tons/year. The main brands are Nv-72, Nv-73, Nv-75, Nv-76. The major brands of NBR/PVC blends produced by Bayer in the emulsion co-deposition method are Per-bunan NT/VC2870, Perbunan NT/VC3470, Perbunan NT/VC2870B, Perbunan NT/VC3470B, and Perbunan NT/VC4370B.
2. Domestic development status China started to research on NBR/PVC blending later. Started in the 1970s. The 1980s was at its peak and it was not until the 1990s that industrialization began. During this period, the Canadian company Bao Lan Shan and Chinese companies had envisaged cooperation to establish a NBR/PVC production and sales base to meet the domestic market.
First, the application of NBR / PVC blends rubber is mainly used for oil pipe and fuel pipe outer plastic, wire and cable jacket, automotive waterproof strip, automotive seals, rubber rollers and rubber rings, automotive molded parts, microporous sponge, foam insulation Layers, soles, and protective coatings.
1. The hose NBR/PVC blends are widely used in rubber hoses, especially oil hoses and gas hoses. The Nanjing 7425 plant uses German Perbun-an NY/VC2870B rubber compound to produce fire-resistant oil hoses. The products have been officially produced. After the customer tests and uses, the general response is better. Pure rubber pipe extrusion molding, extrusion speed, surface smooth black products, good billet stiffness, expansion rate is small, easy to control the size. The rubber camp with braided layer needs to be dried after the woven rubber tube is finished, and the outer layer process is the same as the pure rubber tube extrusion process.
Zhejiang Haimen Rubber Factory and Yining Rubber Factory in Xinjiang used PVC modified NBR to produce textile hoses. The hose is divided into 3 types: YRC-9310 (for wool spinning), YRC-9311 (for cotton spinning) and YRC-9312 (for chemical fiber spinning). The machine has been tested in Yili Textile Factory with good results, especially in terms of wear resistance, aging resistance, life span and breakage rate.
Yizhong Zhongnan Rubber Group Co., Ltd. studied the formula and compounding process for the preparation of rubber hoses using NBR/PVC/CO ternary blends. The blends of Perbunan NT/VC 3470B and chlorohydrin rubber (CO) from Bayer AG were used. The developed oil-resistant hose is used for the accessories near the automobile engine. It is usually a special-shaped hose with a three-dimensional space size. When vulcanizing, the blank needs to be inserted into a shaped mandrel that meets the design requirements.
2, wire and cable NBR / PVC blends are widely used in wire and cable industry, in the field of submarine cables and other special cables can compete with EPDM / PP. There are 7000-8000 small and medium-sized cable factories in China, and the annual consumption of NBR/PVC is very large.
3, seals Seals are mainly automotive rubber seals and plastic window seals.
Automotive rubber seals are mainly used for parts of vehicles such as doors and windows, covers to create gaps, sealing, shock absorption, sound insulation, and decorative effects to prevent external sand, rain, dust, and other harmful substances from intruding into the car to enhance automotive parts. Working life and ride comfort. Automotive seals are the largest category of rubber used in cars except tires. The special materials for waterproof roof strips for automotive roofs are required to have sufficient resilience, hardness, oil resistance, weather resistance, and tightness. Moreover, in order to make the waterproof strips have a long-lasting rigidity, many metal pieces need to be lined, which requires the special materials to have good fluidity and mold filling properties, so as to ensure the simultaneous completion of the compounding in the extrusion process. The special waterproof material for automobile roofs developed by East China University of Science and Technology can be used in the production of Santana car roof weather strips. All performances have met the importation of Santana's Li top waterproof strips and can completely replace imported products. In addition to its use as roof weather strips, this special material can also be used as door trims, hood trims, fender trims and sill trims. Qingdao Institute of Chemical Technology carried out research on the use of powdered acrylonitrile-butadiene rubber modified high-degree-of-polymerization polyvinyl chloride (PVC) with a concealed structure to manufacture automobile weather strips. The pressed weather strips reached the LE608A index of Japanese imports. The Beijing Chemical Research Institute used the United States Good-Year company CHEMIGUMP83 to develop PVC window seals for plastic windows. The performance of the sealing strips can reach GB1200-89. This process can eliminate the need for cutting rubber, open mills, smelting processes and equipment. The process of direct blending, granulation, and extrusion seals. General profile production plants can produce without additional equipment.
4, rubber roller Cots are metal core, covered rubber, processed by a certain process. Due to the slight elastic deformation of the rubber layer of the roller surface, the product is subjected to a certain pressure, and at the same time it does not cause excessive shear stress and damage the product, so it has a very wide range of uses. For a long time, most rubber rollers use pure rubber as the outer core material of the metal core. Polyvinyl chloride (PVC) and nitrile rubber (NBR) blends combine the advantages of both PVC and NBR, with good resistance to oil, chemicals, and ozone. Compared with NBR rubber roller, the tensile strength, tear strength, abrasion resistance, solvent resistance and ozone cracking resistance of PVC/NRB blended and used roller are significantly improved. The adhesive roller made is especially suitable for the occasion where light-colored rubber rollers are required. This is because NBR/PVC has a high strength and can overcome the disadvantages of low-strength defects caused by the inability of carbon black to reinforce light-colored rubber products. At the same time, the NBR/PVC blender rubber roll is bright and colorful and can meet the latex glove linkage production line. , printing, printing and dyeing, textile and other industries. Nanjing Fidelity Rubber Application Technology Research Institute conducted a PVC/NBR/BR ternary blending process to prepare a light-colored rubber roller and studied the formula and process, and obtained a light-colored rubber roller with better overall performance.
Zhongnan Rubber Group Long March Parts Factory adopts NBR and emulsion method PVC to manufacture color printing rubber rollers. The products are oil-resistant, wear-resistant, hard to carry static electricity, the surface is easy to be ground and the ink printing performance is good. Yichang Xinhua Printing Co., Ltd. uses this roller to evaluate its performance: good elasticity, moderate hardness, rebound rate suitable for commercial speed printing, uniform ink transfer, small wear on printing plate, high printing rate, and oil resistance And the chemical resistance is better than the pure rubber type rubber roller; the glue residue phenomenon is not found in use, the radial movement is small, the appearance is smooth, the handle is good, and the processing precision is high. The performance meets the HG2287-92 standard. The printing roller made of the NBR/PVC blending glue is used by Lake Beijing Fengfeng Machinery Co., Ltd. in the supporting export printers. It has good oil resistance and wear resistance, uniform ink transfer, and is not easy to carry static electricity, improving the safety of the use environment. .
5. The shoe sole modified PVC is one of the most widely used kinds of sole material at home and abroad. The modifiers used are mainly NBR, polyurethane (PU), ethylene-vinyl acetate (EVA) containing the third polar component. Terpolymers (Elvaloy 741, 742 from DuPont). Compared with the latter two modifiers, NBR is more effective in improving the oil resistance, solvent resistance, flex crack resistance, and abrasion resistance of the substrate, and its lower price makes it a modified PVC sole material. High performance/price ratio varieties. It is worth mentioning that, since GoodYear and Polysar have successfully developed powder NBRs (Chemigun P83 and Krynac 1122), they can be used in advanced and efficient extrusion-injection processes to obtain pellets because of their convenient use and processing with PVC and additives. With the substrate, the PVC/NBR sole material has been rapidly developed at home and abroad in recent years. Sichuan United University studied domestically produced NBR powders and agglomerates for PVC modification, and used the injection molding method to manufacture the formulas and processing technology for leather shoe substrates. Based on the experimental research, the industrialization test produced a consistent performance CB4492-84. And QB1002-90 domestic modified PVC shoes with pellets and substrates. The trial production of pellets and substrates was tried by a number of plastics factories and shoe factories, which proved that it has good processing fluidity and thermal stability, high product yield, good appearance gloss, strong rubber feel, etc., and can be modified with the use of imports Similar products such as P83 and 741 are comparable. NBR/PVC can be used to produce imitation leather. Nanjing Plastics No. 9 Researched the blend ratio of non-vulcanized PVC/NBR blended imitation leather, anti-aging agent, old agent, mixing time and temperature to PVC/NBR leather. The effect of bottom physical and mechanical properties.
6. Sponge Foam At present, China's production of PVC flexible foam plastic still adopts the method of molding and secondary foaming, that is, the parison containing the foaming agent is first made by the method of molding, and then the parison is put into the oven and the parison is heated. The inner foaming agent releases gas to form a foam. This secondary foaming process is behind. Low production efficiency. After the NBR/PVC flexible foam, the parisons and parisons can be foamed and finished on a hydraulic press. This primary foaming process is more advanced than the secondary foaming process, and the production efficiency is improved. NBR/PVC foam products have excellent properties such as good elasticity, low density, small shrinkage deformation rate, etc., and have cushioning effect, and are widely used in sealing products, sporting goods, and shoe sole materials.
7. Others In addition, NBR/PVC can also be used for protective coatings and various accessories. Qingdao Chemical Engineering Institute has developed chemical fiber aprons with NBR/PVC and its performance has been significantly improved.
II. Development at home and abroad 1. Overview of foreign development As early as 1936, Konard theoretically stated that NBR/PVC blends have both ozone resistance, weather resistance, and cross-linkability of NBR. And oil resistance. With the in-depth study of the blending method. The emulsion coprecipitation method appears, and the research of NBR/PVC blends has attracted more and more attention. NBR/PVC blends are the first industrially produced rubber-plastic blends and are used in mechanical blends, emulsion blends, and solution blends. The blending ratios of foreign mechanical blended NBR/PVC thermoplastic elastomers are 70/30, 60/40, and 50/50, and representative products are Elastar of Japan Zeon Corporation and DenKa of Japan Electrochemical Corporation. DenKaLCS and Tempel of Pilltec, USA. The NBR/PVC representative product produced by the emulsion coprecipitation method is Bayer Perbunan NT/VC.
In 1985, Zeon Corporation first produced NBR/PVC alloys and thermoplastic elastomers by dynamic vulcanization and realized industrialization under the trade name of Elastar. The NBR/PVC blends produced by Zeon are produced at the Kawasaki plant. There are two production methods. One is mixed in the latex state and the other is dry mixing. The dry mixing technology has been exported to South Korea. Elastar has 10 grades of common grade, heat resistance, oil resistance and non-extraction. Among them, ES-3601 introduced in 1987 marks a new breakthrough in NBR/PVC blending technology. All products of Elastar can be molded by extrusion, injection, blow molding and other processing methods, featuring high elasticity, small permanent deformation, oil resistance, aging resistance, ozone resistance, and chemical resistance at high temperatures. The DenKa LCS introduced by DenKa in Japan is a PVC TPE modified with NBR. It has 12 grades and is superior in oil resistance, ozone resistance and sound absorption, and can partially replace EPDM.
Uniroyal Chemical Company of the United States produces OZO, OZO-HA, OZO-515, and X4 grades of NBR/PVC blends. OZO is used for special wire and cable sheathing, shoe soles, hoses, tapes, conveyors, sponges, and mechanical products. . There are two kinds of production methods. One is the use of PVC latex as raw material, the PVC latex in the latex blending process is added to the nitrile latex, coagulation - washing - extrusion dehydration - box drying - tablet cutting - packaging. The other is the use of PVC powder, the PVC powder is added to the agglomerate, the coagulation - washing - extrusion dehydration - mechanical drying - boiling drying - tablet cutting - packaging. Mechanical drying uses the special machinery of Uniroyal Chemical Company. NBR/PVC blends produced by Japan Synthetic Rubber Company (JSR) are dry-processed. The products are not produced at the Yokkaichi plant, but are produced at a subsidiary and the output is 2100-2400 tons/year. The main brands are Nv-72, Nv-73, Nv-75, Nv-76. The major brands of NBR/PVC blends produced by Bayer in the emulsion co-deposition method are Per-bunan NT/VC2870, Perbunan NT/VC3470, Perbunan NT/VC2870B, Perbunan NT/VC3470B, and Perbunan NT/VC4370B.
2. Domestic development status China started to research on NBR/PVC blending later. Started in the 1970s. The 1980s was at its peak and it was not until the 1990s that industrialization began. During this period, the Canadian company Bao Lan Shan and Chinese companies had envisaged cooperation to establish a NBR/PVC production and sales base to meet the domestic market.
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