CN115895175A - Rubber adhesive, rubber composition and non-tire rubber product - Google Patents
Rubber adhesive, rubber composition and non-tire rubber product Download PDFInfo
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- CN115895175A CN115895175A CN202211634704.5A CN202211634704A CN115895175A CN 115895175 A CN115895175 A CN 115895175A CN 202211634704 A CN202211634704 A CN 202211634704A CN 115895175 A CN115895175 A CN 115895175A
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- rubber composition
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 167
- 239000005060 rubber Substances 0.000 title claims abstract description 167
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 56
- 239000000853 adhesive Substances 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 28
- 239000010959 steel Substances 0.000 claims abstract description 28
- -1 organic acid salt Chemical class 0.000 claims abstract description 27
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 239000012190 activator Substances 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 239000006229 carbon black Substances 0.000 claims description 18
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 15
- 239000004014 plasticizer Substances 0.000 claims description 13
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 12
- 229920002943 EPDM rubber Polymers 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 230000003712 anti-aging effect Effects 0.000 claims description 11
- 235000021355 Stearic acid Nutrition 0.000 claims description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000008117 stearic acid Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 239000012763 reinforcing filler Substances 0.000 claims description 7
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 6
- 241000894007 species Species 0.000 claims description 6
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 239000012936 vulcanization activator Substances 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims description 3
- 229920000459 Nitrile rubber Polymers 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229920003052 natural elastomer Polymers 0.000 claims description 3
- 229920001194 natural rubber Polymers 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 229920001195 polyisoprene Polymers 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000004636 vulcanized rubber Substances 0.000 abstract description 26
- 150000002978 peroxides Chemical class 0.000 abstract description 9
- 235000019241 carbon black Nutrition 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000463 material Substances 0.000 description 12
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 10
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 9
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 9
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 9
- 239000005642 Oleic acid Substances 0.000 description 9
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 9
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 7
- 239000004594 Masterbatch (MB) Substances 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 238000010059 sulfur vulcanization Methods 0.000 description 4
- NRVFHZGBTDXOEY-UHFFFAOYSA-N 2-methylprop-2-enoic acid;zinc Chemical compound [Zn].CC(=C)C(O)=O NRVFHZGBTDXOEY-UHFFFAOYSA-N 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000008036 rubber plasticizer Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 2
- 240000007817 Olea europaea Species 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 2
- 229960003656 ricinoleic acid Drugs 0.000 description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000003784 tall oil Substances 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- 230000005653 Brownian motion process Effects 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- HRBZRZSCMANEHQ-UHFFFAOYSA-L calcium;hexadecanoate Chemical compound [Ca+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O HRBZRZSCMANEHQ-UHFFFAOYSA-L 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000010060 peroxide vulcanization Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000006235 reinforcing carbon black Substances 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- MXODCLTZTIFYDV-JHZYRPMRSA-L zinc;(1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Zn+2].C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O.C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O MXODCLTZTIFYDV-JHZYRPMRSA-L 0.000 description 1
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 1
- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical compound [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of rubber, in particular to a rubber adhesive, a rubber composition and a non-tire rubber product. The rubber adhesive provided by the invention comprises the following components in parts by weight: 30 to 75 portions of matrix resin, 20 to 69.9 portions of organic acid salt and 0.1 to 5 portions of activator. A rubber composition comprising the above rubber adhesive. A non-tire rubber article comprising the above rubber composition and a steel cord. The rubber adhesive can improve the bonding property between a peroxide vulcanized rubber system and a steel cord, increase the bonding strength between the rubber and the steel cord under the peroxide vulcanized system, and keep good bonding force between the rubber system and the steel cord even under the condition of high temperature and long-time use.
Description
Technical Field
The invention relates to the technical field of rubber, in particular to a rubber adhesive, a rubber composition and a non-tire rubber product.
Background
In non-tire rubber products, with the improvement of the service life and performance of products, framework materials are generally used to increase the strength of the products, and steel wires, nylon, polyester and the like are generally used as the framework materials. The bonding strength between the rubber and the framework material plays a crucial role in the performance of the whole product; in particular, rubber products used at high temperatures are required to have good heat resistance and good adhesion between rubber and a framework material under high-temperature long-time use conditions, so as to improve the performance and service life of the products.
The rubber sulfur vulcanization system has a good promotion effect on the adhesive strength between rubber and a framework material, but the sulfur vulcanization system has no advantages in the aspects of heat resistance and aging resistance, and the cross-linking bond in the network structure of the peroxide vulcanization system is a C-C bond, so that the bond energy is higher, the thermal stability and the chemical stability are high, the heat resistance and the thermal-oxidative aging resistance are excellent, the vulcanization reversion phenomenon is avoided, the compression permanent deformation of vulcanized rubber is low, and the rubber sulfur vulcanization system is widely applied to static sealing or high-temperature use rubber products; however, compared with the traditional sulfur vulcanization, the organic peroxide vulcanized rubber product has low strength, particularly low peel strength, and low adhesive force between the rubber and the framework material, and the zinc monomethacrylate is used as a more adhesive in the industry at present, but the adhesive force between the rubber and the framework material cannot meet the requirements of product performance.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
It is a first object of the present invention to provide a rubber adhesive that improves the bonding properties of peroxide cured rubber systems.
A second object of the present invention is to provide a rubber composition which is excellent in adhesion property and has excellent adhesive strength with other materials, particularly steel cords.
A third object of the present invention is to provide a non-tire rubber article having excellent adhesion between a rubber composition and a steel cord in the non-tire rubber article, thereby improving the performance and service life of the non-tire rubber article.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a rubber adhesive which comprises the following components in parts by weight: 30 to 75 portions of matrix resin, 20 to 69.9 portions of organic acid salt and 0.1 to 5 portions of activator.
Further, the matrix resin includes one or more of a phenol resin, a petroleum resin, a coumarone resin, and a dicyclopentadiene resin.
Further, the organic acid salt includes organic acid zinc and/or organic acid calcium.
Preferably, the organic acid salt includes a C3-C30 unsaturated fatty acid salt.
Further, the active agent includes a sulfur-containing species.
Preferably, the sulfur-containing species comprise one or more of HTS, KA9188, TB710, and sulfur.
The invention also provides a rubber composition comprising the rubber adhesive.
Preferably, in the rubber composition, the mass percentage of the rubber adhesive is 1-20%.
Further, the rubber composition comprises the following components in parts by weight: 100 parts of rubber, 40-130 parts of reinforcing filler and 1-15 parts of rubber adhesive.
Further, the rubber composition further comprises: an additive, wherein the mass ratio of the additive to the rubber is 13-45: 100.
preferably, the additive comprises the following components in parts by weight: 4-20 parts of vulcanization activator, 1-5 parts of anti-aging agent, 2-10 parts of plasticizer and 6-10 parts of cross-linking agent.
Further, the rubber composition comprises the following components in parts by weight: 100 parts of rubber, 40-100 parts of carbon black, 5-30 parts of white carbon black, 3-15 parts of zinc oxide, 1-5 parts of stearic acid, 2-10 parts of plasticizer, 1-5 parts of anti-aging agent, 1-15 parts of rubber adhesive, 3-5 parts of trimethylolpropane trimethacrylate and 3-5 parts of dicumyl peroxide.
Further, the rubber comprises one or more of ethylene propylene diene monomer, nitrile rubber, natural rubber, polyisoprene rubber, polybutadiene rubber and polybutadiene-styrene rubber.
The present invention also provides a non-tire rubber article comprising the rubber composition as described above and a steel cord.
Compared with the prior art, the invention has the following beneficial effects:
the rubber adhesive provided by the invention can improve the bonding performance of a peroxide vulcanized rubber system and other materials, and increase the bonding strength between the rubber and other materials, especially steel cords, under the peroxide vulcanized system.
The peroxide vulcanized rubber composition has excellent bonding performance by adding the rubber adhesive and mutually matching with other components; the rubber composition has excellent adhesion with a steel cord, and the adhesion between the rubber composition and the steel cord can be kept good even under the condition of high temperature and long-time use, so that the performance and the service life of a non-tire rubber product prepared from the peroxide vulcanized rubber composition and the steel cord can be effectively improved.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
A rubber adhesive, a rubber composition and a non-tire rubber article according to examples of the present invention will be specifically described below.
In some embodiments of the present invention, there is provided a rubber adhesive comprising, in parts by weight: 30 to 75 portions of matrix resin, 20 to 69.9 portions of organic acid salt and 0.1 to 5 portions of active agent.
The rubber adhesive can improve the bonding performance of a peroxide vulcanized rubber system and other materials, and increase the bonding strength between the rubber and other materials, especially steel cords, under the peroxide vulcanized system.
In some embodiments of the invention, typically but not by way of limitation, the base resin is present in an amount of, for example, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, or 75 parts, by weight, or the like; the organic acid salt is 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts or 65 parts by weight and the like; the weight portion of the active agent is 0.5 portion, 1 portion, 1.5 portions, 2 portions, 2.5 portions, 3 portions, 3.5 portions, 4 portions, 4.5 portions or 5 portions, etc.
In some embodiments of the present invention, the rubber adhesive comprises, in parts by weight: 35 to 50 portions of matrix resin, 40 to 60 portions of organic acid salt and 0.5 to 1.5 portions of activator.
In some embodiments of the invention, the matrix resin comprises one or more of a phenolic resin, a petroleum resin, a coumarone resin, and a dicyclopentadiene resin; preferably, the matrix resin comprises a dicyclopentadiene resin (DCPD resin).
In some embodiments of the invention, the organic acid salt comprises zinc and/or calcium organic acid; typically, but not by way of limitation, organic acid salts include zinc and/or calcium salts of at least one of propionic acid, butyric acid, caproic acid, lauric acid, palmitic acid, stearic acid, ricinoleic acid, lactic acid, tartaric acid, glutaric acid, adipic acid, acrylic acid, monomethacrylic acid, dimethacrylate, oleic acid, benzoic acid, coconut oleic acid, corn oleic acid, cotton seed oleic acid, rapeseed oleic acid, rice bran oleic acid, olive oleic acid, abietic acid, and tall oil acid, for example.
In some embodiments of the invention, the organic acid salt comprises one or more of zinc laurate, calcium stearate, zinc stearate, calcium palmitate, zinc oleate, zinc rice bran oleate, zinc acrylate, zinc dimethacrylate, zinc monomethacrylate and zinc abietate.
In some embodiments of the invention, the organic acid salt comprises a C3-C30 unsaturated fatty acid salt.
In some embodiments of the present invention, the C3-C30 unsaturated fatty acid salt comprises a zinc salt and/or a calcium salt of at least one of ricinoleic acid, acrylic acid, monomethacrylic acid, oleic acid, olive oleic acid, and tall oil acid.
In some embodiments of the invention, the active agent comprises a sulfur-containing species; preferably, the sulphur-containing species comprises one or more of HTS, KA9188, TB710 and sulphur.
In some embodiments of the invention, the active agent comprises TB710.
The matrix resin in the rubber adhesive improves the compatibility of the adhesive resin and rubber, so that the rubber adhesive is uniformly dispersed in the rubber, when a rubber composition is vulcanized under certain temperature and pressure, the matrix resin in a molten state diffuses towards the surface of an adherend (rubber and metal) by virtue of Brownian motion, polar groups of the matrix resin and the adherend (rubber and metal) are close to each other, adsorption force is generated, and finally, the matrix resin plays a role in adhesion by virtue of molecular contact and generation of a valence force, and double bonds in the matrix resin form a firm cross-linked network with the rubber in the vulcanization process; under the action of organic acid salt, rubber-metal ionic bond is formed between rubber and metal, so that the interface binding force is improved, meanwhile, unsaturated fatty acid salt is adopted, double bonds in the unsaturated fatty acid salt can also form a cross-linking network with the rubber in the vulcanization process, the double bonds and the network formed by matrix resin are mutually wound and interpenetrated, the binding force between the rubber and the metal is improved, and the activator further promotes the generation of more rubber-metal ionic bonds, so that the interface binding force is greatly improved.
Also provided in some embodiments of the present invention is a method of making the above-described rubber adhesive, comprising the steps of:
and (3) uniformly mixing the matrix resin and the organic acid salt, adding the activator, and uniformly mixing to obtain the rubber adhesive.
Also provided in some embodiments of the invention is a rubber composition comprising the rubber adhesive described above.
In some embodiments of the invention, the rubber composition has a rubber binder content of 1% to 20% by weight; typically, but not by way of limitation, for example, the rubber binder may be present in a mass percent of 1%, 5%, 10%, 15%, or 20%, etc.; preferably, the rubber composition contains 1.5 to 10 mass% of the rubber binder.
In some embodiments of the invention, a rubber composition, in parts by weight, comprises: 100 parts of rubber, 40-130 parts of reinforcing filler and 1-15 parts of rubber adhesive; preferably, the rubber composition comprises, in parts by weight: 100 parts of rubber, 40-100 parts of reinforcing filler and 1-10 parts of rubber adhesive.
The reinforcing filler may be an organic filler, an inorganic filler, and mixtures thereof. Of the organic fillers used as reinforcing fillers in rubber compositions, carbon blacks are the most commonly used, all carbon blacks commonly used in tires being suitable for use in the rubber compositions of the present invention, such as reinforcing carbon blacks of the ASTM grades 100, 200, 300 series (e.g., N115, N234, N330, N375, etc.), or of the higher ASTM grades (e.g., N660, N772, etc.). Among the inorganic fillers used as reinforcing fillers in rubber compositions, siliceous fillers, aluminous fillers and mixtures thereof are generally used. Siliceous type (in particular silicon dioxide (SiO) 2 ) Of the aluminium type (in particular alumina (Al) 3 O 2 ) ) are very suitable as inorganic fillers. As the silica, any one of wet-process silica and dry-process silica classified according to the preparation method thereof may be used.
In some embodiments of the invention, the rubber composition further comprises an additive; preferably, the additive comprises at least one of a vulcanization activator, an anti-aging agent, a plasticizer, and a crosslinking agent.
In some embodiments of the invention, the additive comprises the following components in parts by weight: 4-20 parts of vulcanization activator, 1-5 parts of anti-aging agent, 2-10 parts of plasticizer and 6-10 parts of cross-linking agent.
In some embodiments of the invention, the vulcanizing activator comprises zinc oxide and/or stearic acid.
In some embodiments of the invention, the antioxidant comprises a p-phenylenediamine-based rubber antioxidant and/or a ketoamine-based rubber antioxidant.
In some embodiments of the invention, the plasticizer comprises one or more of a paraffinic rubber plasticizer, an aromatic rubber plasticizer, and a naphthenic rubber plasticizer.
In some embodiments of the invention, the crosslinking agent comprises trimethylolpropane trimethacrylate and/or dicumyl peroxide.
In some embodiments of the present invention, the rubber composition comprises, by weight, 100 parts of rubber, 40 to 100 parts of carbon black, 5 to 30 parts of white carbon black, 3 to 15 parts of zinc oxide, 1 to 5 parts of stearic acid, 2 to 10 parts of a plasticizer, 1 to 5 parts of an antioxidant, 1 to 15 parts of a rubber binder, 3 to 5 parts of trimethylolpropane trimethacrylate, and 3 to 5 parts of dicumyl peroxide.
In some embodiments of the present invention, the rubber composition comprises, in parts by weight: 100 parts of rubber, 40-50 parts of carbon black, 5-15 parts of white carbon black, 5-15 parts of zinc oxide, 1-5 parts of stearic acid, 2-5 parts of plasticizer, 2-5 parts of anti-aging agent, 4-8 parts of rubber adhesive, 3-4 parts of trimethylolpropane trimethacrylate and 3-4 parts of dicumyl peroxide.
The rubber composition of the invention has excellent bonding performance by adding the rubber adhesive and matching with other components; the rubber composition has excellent adhesion to a steel cord, and can maintain good adhesion to the steel cord even under high-temperature long-time use conditions.
In some embodiments of the invention, the rubber comprises one or more of ethylene propylene diene monomer, nitrile rubber, natural rubber, polyisoprene rubber, polybutadiene rubber, and polybutadiene-styrene rubber; preferably, the rubber comprises ethylene propylene diene monomer.
In some embodiments of the invention, a method of preparing a rubber composition comprises the steps of:
mixing the rest components except the trimethylolpropane trimethacrylate and the dicumyl peroxide by adopting a 1.6-liter Banbury mixer to obtain a master batch, standing the master batch for 20-30 h, mixing the master batch with the trimethylolpropane trimethacrylate and the dicumyl peroxide in the 1.6-liter Banbury mixer, and then discharging the master batch out of a sheet by using an open type rubber mixing mill for later use.
In some embodiments of the invention, the rubber composition is vulcanized at a temperature of 150 to 200 ℃ to provide a vulcanized rubber.
Also provided in some embodiments of the present invention is a non-tire rubber article comprising the above rubber composition and a steel cord.
In the non-tire rubber product, the rubber composition and the steel cord have excellent adhesive property, so that the performance and the service life of the non-tire rubber product are effectively improved.
Examples 1 to 6
The vulcanized rubber provided by the embodiment comprises the following raw materials in parts by weight:
100 parts of Ethylene Propylene Diene Monomer (EPDM), 40 parts of carbon black (N330), 10 parts of white carbon black, 10 parts of zinc oxide, 1 part of stearic acid, 2 parts of plasticizer (TP 759), 2 parts of p-phenylenediamine anti-aging agent, 3 parts of rubber adhesive, 3.7 parts of trimethylolpropane trimethacrylate (TMPTMA, 60% active ingredient) and 3.7 parts of dicumyl peroxide (DCP, 40% active ingredient).
The preparation method of the vulcanized rubber comprises the following steps:
the remaining components except trimethylolpropane trimethacrylate and dicumyl peroxide were mixed for 6min with a 1.6-liter Banbury mixer to obtain a master batch, which was left to stand for 24 hours, mixed with trimethylolpropane trimethacrylate and dicumyl peroxide in a 1.6-liter Banbury mixer for 3.5min, and then discharged for standby using an open mill to obtain a rubber composition, which was vulcanized at a temperature of 170 ℃ for 30min to obtain a vulcanized rubber.
The preparation method of the rubber adhesive provided by the embodiment comprises the following steps:
and crushing the matrix resin by using a high-speed stirrer, adding an organic acid salt, uniformly mixing, adding an activating agent, further crushing and mixing to obtain the rubber adhesive.
The methods of preparing the vulcanizates provided in examples 1 to 6 were all the same, except that the rubber binder was different in composition and amount. The components and amounts of the rubber adhesives of examples 1 to 6 are shown in Table 1. The rubber adhesive general specification appearance and heating loss (100 ℃) are reported in Table 1.
TABLE 1
Example 7
The vulcanized rubber and the preparation method thereof provided in this example are referred to example 3, except that the rubber binder is 1 part by weight.
Example 8
The vulcanized rubber and the preparation method thereof provided in this example refer to example 3, except that the rubber adhesive is 5 parts by weight.
Comparative example 1
The vulcanized rubber provided by the comparative example comprises the following raw materials in parts by weight:
100 parts of Ethylene Propylene Diene Monomer (EPDM), 40 parts of carbon black (N330), 10 parts of white carbon black, 10 parts of zinc oxide, 1 part of stearic acid, 2 parts of plasticizer (TP 759), 2 parts of p-phenylenediamine anti-aging agent, 3 parts of zinc monomethacrylate (rubber adhesive), 3.7 parts of trimethylolpropane trimethacrylate (TMPTMA, 60 percent active ingredient) and 3.7 parts of dicumyl peroxide (40 percent active ingredient).
The process for the preparation of the vulcanized rubber of this comparative example refers to example 1.
Comparative example 2
The vulcanized rubber provided by the comparative example comprises the following raw materials in parts by weight:
100 parts of Ethylene Propylene Diene Monomer (EPDM), 40 parts of carbon black (N330), 10 parts of white carbon black, 10 parts of zinc oxide, 1 part of stearic acid, 2 parts of plasticizer (TP 759), 2 parts of p-phenylenediamine anti-aging agent, 1 part of resorcinol, 0.5 part of cobalt salt, 1.5 parts of hexamethylol melamine hexa methyl ether (HMMM, RA 65), 1.4 parts of sulfur and 1 part of accelerator (NS).
The process for preparing the vulcanized rubber of this comparative example comprises the steps of:
the remaining components except sulfur and the accelerator (NS) were mixed for 6min with a 1.6-liter Banbury mixer to obtain a master batch, which was left to stand for 24 hours, mixed with sulfur and the accelerator (NS) in the 1.6-liter Banbury mixer for 3.5min, and then discharged for use with an open mill to obtain a rubber composition, which was vulcanized at a temperature of 150 ℃ for 30min to obtain a vulcanized rubber.
Comparative example 3
The vulcanized rubber provided by the comparative example comprises the following raw materials in parts by weight:
100 parts of Ethylene Propylene Diene Monomer (EPDM), 40 parts of carbon black (N330), 10 parts of white carbon black, 10 parts of zinc oxide, 1 part of stearic acid, 2 parts of plasticizer (TP 759), 2 parts of p-phenylenediamine anti-aging agent, 3 parts of DCPD resin (rubber adhesive), 3.7 parts of trimethylolpropane trimethacrylate (TMPTMA, 60% active ingredient) and 3.7 parts of dicumyl peroxide (40% active ingredient).
The process for the preparation of the vulcanized rubber of this comparative example refers to example 1.
Test example 1
The properties of the vulcanizates obtained in examples 1 to 3, 7 and 8 were measured, and the results are shown in Table 2; the properties of the vulcanizates obtained in comparative examples 1 to 3 were measured, and the results are shown in Table 3.
Among these, the test of tensile properties: testing the breaking strength and the breaking elongation of the vulcanized rubber according to the standard GB/T528-2009; tensile strength at break-tensile stress recorded at the moment of rupture in units MPa; elongation at break-the elongation at break of the test specimen in%.
Testing of Shore hardness: the Shore hardness of the vulcanizates was evaluated according to the standard GB/T531.1-2008. The higher the hardness value, the higher the rigidity of the vulcanized rubber.
TABLE 2
TABLE 3
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| 50% stress at definite elongation (MPa) | 2.6 | 2.5 | 2.4 |
| 100% stress at definite elongation (MPa) | 4.9 | 4.0 | 3.8 |
| Tensile strength (Mpa) | 19.2 | 15.8 | 16.9 |
| Elongation at Break (%) | 226 | 283 | 311 |
| Shore hardness A (degree) | 76 | 76 | 75 |
The adhesion of the vulcanized rubbers obtained in examples 1 to 3, 7 and 8 and comparative examples 1 to 3 to steel wires was measured, and the results are shown in Table 4.
And (3) measuring the adhesive strength between the vulcanized rubber and the steel cord: the adhesion of the vulcanized rubber to the steel cord was tested according to the standard GB/T16586-2014. The detection speed is 100mm/min, the thickness of the steel cord embedded in the rubber is 25mm, the steel cord is pulled out from the vulcanized rubber, the maximum force value of the steel cord pulled out is tested, and the larger the force value is, the better the adhesive force is represented.
TABLE 4
From tables 2, 3 and 4, it can be seen that the rubber adhesives of the examples have improved tensile strength of the rubber compound and prolonged elongation at break compared with the comparative examples, and have certain influence on the stress at definite elongation of the vulcanized rubber compound, and in the aspect of the steel wire adhesion, the rubber adhesives of the examples 3 have obvious advantages in the steel wire adhesion before aging and after aging compared with the comparative examples 1, 2 and 3, mainly that the double bonds of the matrix resin containing the double bonds of the rubber adhesives of the examples 3 and the fatty acid metal salt form firm cross-linked networks with the rubber respectively, and the two networks are mutually wound and mutually interpenetrated to act synergistically, and meanwhile, under the action of the organic acid salt, the rubber-metal ionic bonds are formed between the rubber and the metal, and the components of the rubber adhesives are mutually interacted, so that the adhesion of the rubber and the steel wire is improved. With the increase of the dosage of the binding resin, the binding force of the rubber and the steel wire is also improved, and the binding force is reduced after the dosage of the binding resin reaches a certain proportion.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A rubber adhesive is characterized by comprising the following components in parts by weight: 30 to 75 portions of matrix resin, 20 to 69.9 portions of organic acid salt and 0.1 to 5 portions of activator.
2. The rubber adhesive of claim 1, wherein the matrix resin comprises one or more of a phenolic resin, a petroleum resin, a coumarone resin, and a dicyclopentadiene resin.
3. A rubber adhesive according to claim 1, wherein the organic acid salt comprises zinc and/or calcium organic acid;
preferably, the organic acid salt includes a C3-C30 unsaturated fatty acid salt.
4. The rubber adhesive of claim 1, wherein the active agent comprises a sulfur-containing species;
preferably, the sulphur-containing species comprises one or more of HTS, KA9188, TB710 and sulphur.
5. A rubber composition comprising the rubber adhesive according to any one of claims 1 to 4;
preferably, in the rubber composition, the mass percentage of the rubber adhesive is 1% to 20%.
6. The rubber composition according to claim 5, comprising, in parts by weight: 100 parts of rubber, 40-130 parts of reinforcing filler and 1-15 parts of rubber adhesive.
7. The rubber composition according to claim 5 or 6, further comprising: an additive, wherein the mass ratio of the additive to the rubber is 13-45: 100, respectively;
preferably, the additive comprises the following components in parts by weight: 4-20 parts of vulcanization activator, 1-5 parts of anti-aging agent, 2-10 parts of plasticizer and 6-10 parts of cross-linking agent.
8. A rubber composition according to claim 5 or 6, comprising, in parts by weight: 100 parts of rubber, 40-100 parts of carbon black, 5-30 parts of white carbon black, 3-15 parts of zinc oxide, 1-5 parts of stearic acid, 2-10 parts of plasticizer, 1-5 parts of anti-aging agent, 1-15 parts of rubber adhesive, 3-5 parts of trimethylolpropane trimethacrylate and 3-5 parts of dicumyl peroxide.
9. The rubber composition of claim 6, wherein the rubber comprises one or more of ethylene propylene diene monomer, nitrile rubber, natural rubber, polyisoprene rubber, polybutadiene rubber, and polybutadiene-styrene rubber.
10. A non-tire rubber product comprising the rubber composition according to any one of claims 5 to 9 and a steel cord.
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