NBR / PVC blended rubber-plastic material and anti-cracking hose

Abstract

The present application relates to the technical field of rubber and plastic materials, and specifically provides a NBR / PVC blended rubber and plastic material and an anti-cracking hose. The NBR / PVC blended rubber and plastic material of the present application, by weight, includes the following raw material components, 100 parts of NBR / PVC alloy, 30-70 parts of carbon black, 2-5 parts of accelerator, 4-10 parts of activator, 0.5-2 parts of stearic acid, 0.5-3 parts of vulcanizing agent, 1-5 parts of anti-aging agent, 20-60 parts of plasticizer, 1-5 parts of heat stabilizer, 3-10 parts of double-terminated amino liquid nitrile rubber and 0.1-1 parts of maleic anhydride grafted ABS. The hose obtained by processing the NBR / PVC blended rubber and plastic material of the present application has good tensile strength, especially still has good tensile strength at high temperature, and is not easy to crack when expanding at high temperature.

Description

Technical Field

[0001] The present application relates to the technical field of rubber and plastic materials, and in particular to an NBR / PVC blended rubber and plastic material and an anti-cracking hose. Background Art

[0002] NBR / PVC blended rubber and plastic materials have the oil resistance and cross-linking properties of NBR (nitrile rubber) and the ozone resistance and flexibility of PVC. They have been used in automotive power steering pipes, fuel hoses, crankcase ventilation hoses, etc. With the advancement of automobile manufacturing technology, NBR / PVC blended rubber and plastic hoses are required to be expanded at high temperatures (such as 150°C). Existing NBR / PVC blended plastic hoses are prone to cracking when expanded at high temperatures, resulting in the hose being directly scrapped.

[0003] Therefore, it is necessary to improve the anti-cracking performance of NBR / PVC blended plastic hose when expanding at high temperature. Summary of the invention

[0004] The inventors found that the expansion of the hose at high temperature requires good tensile strength to prevent cracking, but the tensile strength of the NBR / PVC blended plastic hose at high temperature is poor, so it is easy to crack. In order to solve the above technical problems, the present application provides an NBR / PVC blended rubber-plastic material and an anti-cracking hose.

[0005] This application adopts the following technical solutions:

[0006] A NBR / PVC blended rubber and plastic material comprises the following raw material components by weight: 100 parts of NBR / PVC alloy, 30-70 parts of carbon black, 2-5 parts of accelerator, 4-10 parts of activator, 0.5-2 parts of stearic acid, 0.5-3 parts of vulcanizer, 1-5 parts of anti-aging agent, 20-60 parts of plasticizer, 1-5 parts of heat stabilizer, 3-10 parts of double-terminated amino liquid nitrile rubber and 0.1-1 parts of maleic anhydride grafted ABS.

[0007] Preferably, the NBR / PVC alloy consists of NBR and PVC in a weight ratio of 1:9-9:1.

[0008] Preferably, the accelerator is selected from one or a combination of two of vulcanization accelerator D, vulcanization accelerator TMTD, vulcanization accelerator M, vulcanization accelerator ZDMC, vulcanization accelerator NA-22 and vulcanization accelerator CZ.

[0009] Preferably, the activator is selected from one or two of zinc oxide, magnesium oxide, zinc stearate, magnesium stearate and calcium stearate.

[0010] Preferably, the vulcanizing agent is selected from sulfur or dicumyl peroxide.

[0011] Preferably, the plasticizer is selected from one or more of tributyl citrate, acetyl tributyl citrate, acetyl trioctyl citrate, trioctyl citrate, dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate, diisononyl phthalate, diisoundecyl phthalate, triisooctyl trimellitate, triisononyl trimellitate, triisotridecyl trimellitate, dioctyl sebacate, dioctyl butyl sebacate, dioctyl oxalate, diisooctyl adipate and diisooctyl sebacate.

[0012] Preferably, the average molecular weight of the double-terminated amino liquid nitrile rubber is 1000-5000.

[0013] Preferably, the grafting rate of the maleic anhydride grafted ABS is 1-8wt%.

[0014] Preferably, the raw material components also include a lubricant.

[0015] An anti-cracking rubber hose is obtained by using the NBR / PVC blended rubber and plastic material described in any of the above implementation schemes as a raw material, mixing evenly, extruding, and heating and vulcanizing.

[0016] In summary, this application has the following beneficial effects:

[0017] 1. In the present application, double-terminated amino liquid nitrile rubber and maleic anhydride grafted ABS are added to the NBR / PVC blended rubber and plastic material. Both the double-terminated amino liquid nitrile rubber and the maleic anhydride grafted ABS can play a toughening role, and the amino group of the double-terminated amino liquid nitrile rubber and the maleic anhydride group on the maleic anhydride grafted ABS can react quickly at high temperature to form a cross-linked structure, thereby improving the stability of NBR / PVC at high temperature and still having good tensile strength at high temperature.

[0018] 2. ABS has some non-polar segments, which may affect the stability of the hose in fuel. This application controls the amount of maleic anhydride grafted to ABS, which can not only achieve toughening and improve tensile strength, but also produce a cross-linking reaction with double-terminated amino liquid nitrile rubber, and the cross-linking reaction can reduce the impact of fuel.

[0019] 3. In the present application, the NBR / PVC alloy material can be vulcanized into a cross-linked structure under a vulcanizing agent, and the cross-linked structure formed by the double-terminated amino liquid nitrile rubber and the maleic anhydride grafted ABS forms an interpenetrating polymer network structure, thereby improving the stability of the tensile strength of the hose at high temperature and reducing the impact of the fuel brought by ABS.

[0020] 4. The anti-cracking hose of the present application has high tensile strength at high temperatures, is not prone to cracking during expansion, and has good fuel resistance stability. DETAILED DESCRIPTION

[0021] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described in detail below.

[0022] Throughout the specification, unless otherwise specifically stated, the terms used herein should be understood as meanings commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. In the event of a conflict, the present specification takes precedence.

[0023] On the one hand, the present application proposes an NBR / PVC blended rubber and plastic material, which includes the following raw material components, by weight, 100 parts of NBR / PVC alloy, 30-70 parts of carbon black, 2-5 parts of accelerator, 4-10 parts of activator, 0.5-2 parts of stearic acid, 0.5-3 parts of vulcanizer, 1-5 parts of anti-aging agent, 20-60 parts of plasticizer, 1-5 parts of heat stabilizer, 3-10 parts of double-terminated amino liquid nitrile rubber and 0.1-1 parts of maleic anhydride grafted ABS.

[0024] In the present application, there is no particular limitation on carbon black, which can be selected from N550, N220, N774, N330, N660, etc.; in the present application, there is no particular limitation on the anti-aging agent, which can be selected from anti-aging agent 1010, anti-aging agent 1076, anti-aging agent 168, etc.; in the present application, there is no particular limitation on the heat stabilizer, which can be selected from barium zinc stabilizer, calcium zinc stabilizer, etc.

[0025] In the present application, further, the NBR / PVC alloy is composed of NBR and PVC in a weight ratio of 1:9-9:1. Both NBR and PVC are polar polymer materials with good compatibility and can be mixed in any proportion to make up for their respective defects and give full play to the advantages of both. Further, the NBR / PVC alloy is composed of NBR and PVC in a weight ratio of 2:8-7:3.

[0026] Vulcanization accelerator can shorten the vulcanization time, reduce the vulcanization temperature, reduce the amount of vulcanizing agent, and promote vulcanization more completely, improve the physical and mechanical properties of rubber and plastic materials. In the present application, further, the accelerator can be selected from aldehyde amine vulcanization accelerator, guanidine vulcanization accelerator, thiuram vulcanization accelerator, thiazole vulcanization accelerator, dithiocarbamate vulcanization accelerator, xanthate vulcanization accelerator, thiourea vulcanization accelerator, sulfonamide vulcanization accelerator, etc., specifically, the vulcanization accelerator can be selected from one or two combinations of vulcanization accelerator D, vulcanization accelerator TMTD, vulcanization accelerator M, vulcanization accelerator ZDMC, vulcanization accelerator NA-22 and vulcanization accelerator CZ. Further, the accelerator can be selected from thiuram accelerators, such as vulcanization accelerator TMTD, vulcanization accelerator TMTM, vulcanization accelerator TETD, vulcanization accelerator DPTT, etc.

[0027] The activator is a processing aid that promotes the vulcanization reaction. In the present application, further, the activator can be selected from one or more of an inorganic vulcanization activator and an organic vulcanization activator. The inorganic vulcanization activator can be selected from zinc oxide or magnesium oxide, and the organic vulcanization activator can be selected from stearic acid, palmitic acid, lauric acid and its zinc salt, magnesium salt or calcium salt, etc. Specifically, the activator can be selected from one or two of zinc oxide, magnesium oxide, zinc stearate, magnesium stearate and calcium stearate.

[0028] In the present application, further, the vulcanizing agent is selected from sulfur or dicumyl peroxide. The sulfur can be one or a mixture of sulfur powder, sublimated sulfur and precipitated sulfur.

[0029] In the present application, further, the plasticizer is not particularly limited and can be selected from one or more of tributyl citrate, acetyl tributyl citrate, trioctyl acetyl citrate, trioctyl citrate, dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate, diisononyl phthalate, diisoundecyl phthalate, triisooctyl trimellitate, triisononyl trimellitate, triisotridecyl trimellitate, dioctyl sebacate, dioctyl butyl sebacate, dioctyl oxalate, diisooctyl adipate and diisooctyl sebacate. In the present application, the plasticizer can also be selected from epoxidized soybean oil, polyester plasticizer, etc., or a combination of epoxidized soybean oil, polyester plasticizer, etc. and the above-mentioned plasticizer.

[0030] In the present application, further, the mean molecular weight of the double-terminated amino liquid acrylonitrile rubber is 1000-5000. Two amino groups are located at two end groups in the molecular structure of the double-terminated amino liquid acrylonitrile rubber. The double-terminated amino liquid acrylonitrile rubber can be used as a toughening agent except itself, and the molecular weight is larger, and the toughness at high temperature is better, and the reactivity of amino and anhydride can also be utilized, and the double-terminated amino liquid acrylonitrile rubber reacts with maleic anhydride grafted ABS to form a cross-linked structure, further improves the tensile strength of the hose at high temperature, and can also form an interpenetrating polymer network structure with the cross-linked NBR / PVC structure, except further improving the tensile strength of the hose, the tensile strength of the hose at high temperature can also be further improved. Further, the mean molecular weight of the double-terminated amino liquid acrylonitrile rubber is 1000-3000.

[0031] In the present application, further, the grafting rate of maleic anhydride grafted ABS is 1-8wt%. In the present application, the weight of maleic anhydride grafted ABS and the grafting rate have an influence on the cross-linking structure of maleic anhydride grafted ABS and double amino-terminated liquid nitrile rubber, and then affect the tensile strength and fuel resistance of the hose at high temperature. Further, when the weight of maleic anhydride grafted ABS is 0.1-0.5 parts, the grafting rate of maleic anhydride grafted ABS can be 5-8wt%, so that the cross-linking degree of the cross-linking reaction of maleic anhydride grafted ABS and double amino-terminated liquid nitrile rubber can be maintained in a more suitable range; when the weight of maleic anhydride grafted ABS is 0.5-1 parts, the grafting rate of maleic anhydride grafted ABS is 1-5wt%, so that the cross-linking degree of the cross-linking reaction of maleic anhydride grafted ABS and double amino-terminated liquid nitrile rubber can be maintained in a more suitable range. Furthermore, the weight portion of maleic anhydride grafted ABS is 0.3-0.7 parts, and the grafting rate of maleic anhydride grafted ABS is 3-6wt%. Furthermore, in the present application, the melt index (200°C, 5Kg) of maleic anhydride grafted ABS is 1-5g / min.

[0032] In the present application, further, the raw material components also include lubricants. The lubricants can improve the processing properties of the NBR / PVC blended rubber and plastic materials, and can be selected from oxidized polyethylene wax, polytetrafluoroethylene powder, fluororubber powder, etc. The weight proportion of the lubricants can be 2-5 parts.

[0033] On the other hand, the present application provides an anti-cracking rubber hose, which is obtained by using the NBR / PVC blended rubber and plastic material described in any of the above embodiments as a raw material, mixing evenly, extruding, and heating and vulcanizing.

[0034] In the present application, the heating temperature of the heating vulcanization can be 130-180° C. and the time can be 10-30 minutes.

[0035] The mixing of NBR / PVC blended rubber and plastic materials can be carried out according to the following procedures:

[0036] S1, mixing NBR / PVC alloy, plasticizer, heat stabilizer, accelerator, anti-aging agent, maleic anhydride grafted ABS, stearic acid (or lubricant) to obtain mixing component A;

[0037] S2, adding carbon black to the mixed component A in batches, mixing, and obtaining a mixed component B;

[0038] S3, adding double-terminated amino liquid nitrile rubber, vulcanizing agent and activator to the above mixing component B, and mixing evenly.

[0039] In the above step S1, the mixing temperature may be 120-150° C., and the mixing time may be 5-10 minutes.

[0040] In the above step S2, the mixing temperature can be 50-100°C, the mixing time for each batch of carbon black can be 2-5 minutes, and the carbon black can be added in 2-5 batches.

[0041] In the above step S3, the mixing temperature can be 10-30° C., and the mixing time can be 2-5 minutes.

[0042] The technical solution of the present application will be described in detail below with reference to embodiments, comparative examples and experimental data.

[0043] Example 1

[0044] The NBR / PVC alloy is composed of NBR (acrylonitrile content 45wt%) and PVC in a weight ratio of 2:1. The average molecular weight of the double-ended liquid nitrile rubber is 1200, the melt index (200℃, 5Kg) of maleic anhydride grafted ABS is 3g / min, and the grafting rate is 1.5wt%.

[0045] According to the formula: 100 parts of NBR / PVC alloy, 45 parts of carbon black N330, 3 parts of accelerator TMTD, 6 parts of zinc oxide activator, 1.2 parts of stearic acid, 2 parts of sublimated sulfur, 2 parts of antioxidant 1010, 40 parts of dibutyl sebacate, 2.5 parts of barium zinc heat stabilizer, 6 parts of double-terminated amino liquid nitrile rubber and 0.7 parts of maleic anhydride grafted ABS.

[0046] NBR / PVC alloy, dioctyl butyl sebacate, barium zinc heat stabilizer, accelerator TMTD, anti-aging agent 1010, maleic anhydride grafted ABS, and stearic acid are mixed at 140-145°C for 6 minutes to obtain mixing component A; carbon black N330 is added to the mixing component A in 3 batches, and mixed at 55-60°C for 3 minutes each time to obtain mixing component B; double-terminated amino liquid nitrile rubber, sublimated sulfur, and zinc oxide are added to the mixing component B, mixed at 20-25°C for 4 minutes, extruded, and heated at 165°C for 15 minutes for vulcanization to obtain a hose.

[0047] Example 2

[0048] In Example 1, the amount of maleic anhydride grafted ABS was adjusted from 0.7 parts to 1 part, and the other steps remained unchanged.

[0049] Example 3

[0050] In Example 1, the amount of the double-terminated amino liquid nitrile rubber was adjusted from 6 parts to 4 parts, and the other steps remained unchanged.

[0051] Example 4

[0052] In Example 1, the double-terminated amino liquid nitrile rubber is adjusted from 6 parts to 9 parts, and the other steps remain unchanged.

[0053] Example 5

[0054] The NBR / PVC alloy is composed of NBR (acrylonitrile content 38wt%) and PVC in a weight ratio of 1:1. The average molecular weight of the double-ended liquid nitrile rubber is 1500, the melt index (200℃, 5Kg) of maleic anhydride grafted ABS is 2.2g / min, and the grafting rate is 7.2wt%.

[0055] According to the formula: 100 parts of NBR / PVC alloy, 40 parts of carbon black N550, 3.5 parts of accelerator TMTD, 6 parts of zinc oxide activator, 1.5 parts of stearic acid, 2 parts of sublimated sulfur, 3 parts of antioxidant 168, 45 parts of diisooctyl sebacate, 2.5 parts of barium zinc heat stabilizer, 5 parts of double-terminated amino liquid nitrile rubber and 0.3 parts of maleic anhydride grafted ABS.

[0056] Prepare according to the preparation process of Example 1.

[0057] Example 6

[0058] In Example 5, the amount of maleic anhydride grafted ABS was adjusted from 0.3 parts to 0.15 parts, and the other steps remained unchanged.

[0059] Example 7

[0060] In Example 5, the amount of maleic anhydride grafted ABS was adjusted from 0.3 parts to 0.45 parts, and the other steps remained unchanged.

[0061] Example 8

[0062] In Example 5, the amount of the double-terminated amino liquid nitrile rubber is adjusted from 5 parts to 7 parts, and the other steps remain unchanged.

[0063] Example 9

[0064] In Example 5, the double-terminated amino liquid nitrile rubber is adjusted from 5 parts to 9 parts, and the other steps remain unchanged.

[0065] Comparative Example 1

[0066] In Example 1, no double-terminated amino liquid nitrile rubber and maleic anhydride grafted ABS were added, and the remaining steps remained unchanged.

[0067] Comparative Example 2

[0068] In Example 1, maleic anhydride was not added to graft ABS, and the other steps remained unchanged.

[0069] Comparative Example 3

[0070] In Example 1, no double-terminated amino liquid nitrile rubber is added, and the other steps remain unchanged.

[0071] Comparative Example 4

[0072] In Example 1, maleic anhydride grafted ABS replaced maleic anhydride grafted polypropylene in equal parts by weight (grafting rate 1.3 wt %), and the other steps remained unchanged.

[0073] Performance Testing

[0074] Fuel resistance: 5±0.1g of the hose to be tested is immersed in 23℃ fuel B for 72 hours, taken out, the fuel on the surface is wiped off, weighed, and the swelling rate is tested. Swelling rate = (weight after swelling - initial weight) / initial weight × 100%.

[0075] Tensile strength test: An electronic tensile testing machine was used to test the tensile strength at room temperature (25°C) and high temperature (150°C).

[0076] Expansion cracking test: 1000 hoses were taken and expanded by 30% at 150℃, and the cracking ratio was counted.

[0077] The results are shown in Table 1.

[0078] Table 1

[0079]

[0080]

[0081] From the results in Table 1, it can be seen that the addition of amino-terminated liquid nitrile rubber and maleic anhydride grafted ABS to the raw materials of the hose of the present application has higher room temperature tensile strength and high temperature tensile strength without affecting the fuel resistance, and the high temperature tensile strength is about 30-35% of the room temperature tensile strength (i.e., the high temperature maintenance rate of the tensile strength). In contrast, the high temperature maintenance rate of the tensile strength of the hose to which amino-terminated liquid nitrile rubber and maleic anhydride grafted ABS are not fully added is about 10-17%; replacing the maleic anhydride grafted ABS with maleic anhydride grafted polypropylene not only deteriorates the fuel resistance, but also deteriorates the room temperature and high temperature tensile strength and the high temperature maintenance rate of the tensile strength. This may be due to the non-polarity of the polypropylene segment, which leads to poor fuel resistance and poor compatibility with NBR / PVC.

[0082] In addition, the cracking ratio of the rubber hose of the present application in the expansion sleeve connection at high temperature is less than 2%, which is significantly better than the comparative example.

[0083] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A NBR / PVC blended rubber-plastic material, characterized in that: The raw material components include, by weight, 100 parts of NBR / PVC alloy, 30-70 parts of carbon black, 2-5 parts of accelerator, 4-10 parts of activator, 0.5-2 parts of stearic acid, 0.5-3 parts of vulcanizer, 1-5 parts of anti-aging agent, 20-60 parts of plasticizer, 1-5 parts of heat stabilizer, 3-10 parts of double-terminated amino liquid nitrile rubber and 0.1-1 parts of maleic anhydride grafted ABS; The NBR / PVC alloy is composed of NBR and PVC in a weight ratio of 1:9-9:1; The accelerator is selected from one or a combination of two of vulcanization accelerator D, vulcanization accelerator TMTD, vulcanization accelerator M, vulcanization accelerator ZDMC, vulcanization accelerator NA-22 and vulcanization accelerator CZ; The plasticizer is selected from one or more of tributyl citrate, acetyl tributyl citrate, acetyl trioctyl citrate, trioctyl citrate, dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate, diisononyl phthalate, diisoundecyl phthalate, triisooctyl trimellitate, triisononyl trimellitate, triisotridecyl trimellitate, dioctyl sebacate, dibutyl sebacate, dioctyl oxalate, diisooctyl adipate and diisooctyl sebacate; The average molecular weight of the double-terminated amino liquid nitrile rubber is 1000-5000; The grafting rate of the maleic anhydride grafted ABS is 1-8wt%; The activator is selected from one or two of zinc oxide, magnesium oxide, zinc stearate, magnesium stearate and calcium stearate.

2. The NBR / PVC blended rubber-plastic material according to claim 1, characterized in that: The vulcanizing agent is selected from sulfur or dicumyl peroxide.

3. The NBR / PVC blended rubber-plastic material according to claim 1, characterized in that: The feedstock components also include a lubricant.

4. An anti-cracking hose, characterized in that: The NBR / PVC blended rubber and plastic material according to any one of claims 1 to 3 is used as a raw material, mixed evenly, extruded, and heated and vulcanized to obtain the product.

Images