CN109912868B - Hydrogenated nitrile rubber and unsaturated nonpolar rubber laminated composite bonding transition layer sizing material - Google Patents
Hydrogenated nitrile rubber and unsaturated nonpolar rubber laminated composite bonding transition layer sizing material Download PDFInfo
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- CN109912868B CN109912868B CN201910241768.0A CN201910241768A CN109912868B CN 109912868 B CN109912868 B CN 109912868B CN 201910241768 A CN201910241768 A CN 201910241768A CN 109912868 B CN109912868 B CN 109912868B
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- 239000005060 rubber Substances 0.000 title claims abstract description 106
- 229920001971 elastomer Polymers 0.000 title claims abstract description 104
- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 74
- 230000007704 transition Effects 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims description 22
- 238000004513 sizing Methods 0.000 title description 9
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 41
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 41
- 229920001194 natural rubber Polymers 0.000 claims abstract description 41
- 239000006229 carbon black Substances 0.000 claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- STSDHUBQQWBRBH-UHFFFAOYSA-N n-cyclohexyl-1,3-benzothiazole-2-sulfonamide Chemical compound N=1C2=CC=CC=C2SC=1S(=O)(=O)NC1CCCCC1 STSDHUBQQWBRBH-UHFFFAOYSA-N 0.000 claims description 9
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 9
- 229960002447 thiram Drugs 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical group CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- -1 alkyl phenol-formaldehyde resin Chemical compound 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 30
- 239000011787 zinc oxide Substances 0.000 abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 14
- 235000021355 Stearic acid Nutrition 0.000 abstract description 13
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 abstract description 13
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 abstract description 13
- 239000008117 stearic acid Substances 0.000 abstract description 13
- 235000019241 carbon black Nutrition 0.000 description 33
- 239000005062 Polybutadiene Substances 0.000 description 11
- 230000003712 anti-aging effect Effects 0.000 description 11
- 229920002857 polybutadiene Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 description 7
- 239000004200 microcrystalline wax Substances 0.000 description 6
- 235000019808 microcrystalline wax Nutrition 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical group C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010058 rubber compounding Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- VDPNETBCJVBFIO-UHFFFAOYSA-M C(CCCCCCCCCCCCCCCCC)(=O)[O-].[I+] Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)[O-].[I+] VDPNETBCJVBFIO-UHFFFAOYSA-M 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a compound bonding transition layer rubber material laminated by hydrogenated nitrile rubber and unsaturated nonpolar rubber and a preparation method thereof. The transition layer rubber material comprises the following components in parts by weight: 60-70 parts of carboxyl nitrile rubber; 30-40 parts of natural rubber; 20-40 parts of general carbon black; 10-20 parts of white carbon black; 4-6 parts of a silane coupling agent; 4-6 parts of tackifying resin; 5-8 parts of zinc oxide; 1-2 parts of stearic acid; 3-3.5 parts of an accelerator; and 1-1.5 parts of a vulcanizing agent.
Description
Technical Field
The invention relates to a composite rubber product, in particular to a compound bonding transition layer rubber material laminated by hydrogenated nitrile rubber and unsaturated nonpolar rubber.
Background
Unsaturated nonpolar rubbers such as Natural Rubber (NR), Styrene Butadiene Rubber (SBR), Butadiene Rubber (BR), etc., have good elasticity, high strength, low heat generation, good flex resistance, and small hysteresis loss, but have poor heat resistance, poor oil resistance, poor solvent resistance, and poor aging resistance, and the use range of the unsaturated nonpolar rubbers is greatly limited.
The hydrogenated nitrile rubber (HNBR) not only maintains the oil resistance of unsaturated nonpolar rubber, has excellent wear resistance, but also has excellent heat resistance, weather resistance, oxygen resistance, chemical corrosion resistance and high tensile strength, and particularly has greatly improved heat resistance. However, unsaturated nonpolar rubber and hydrogenated nitrile rubber are difficult to be directly vulcanized and bonded, for multilayer composite rubber products (such as tires, rubber rollers and other products), the most critical factor influencing the product quality is the surface rubber performance directly contacting with the outside, if the vulcanization bonding problem of the unsaturated nonpolar rubber and the hydrogenated nitrile rubber can be solved, HNBR is applied to the outermost layer of the product, the performance advantages of wear resistance, heat resistance, weather resistance, oxygen resistance, chemical corrosion resistance and high tensile strength are fully exerted, and meanwhile, the superiorities of high elasticity, high strength, low heat generation, good flexibility resistance, small hysteresis loss and the like of the unsaturated nonpolar rubber are fully utilized, so that the using effect of the product can be greatly improved, and the service life can be prolonged.
Accordingly, there is a great need in the art to provide a compound that can effectively bond hydrogenated nitrile rubber to unsaturated non-polar rubber, and methods of making and using the same.
Disclosure of Invention
The invention aims to provide a compound bonding transition layer rubber material for laminating hydrogenated nitrile rubber and unsaturated nonpolar rubber.
In a first aspect of the invention, a compound bonding transition layer rubber material for laminating hydrogenated nitrile rubber and unsaturated nonpolar rubber is provided, which comprises the following components in parts by weight:
in another preferred embodiment, the components comprise the following components in parts by weight:
in another preferred embodiment, in the compound lamination bonding transition layer rubber material of hydrogenated nitrile rubber and unsaturated nonpolar rubber provided by the invention, the carboxyl content of the carboxyl nitrile rubber is 5-10%, the acrylonitrile content is 27-33%, and the Mooney viscosity (ML100 ℃, 1+4) is 20-50 calculated by the total weight of the carboxyl nitrile rubber.
In another preferred embodiment, in the compound lamination bonding transition layer rubber compound of the hydrogenated nitrile rubber and the unsaturated nonpolar rubber provided by the invention, the natural rubber is standard rubber.
In another preferred embodiment, the tackifying resin is an alkyl phenol-formaldehyde resin.
In another preferred embodiment, the silane coupling agent is bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide.
In another preferred embodiment, the accelerator is selected from one or two or more of the following: n-cyclohexyl-2-benzothiazole sulfonamide, 2' -dithiodibenzothiazole and tetramethyl thiuram disulfide.
In another preferred embodiment, the universal carbon black is selected from one or two or more of the following: n220 carbon black, N115 carbon black, N550 carbon black; the vulcanizing agent is sulfur.
In a second aspect of the present invention, there is provided a process for preparing a composite bonding transition layer compound of hydrogenated nitrile rubber and unsaturated non-polar rubber laminated composite bonding, as described above, said process comprising the steps of:
providing the components of the hydrogenated nitrile rubber and unsaturated nonpolar rubber laminated composite bonding transition layer rubber material;
and mixing and discharging the components of the transition layer rubber material to obtain the hydrogenated nitrile-butadiene rubber and unsaturated nonpolar rubber laminated composite bonding transition layer rubber material.
In a third aspect of the invention, there is provided the use of a hydrogenated nitrile rubber according to the invention as described above in laminating a composite adhesive transition layer compound with an unsaturated non-polar rubber.
Accordingly, the invention provides a rubber material capable of effectively bonding hydrogenated nitrile rubber and unsaturated nonpolar rubber, and a preparation method and application thereof.
Detailed Description
The inventor has found that the combination of the carboxylated nitrile rubber and a certain proportion of natural rubber can effectively solve the problem that the unsaturated nonpolar rubber and the hydrogenated nitrile rubber are difficult to be directly vulcanized and bonded, and effectively keeps the excellent properties of the two rubbers. On the basis of this, the present invention has been completed.
As used herein, the term "comprising" or "includes" means that the various ingredients can be used together in a mixture or composition of the invention. Thus, the terms "consisting essentially of and" consisting of are encompassed by the terms "comprising" or "including".
In the present invention, the "unsaturated nonpolar rubber" refers to Natural Rubber (NR), Styrene Butadiene Rubber (SBR), Butadiene Rubber (BR), or the like, or a rubber used in combination thereof.
In the present invention, "hydrogenated nitrile rubber (HNBR)" refers to a highly saturated elastomer obtained by the specific hydrogenation of nitrile rubber.
Various aspects of the invention are described in detail below:
transition layer sizing material
The invention provides a compound bonding transition layer rubber material laminated by hydrogenated nitrile rubber and unsaturated nonpolar rubber, which comprises the following components:
carboxylated nitrile rubber
The transition layer rubber material provided by the invention contains 60-70 parts by weight of carboxyl nitrile rubber, wherein the Mooney viscosity (ML100 ℃, 1+4) of the carboxyl nitrile rubber is 20-50, the carboxyl content is 5-10% and the acrylonitrile content is 27-33% based on the total weight of the carboxyl nitrile rubber.
Natural rubber
The transition layer rubber material provided by the invention contains 30-40 parts by weight of natural rubber, and the natural rubber is selected from standard rubber, such as but not limited to 20# standard rubber (Malaysia).
Universal carbon blacks
The transition layer rubber material provided by the invention contains 20-40 parts by weight of universal carbon black.
In one embodiment of the invention, the general carbon black particle size of 330-.
In a preferred embodiment, the universal carbon black is N220, N115, N550, or a combination thereof.
White carbon black
The transition layer sizing material provided by the invention contains 10-20 parts by weight of white carbon black.
Silane coupling agent
The transition layer sizing material provided by the invention contains 4-6 parts by weight of silane coupling agent.
In one embodiment of the present invention, bis- [ γ - (triethoxysilyl) propyl ] tetrasulfide (Si-69) is used as the silane coupling agent.
Tackifying resins
The transition layer rubber material provided by the invention contains 4-6 parts by weight of tackifying resin, wherein the tackifying resin is condensation resin.
In one embodiment of the invention, the tackifying resin is an alkyl phenol-formaldehyde resin; for example, but not limited to, phenolic tackifying resin SP-1068, which is a clear colorless to yellowish particulate having a softening point: 85-95 ℃, acid value: less than or equal to 65 mgKOH/g.
Zinc oxide
The transition layer rubber material provided by the invention contains 5-8 parts by weight of zinc oxide.
Stearic acid
The transition layer rubber material provided by the invention contains 1-2 parts by weight of stearic acid.
In one embodiment of the invention, the iodine stearate value is 7-9, the melting point is 52.5-63.5 ℃, and the relative density is 0.9-1.02g/cm3。
Accelerator
The transition layer rubber material provided by the invention contains 3-3.5 parts by weight of an accelerator.
In one embodiment of the invention, the accelerator is a thiuram, a thiazole, a sulfenamide, or a combination thereof.
In a preferred embodiment, the accelerator is N-cyclohexyl-2-benzothiazolesulfenamide, 2' -dithiodibenzothiazole, tetramethylthiuram disulfide, or a combination thereof.
Vulcanizing agent
The transition layer rubber material provided by the invention contains 1-1.5 parts by weight of vulcanizing agent.
In one embodiment of the invention, the vulcanizing agent is sulfur.
Preparation method
The second aspect of the invention provides a preparation method of the hydrogenated nitrile rubber and unsaturated nonpolar rubber laminated composite bonding transition layer rubber material, after preparing the components according to the required amount of the invention, the components comprise carboxyl nitrile rubber, natural rubber, universal carbon black, white carbon black, silane coupling agent, tackifying resin, zinc oxide, stearic acid, accelerator and vulcanizing agent;
the method comprises the following process steps:
firstly, mixing carboxyl nitrile rubber and natural rubber;
secondly, adding general carbon black, white carbon black, a silane coupling agent, tackifying resin, zinc oxide, stearic acid, an accelerator and a vulcanizing agent for thin pass plastication;
and thirdly, mixing and then discharging to obtain the hydrogenated nitrile rubber and unsaturated nonpolar rubber laminated composite bonding transition layer rubber material.
In one embodiment of the present invention, the carboxylated nitrile rubber and the natural rubber are mixed in the first step on an open mill.
In one embodiment of the invention, the above-mentioned second step is performed 4 to 8 passes.
In one embodiment of the present invention, the mixture is kneaded uniformly in the third step and then fed into a sheet.
Unless otherwise specified, the starting materials of the present invention are commercially available; or prepared according to conventional methods in the art. Unless defined or stated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
Use of
The transition layer rubber material provided by the invention can be bonded with hydrogenated nitrile rubber and also can be bonded with unsaturated nonpolar rubber, so that the hydrogenated nitrile rubber and the unsaturated nonpolar rubber can be laminated, compounded and bonded, and the transition layer rubber material can be used for manufacturing composite rubber products, such as but not limited to tires, rubber roller rubber tubes and the like.
The features mentioned above with reference to the invention, or the features mentioned with reference to the embodiments, can be combined arbitrarily. All the features disclosed in this specification may be combined in any combination, and each feature disclosed in this specification may be replaced by alternative features serving the same, equivalent or similar purpose. Thus, unless expressly stated otherwise, the features disclosed are merely generic examples of equivalent or similar features.
The main advantages of the invention are:
1. the invention solves the problem of poor adhesiveness with non-polar unsaturated rubber after the natural rubber is used in the carboxylated nitrile according to a certain proportion, and can still maintain the adhesiveness with hydrogenated nitrile rubber.
2. For a multilayer composite rubber product, the transition layer rubber material provided by the invention can solve the vulcanization adhesion problem of unsaturated nonpolar rubber and hydrogenated nitrile rubber, fully exerts the performance advantages of wear resistance, heat resistance, weather resistance, oxygen resistance, chemical corrosion resistance and high tensile strength of the hydrogenated nitrile rubber, and fully utilizes the advantages of high elasticity, high strength, low heat generation, good flexing resistance, small hysteresis loss and the like of the unsaturated nonpolar rubber, so that the use effect of the product can be greatly improved, and the service life can be prolonged.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards. If there is no corresponding national standard, it is carried out according to the usual international standards, to the conventional conditions or to the conditions recommended by the manufacturer. Unless otherwise indicated, all parts are parts by weight, all percentages are percentages by weight, and the molecular weight of the polymer is the number average molecular weight.
Unless defined or stated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
The transition layer compound in the following examples was obtained by the following steps:
-preparing the components according to the mass fractions listed in the table;
-mixing the carboxylated nitrile rubber and the natural rubber on an open mill;
adding carbon black, small materials (zinc oxide, stearic acid, a silane coupling agent and tackifying resin), an accelerator and a vulcanizing agent, and performing triangular wrapping and thinning for 6 times;
and (4) mixing uniformly and then discharging.
Example 1
Transition layer sizing material
1. The transition layer rubber material is prepared from the following raw materials in percentage by mass:
| transition layer sizing material | |
| Carboxylic nitrile rubber (Nandi 1072CG) | 60 portions of |
| Natural rubber | 40 portions of |
| N550 carbon Black | 40 portions of |
| White carbon black | 10 portions of |
| Silane coupling agent bis- [ gamma- (triethoxysilyl) propyl]Tetrasulfide compounds | 4 portions of |
| Tackifying resin (phenolic tackifying resin SP-1068) | 6 portions of |
| Zinc oxide | 5 portions of |
| Stearic acid | 1 part of |
| Accelerating agent N-cyclohexyl-2-benzothiazole sulfonamide | 2 portions of |
| Accelerator tetramethylthiuram disulfide | 1 part of |
| Vulcanizing agent insoluble sulfur | 0.6 part |
2. The transition layer rubber material is respectively bonded with hydrogenated nitrile rubber, natural rubber/butadiene styrene rubber mixed rubber and natural rubber/butadiene rubber mixed rubber (two rubber materials to be bonded are made into rubber sheets with the same thickness on an open mill by calendaring and are made into standard samples by utilizing a flat vulcanizing agent), wherein,
the formula of the hydrogenated nitrile rubber and the natural rubber is as follows:
the formula of the natural rubber/styrene butadiene rubber blended rubber comprises the following components:
the formula of the natural rubber/butadiene rubber blend is as follows:
3. the rubber peel test was performed, with the following test methods and results:
example 2
Transition layer sizing material
1. The transition layer rubber material is prepared from the following raw materials in percentage by mass:
| transition layer sizing material | |
| Carboxylic nitrile rubber (Nandi 1072CG) | 70 portions of |
| Natural rubber | 30 portions of |
| N550 carbon Black | 30 portions of |
| White carbon black | 20 portions of |
| Silane coupling agent bis- [ gamma- (triethoxysilyl) propyl]Tetrasulfide compounds | 6 portions of |
| Tackifying resin (phenolic tackifying resin SP-1068) | 4 portions of |
| Zinc oxide | 8 portions of |
| Stearic acid | 2 portions of |
| Accelerating agent N-cyclohexyl-2-benzothiazole sulfonamide | 2 portions of |
| Accelerator tetramethylthiuram disulfide | 1.5 parts of |
| Vulcanizing agent insoluble sulfur | 1.5 parts of |
2. The transition layer rubber material is respectively bonded with hydrogenated nitrile rubber, natural rubber/butadiene styrene rubber mixed rubber and natural rubber/butadiene rubber mixed rubber (two rubber materials to be bonded are made into rubber sheets with the same thickness on an open mill by calendaring and are made into standard samples by utilizing a flat vulcanizing agent), wherein,
the formula of the hydrogenated nitrile rubber and the natural rubber is as follows:
the formula of the natural rubber/styrene butadiene rubber blended rubber comprises the following components:
the formula of the natural rubber/butadiene rubber blend is as follows:
3. the rubber peel test was performed, with the following test methods and results:
comparative example 1
Direct bonding of hydrogenated nitrile rubber to natural rubber
The hydrogenated nitrile rubber is prepared from the following raw materials in percentage by mass: hydrogenated nitrile rubber
100 parts of carboxyl nitrile rubber, 10 parts of N220 carbon black, 40 parts of white carbon black, and a silane coupling agent bis- [ gamma- (triethoxysilyl) propyl ] silane]2 parts of tetrasulfide, 10 parts of zinc oxide, 1 part of 4020 anti-aging agent, 1 part of AW-66 anti-aging agent, 1 part of microcrystalline wax, 1.5 parts of accelerator N-cyclohexyl-2-benzothiazole sulfonamide, 1.5 parts of accelerator tetramethyl thiuram disulfide and 0.6 part of vulcanizing agent insoluble sulfur; the natural rubber is prepared from the following raw materials in percentage by mass: 100 parts of natural rubber, 40 parts of N115 carbon black, 15 parts of white carbon black, and a silane coupling agent bis- [ gamma- (triethoxysilyl) propyl group]2 parts of tetrasulfide, 6 parts of zinc oxide, 3 parts of stearic acid, 2 parts of 4020 anti-aging agent and RD protectant1 part of ageing agent, 1 part of microcrystalline wax, 1.5 parts of accelerator N-cyclohexyl-2-benzothiazole sulfonamide, 1 part of accelerator 2, 2' -dithiodibenzothiazyl and 1.5 parts of vulcanizing agent insoluble sulfur.
The same tests as in examples 1 and 2 above were carried out, the test methods and results being as follows:
comparative example 2
Hydrogenated nitrile rubber and natural rubber/styrene butadiene rubber combined rubber direct bonding
The hydrogenated nitrile rubber formulation was the same as in comparative example 1; the natural rubber/styrene butadiene rubber is prepared from the following raw materials in percentage by mass: 70 parts of natural rubber, 30 parts of styrene-butadiene rubber, 40 parts of N115 carbon black, 15 parts of white carbon black, 2 parts of silane coupling agent bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, 6 parts of zinc oxide, 3 parts of stearic acid, 2 parts of 4020 anti-aging agent, 1 part of RD anti-aging agent, 1 part of microcrystalline wax, 1.5 parts of accelerator N-cyclohexyl-2-benzothiazole sulfenamide, 1 part of accelerator 2, 2' -dithiodibenzothiazole and 1.5 parts of vulcanizing agent insoluble sulfur.
The same test as in comparative example 1 above was carried out, the test methods and results being as follows:
comparative example 3
Direct bonding of hydrogenated nitrile rubber and natural rubber/butadiene rubber blend
The hydrogenated nitrile rubber formulation was the same as in comparative example 1; the natural rubber/butadiene rubber is prepared from the following raw materials in percentage by mass: 70 parts of natural rubber, 30 parts of butadiene rubber, 40 parts of N115 carbon black, 15 parts of white carbon black, 2 parts of silane coupling agent bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, 6 parts of zinc oxide, 3 parts of stearic acid, 2 parts of 4020 anti-aging agent, 1 part of RD anti-aging agent, 1 part of microcrystalline wax, 1.5 parts of accelerator N-cyclohexyl-2-benzothiazole sulfenamide, 1 part of accelerator 2, 2' -dithiodibenzothiazole and 1.5 parts of vulcanizing agent insoluble sulfur.
The same test as in comparative example 1 above was carried out, the test methods and results being as follows:
comparative example 4
Selecting carboxyl nitrile rubber to prepare a transition layer to be respectively bonded with hydrogenated nitrile rubber and natural rubber
The carboxyl nitrile rubber is prepared from the following raw materials in percentage by mass: 100 parts of carboxyl nitrile rubber (Nadi 1072CG), 20 parts of N550 carbon black, 25 parts of argil, 15 parts of white carbon black, 5 parts of zinc oxide, 1 part of stearic acid, 2 parts of an accelerator N-cyclohexyl-2-benzothiazole sulfonamide, 1 part of an accelerator tetramethyl thiuram disulfide and 0.8 part of vulcanizing agent insoluble sulfur; the hydrogenated nitrile rubber is prepared from the following raw materials in percentage by mass: hydrogenated nitrile rubber
100 parts of carboxyl nitrile rubber (Nadi 1072CG)10 parts, 40 parts of N220 carbon black, 40 parts of white carbon black, and a silane coupling agent bis- [ gamma- (triethoxy silicon) propyl]2 parts of tetrasulfide, 10 parts of zinc oxide, 1 part of 4020 anti-aging agent, 1 part of AW-66 anti-aging agent, 1 part of microcrystalline wax, 1.5 parts of accelerator N-cyclohexyl-2-benzothiazole sulfonamide, 1.5 parts of accelerator tetramethyl thiuram disulfide and 0.6 part of vulcanizing agent insoluble sulfur; the natural rubber is prepared from the following raw materials in percentage by mass: 100 parts of natural rubber, 40 parts of N115 carbon black, 15 parts of white carbon black, and a silane coupling agent bis- [ gamma- (triethoxysilyl) propyl group]2 parts of tetrasulfide, 6 parts of zinc oxide, 3 parts of stearic acid, 2 parts of 4020 anti-aging agent, 1 part of RD anti-aging agent, 1 part of microcrystalline wax, 1.5 parts of accelerator N-cyclohexyl-2-benzothiazole sulfonamide, 1 part of accelerator 2, 2' -dithiodibenzothiazyl and 1.5 parts of vulcanizing agent insoluble sulfur.
The same test as in comparative example 1 above was carried out, the test methods and results being as follows:
comparative example 5
In the transition layer rubber mixtures provided in examples 1 and 2, the carboxylated nitrile rubber and the natural rubber were used in a weight ratio of 80: 20, and the results showed no bonding.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications can be made by those skilled in the art after reading the above disclosure, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. A compound bonding transition layer rubber material laminated by hydrogenated nitrile rubber and unsaturated nonpolar rubber comprises the following components in parts by weight:
2. the compound bonding transition layer rubber material laminated by the hydrogenated nitrile rubber and the unsaturated nonpolar rubber according to claim 1, wherein the compound bonding transition layer rubber material comprises the following components in parts by weight:
3. the hydrogenated nitrile rubber and unsaturated non-polar rubber laminate composite tie coat compound of claim 1 or 2,
the carboxyl content of the carboxyl nitrile rubber is 5-10%, the content of acrylonitrile is 27-33%, and the Mooney viscosity ML (1+4) is 20-50 at 100 ℃ calculated by the total weight of the carboxyl nitrile rubber.
4. The hydrogenated nitrile rubber and unsaturated non-polar rubber laminated composite bond transition layer compound according to claim 1 or 2, wherein the natural rubber is a standard rubber.
5. The hydrogenated nitrile rubber and unsaturated non-polar rubber laminate composite tie coat compound of claim 1 or 2, wherein said tackifying resin is an alkyl phenol-formaldehyde resin.
6. The compound bonding transition layer compound of hydrogenated nitrile rubber and unsaturated nonpolar rubber laminate according to claim 1 or 2, wherein the silane coupling agent is bis- [ γ - (triethoxysilyl) propyl ] tetrasulfide.
7. The hydrogenated nitrile rubber and unsaturated non-polar rubber laminate composite tie coat compound of claim 1 or 2, wherein the accelerator is selected from one or more of the following: n-cyclohexyl-2-benzothiazole sulfonamide, 2' -dithiodibenzothiazole and tetramethyl thiuram disulfide.
8. The hydrogenated nitrile rubber and unsaturated non-polar rubber laminate composite tie coat compound of claim 1 or 2, wherein said universal carbon black is selected from one or more of the following: n220 carbon black, N115 carbon black, N550 carbon black; the vulcanizing agent is sulfur.
9. A process for the preparation of a hydrogenated nitrile rubber and unsaturated non-polar rubber laminate composite tie coat compound according to any of claims 1 to 8, wherein said process comprises the steps of:
providing the hydrogenated nitrile rubber according to any of claims 1 to 8 with an unsaturated non-polar rubber laminate composite tie coat compound composition;
mixing and discharging the components of the transition layer rubber material to obtain the hydrogenated nitrile-butadiene rubber and unsaturated nonpolar rubber laminated composite bonding transition layer rubber material according to any one of claims 1 to 8.
10. Use of a hydrogenated nitrile rubber according to any of claims 1 to 8 in a composite bonding transition layer compound with an unsaturated non-polar rubber.
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