CN114605259A - Modified cashew nut oil, rubber plasticizer, and preparation method and application thereof - Google Patents
Modified cashew nut oil, rubber plasticizer, and preparation method and application thereof Download PDFInfo
- Publication number
- CN114605259A CN114605259A CN202210177635.3A CN202210177635A CN114605259A CN 114605259 A CN114605259 A CN 114605259A CN 202210177635 A CN202210177635 A CN 202210177635A CN 114605259 A CN114605259 A CN 114605259A
- Authority
- CN
- China
- Prior art keywords
- rubber
- cashew nut
- acid
- nut oil
- rubber plasticizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 244000226021 Anacardium occidentale Species 0.000 title claims abstract description 51
- 235000020226 cashew nut Nutrition 0.000 title claims abstract description 51
- 239000010466 nut oil Substances 0.000 title claims abstract description 50
- 239000008036 rubber plasticizer Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 57
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 43
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 32
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 30
- 235000019492 Cashew oil Nutrition 0.000 claims description 24
- 239000010467 cashew oil Substances 0.000 claims description 24
- 229940059459 cashew oil Drugs 0.000 claims description 22
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 19
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims description 16
- 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 16
- KUKRLSJNTMLPPK-UHFFFAOYSA-N 4,7,7-trimethylbicyclo[2.2.1]hept-2-ene Chemical group C1CC2(C)C=CC1C2(C)C KUKRLSJNTMLPPK-UHFFFAOYSA-N 0.000 claims description 16
- GLVKGYRREXOCIB-UHFFFAOYSA-N Bornylene Natural products CC1CCC(C(C)(C)C)C=C1 GLVKGYRREXOCIB-UHFFFAOYSA-N 0.000 claims description 16
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 12
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 12
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 12
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 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 claims description 9
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 9
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 9
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 9
- 229920002866 paraformaldehyde Polymers 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 5
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 5
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 claims description 4
- 238000010057 rubber processing Methods 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- 239000011973 solid acid Substances 0.000 claims description 3
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012346 acetyl chloride Substances 0.000 claims description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 claims description 2
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 2
- FMKOJHQHASLBPH-UHFFFAOYSA-N isopropyl iodide Chemical compound CC(C)I FMKOJHQHASLBPH-UHFFFAOYSA-N 0.000 claims description 2
- 229940102396 methyl bromide Drugs 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims 1
- LZTRCELOJRDYMQ-UHFFFAOYSA-N triphenylmethanol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C1=CC=CC=C1 LZTRCELOJRDYMQ-UHFFFAOYSA-N 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 18
- 239000005060 rubber Substances 0.000 abstract description 18
- 238000012545 processing Methods 0.000 abstract description 8
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000003208 petroleum Substances 0.000 abstract description 4
- 238000004073 vulcanization Methods 0.000 abstract description 4
- 238000004513 sizing Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- FMMWHPNWAFZXNH-UHFFFAOYSA-N ERM-AC051 Natural products C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000002035 prolonged effect Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- KHNYNFUTFKJLDD-UHFFFAOYSA-N BCR-49 Natural products C1=CC(C=2C3=CC=CC=C3C=CC=22)=C3C2=CC=CC3=C1 KHNYNFUTFKJLDD-UHFFFAOYSA-N 0.000 description 3
- TXVHTIQJNYSSKO-UHFFFAOYSA-N BeP Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC4=CC=C1C2=C34 TXVHTIQJNYSSKO-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- HAXBIWFMXWRORI-UHFFFAOYSA-N Benzo[k]fluoranthene Chemical compound C1=CC(C2=CC3=CC=CC=C3C=C22)=C3C2=CC=CC3=C1 HAXBIWFMXWRORI-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- BDSBMINFNXSZQP-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid;methanol Chemical compound OC.OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 BDSBMINFNXSZQP-UHFFFAOYSA-N 0.000 description 1
- FTOVXSOBNPWTSH-UHFFFAOYSA-N benzo[b]fluoranthene Chemical compound C12=CC=CC=C1C1=CC3=CC=CC=C3C3=C1C2=CC=C3 FTOVXSOBNPWTSH-UHFFFAOYSA-N 0.000 description 1
- -1 bipyridineEthylamine Chemical compound 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- LHRCREOYAASXPZ-UHFFFAOYSA-N dibenz[a,h]anthracene Chemical compound C1=CC=C2C(C=C3C=CC=4C(C3=C3)=CC=CC=4)=C3C=CC2=C1 LHRCREOYAASXPZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical class O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses modified cashew nut oil, a rubber plasticizer, a preparation method and application thereof. The modified cashew nut oil provided by the invention can be used as a rubber plasticizer, the rubber plasticizer provided by the invention can obviously prolong the scorching time of rubber, and the problem of processing safety is effectively solved; the preparation method of the rubber plasticizer is simple in process, low in cost, environment-friendly and beneficial to industrial popularization, and the problem of polycyclic aromatic hydrocarbon content of petroleum rubber plasticizers is solved. According to different choices of the types of the end-capping reagent and the cross-linking agent, the method has obvious adjustability on the scorching time and the vulcanization time; in addition, the invention can improve the processing performance and simultaneously can not cause obvious influence on the mechanical property of the sizing material.
Description
Technical Field
The invention relates to the technical field of rubber industry, in particular to modified cashew nut oil, a rubber plasticizer and a preparation method thereof.
Background
The rubber processing oil is a processing aid used in rubber production, is one of rubber plasticizers, can obviously improve the processability of rubber, and directly influences the quality of rubber products. The ideal process oil should have the following conditions: (1) the compatibility is good; (2) the volatility is low; (3) the processability, the damageability and the lubricity are good; (4) the stability is good; (5) the source is sufficient.
At present, the commonly used petroleum-based operating oil contains a certain amount of polycyclic aromatic hydrocarbon, pollutes the environment when in use and waste treatment, is not only non-renewable, but also has carcinogenic effect on human bodies, and is more and more strictly limited in use. In contrast, bio-based oils are receiving increasing attention as renewable resources with low cost, wide sources and low toxicity.
Cashew nut oil is a byproduct of the processing process of cashew nuts, is an industrial raw material with wide sources, and has good compatibility with most rubbers. The cashew nut oil mainly comprises a formula (a), and is characterized in that a functional group comprises a phenolic hydroxyl group, a long-chain alkane containing fifteen carbons and a plurality of carbon-carbon double bonds on the chain. The long-chain alkane can play a role in plasticization, the viscosity of the rubber compound is reduced within a certain dosage range, and the mixing of the filler is facilitated, so that the tensile property and the tear resistance of the vulcanized rubber are improved; the carbon-carbon double bond can participate in and promote the cross-linking reaction of the rubber, thereby enhancing certain mechanical properties of the rubber material; the phenolic hydroxyl group can form a hydrogen bond with the inorganic filler, is beneficial to the uniform dispersion of the filler, and can be used as a free radical trapping agent to play a role of a reactive anti-aging agent, so that the thermal-oxidative aging resistance and the oil resistance of the vulcanized rubber are improved.
However, cashew oil has a drawback when used as a rubber plasticizer: which affects the vulcanization characteristics of the compound and in particular leads to a severe reduction in scorch time. Researchers have investigated the processability of cashew nut oil in nitrile rubber, with the increase of the amount of cashew nut oil, the minimum torque (ML) and the maximum torque (MH) of the compound are obviously reduced, and the scorching time (t10) and the vulcanizing time (t90) of the compound are obviously shortened; it has also been found that the scorch times (t5, t10, t50) are reduced to some extent when phosphorylated cashew nut oil is used as a plasticizer for polyvinyl chloride; and the modified cashew nut oil is used as a plasticizer of the ethylene propylene diene monomer rubber, and the scorching time and the torque are reduced along with the increase of the using amount.
The short scorching time undoubtedly reduces the processing safety of the rubber, and although the rubber has the advantages of strong plasticity, good compatibility, environmental protection, low toxicity and the like, the defect greatly limits the development prospect of the rubber.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the modified cashew nut oil, the rubber plasticizer, the preparation method and the application thereof, the reaction process is simple, and all raw materials are suitable for industrial production. The scorching time of the modified cashew nut oil provided by the invention is obviously prolonged when the modified cashew nut oil is used as a rubber plasticizer, and the problem of processing safety is effectively solved; and overcomes the polycyclic aromatic hydrocarbon content problem of petroleum plasticizers.
The method is realized by the following technical scheme:
a rubber plasticizer characterized by comprising the following structural formula:
wherein R ═ C15H31-nN is 0, 2, 4 or 6,
R1is any one of methyl, ethyl, isopropyl, acetyl, propionyl, butyryl, acryloyl, epoxypropyl or isocyanate.
The preparation method of the rubber plasticizer comprises the following steps:
s1 mixing cashew nut oil and catalyst C1And mixing the cardanol with an end-capping reagent, and reacting at room temperature to obtain the hydroxy end-capped cardanol.
Further, in step S1, the end-capping agent is one or more of methyl iodide, methyl bromide, ethyl iodide, ethyl bromide, isopropyl iodide, isopropyl bromide, acetic anhydride, propionic anhydride, butyric anhydride, acetyl chloride, propionyl chloride, butyryl chloride, acryloyl chloride, methyl acetate, ethyl acetate, methyl propionate, ethyl butyrate, epichlorohydrin and isocyanate.
Further, in step S1, the catalyst C1Is one or more of inorganic acid, acidic inorganic salt, organic acid, solid acid, Lewis acid, organic base, inorganic base or basic inorganic salt.
The inorganic acids include, but are not limited to, sulfuric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, and perchloric acid; the acidic inorganic salts include, but are not limited to, zinc perchlorate and sodium bisulfite; such organic acids include, but are not limited to, oxalic acid, citric acid, and p-toluenesulfonic acid; the solid acids include, but are not limited to, perfluorosulfonic acid resins, acidic bentonite, and activated tin dioxide; the Lewis acid includes but is not limited to AlCl3、FeCl3、BF3(ii) a The organic base includes, but is not limited to, pyridine, bipyridineEthylamine, triethylamine and tributylamine; the inorganic base includes, but is not limited to, sodium hydroxide or potassium hydroxide; the basic inorganic salt includes, but is not limited to, sodium carbonate, potassium carbonate, sodium sulfate, potassium sulfate, or sodium bicarbonate.
Preferably, in step S1, the reaction time is 12-24 hours.
The invention also provides a modified cashew nut oil, which comprises the following structural formula:
wherein R ═ C15H31-n，R2Is positioned at ortho-position or para-position of the benzene ring, n is 0, 2, 4 or 6, m is more than or equal to 2 and less than or equal to 6, and m is a positive integer;
R3is H, R2Is a group of any one compound of ethylene glycol, glycerol, pentaerythritol, bornylene, ethylidene norbornene, dicyclopentadiene, coumarone resin, divinylbenzene, p-xylene glycol or trimesic alcohol without one or two hydrogen atoms. When R is2At the terminal position of the polymer, R2Is a group of any one compound of ethylene glycol, glycerol, pentaerythritol, bornylene, ethylidene norbornene, dicyclopentadiene, coumarone resin, divinylbenzene, p-xylene glycol or trimesic alcohol without one hydrogen atom; when R is2In a non-terminal position of the polymer, R2Is a group obtained by removing two hydrogen atoms from any one compound of ethylene glycol, glycerol, pentaerythritol, bornylene, ethylidene norbornene, dicyclopentadiene, coumarone resin, divinylbenzene, p-xylene glycol or trimesic alcohol.
The invention also provides another modified cashew nut oil, which comprises the following structural formula:
wherein R is C15H31-n，R2In the ortho position of the phenyl ring orPara, n is 0, 2, 4 or 6, m is more than or equal to 2 and less than or equal to 6, and m is a positive integer;
R3is one of methyl, ethyl, isopropyl, acetyl, propionyl, butyryl or acryloyl; r2Is a group obtained by removing one or two hydrogen atoms from any one compound of formaldehyde, paraformaldehyde, ethylene glycol, glycerol, pentaerythritol, urotropine, bornylene, ethylidene norbornene, dicyclopentadiene, coumarone resin, hexamethoxy methyl melamine, furfural, divinylbenzene, p-xylene glycol or trimesic alcohol. When R is2At the terminal position of the polymer, R2Is a group of any one compound of formaldehyde, paraformaldehyde, ethylene glycol, glycerol, pentaerythritol, urotropine, bornylene, ethylidene norbornene, dicyclopentadiene, coumarone resin, hexamethoxy methyl melamine, furfural, divinylbenzene, p-xylene glycol or trimesic alcohol without one hydrogen atom; when R is2In a non-terminal position of the polymer, R2Is a group obtained by removing two hydrogen atoms from any one compound of formaldehyde, paraformaldehyde, ethylene glycol, glycerol, pentaerythritol, urotropine, bornylene, ethylidene norbornene, dicyclopentadiene, coumarone resin, hexamethoxy methyl melamine, furfural, divinylbenzene, p-xylene glycol or trimesic alcohol.
The invention also provides a rubber plasticizer, which comprises the following structural formula:
wherein R ═ C15H31-nAnd n is 0, 2, 4 or 6.
When R is3When is H, R2Is a group of any one compound of ethylene glycol, glycerol, pentaerythritol, bornylene, ethylidene norbornene, dicyclopentadiene, coumarone resin, divinylbenzene, p-xylene glycol or trimesic alcohol without one or two hydrogen atoms. When R is2At the terminal position of the polymer, R2Is ethylene glycol, propylene glycolA group obtained by removing one hydrogen atom from any one compound of triol, pentaerythritol, bornene, ethylidene norbornene, dicyclopentadiene, coumarone resin, divinylbenzene, terephthalyl alcohol or trimesic acid methanol; when R is2In a non-terminal position of the polymer, R2Is a group obtained by removing two hydrogen atoms from any one compound of ethylene glycol, glycerol, pentaerythritol, bornylene, ethylidene norbornene, dicyclopentadiene, coumarone resin, divinylbenzene, p-xylene glycol or trimesic alcohol.
When R is3When the substituent is one of methyl, ethyl, isopropyl, acetyl, propionyl, butyryl or acryloyl; r2Is a group obtained by removing one or two hydrogen atoms from any one compound of formaldehyde, paraformaldehyde, ethylene glycol, glycerol, pentaerythritol, urotropine, bornylene, ethylidene norbornene, dicyclopentadiene, coumarone resin, hexamethoxy methyl melamine, furfural, divinylbenzene, p-xylene glycol or trimesic alcohol. When R is2At the terminal position of the polymer, R2Is a group of any one compound of formaldehyde, paraformaldehyde, ethylene glycol, glycerol, pentaerythritol, urotropine, bornylene, ethylidene norbornene, dicyclopentadiene, coumarone resin, hexamethoxy methyl melamine, furfural, divinylbenzene, p-xylene glycol or trimesic alcohol without one hydrogen atom; when R is2In a non-terminal position of the polymer, R2Is a group obtained by removing two hydrogen atoms from any one compound of formaldehyde, paraformaldehyde, ethylene glycol, glycerol, pentaerythritol, urotropine, bornylene, ethylidene norbornene, dicyclopentadiene, coumarone resin, hexamethoxy methyl melamine, furfural, divinylbenzene, p-xylene glycol or trimesic alcohol.
The preparation method of the modified cashew nut oil or rubber plasticizer comprises the following steps:
s2: the cardanol with the end capped by hydroxyl, a cross-linking agent and a catalyst C2Mixing, heating and reacting to obtain the modified cashew nut oil or rubber plasticizer.
Further, in step S2, the crosslinking agent is one or more of formaldehyde, paraformaldehyde, ethylene glycol, glycerol, pentaerythritol, urotropine, bornylene, ethylidene norbornene, dicyclopentadiene, coumarone resin, hexamethoxy methyl melamine, furfural, divinylbenzene, p-xylene glycol, or trimesic alcohol.
Further, in step S2, the catalyst C2Is sulfuric acid, hydrochloric acid, phosphoric acid, oxalic acid, citric acid, p-toluenesulfonic acid, AlCl3、FeCl3、BF3One or more of (a).
Preferably, in step S2, the reaction time is 1 to 3 hours;
preferably, in step S2, the heating temperature is 90-140 ℃.
The invention also provides application of the rubber plasticizer or the modified cashew nut oil in tire rubber processing, in particular application in adjusting scorching time and vulcanization time.
Compared with the prior art, the invention has the beneficial effects that:
the rubber plasticizer provided by the invention has the advantages of wide raw material source, simple preparation process, low cost and environmental friendliness, is beneficial to industrial popularization, and overcomes the polycyclic aromatic hydrocarbon content problem of petroleum plasticizers; the scorching time can be obviously prolonged, and the problem of processing safety is effectively solved; the key components of the invention are the end-capping reagent and the cross-linking agent, which can be selected according to different types of the end-capping reagent and the cross-linking agent, and the invention has obvious adjustability on the sintering time and the vulcanizing time; in addition, the invention can improve the processing performance and simultaneously can not cause obvious influence on the mechanical property of the sizing material.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Comparative example
Unmodified cashew nut oil (raw material) was used as cashew nut oil a.
Example 1 (preparation of modified cashew oil b)
The synthetic route is as follows:
the method comprises the following specific steps:
s2: adding 300g of cashew nut oil and 5g of oxalic acid into a flask, uniformly stirring and heating to 100 ℃; slowly dripping 21g of 37-40% formaldehyde aqueous solution into the flask by using a constant-pressure dropping funnel, and preserving heat for 3 hours at 90 ℃ after dripping is finished; and (4) distilling under reduced pressure to remove water and unreacted formaldehyde to obtain the modified cashew nut oil b.
Example 2 (preparation of modified cashew oil c)
The synthetic route is as follows:
the method comprises the following specific steps:
s1: adding 340g of cashew nut oil and 120g of acetic anhydride into a flask, and uniformly mixing and stirring; adding 3g of citric acid into the flask, and stirring for 15 hours at room temperature; and distilling under reduced pressure to remove unreacted acetic anhydride and generated acetic acid to obtain the modified cashew nut oil c.
Example 3 (preparation of modified cashew oil d)
The synthetic route is as follows:
the method comprises the following specific steps:
s1, adding 375g of cashew nut oil and 125g of acetic anhydride into the flask, and uniformly stirring at room temperature; 5g of sodium hydrogen sulfite was further added thereto, followed by further stirring at room temperature for 12 hours; residual acetic acid and acetic anhydride were distilled off under reduced pressure to obtain hydroxy-terminated cardanol (intermediate).
S2: adding 300g of the hydroxyl-terminated cardanol (intermediate) and 22g of 37-40% formaldehyde aqueous solution into a flask, uniformly mixing, heating to 90 ℃, adding 5g of hydrochloric acid, and continuously reacting for 2 hours; and (4) distilling under reduced pressure to remove the generated water and unreacted formaldehyde to obtain the modified cashew nut oil d.
Example 4 (preparation of modified cashew oil e)
The synthetic route is as follows:
the method comprises the following specific steps:
s1: adding 480g of cashew nut oil and 120g of epoxy chloropropane into a flask, and uniformly mixing and stirring; adding 6g of sodium hydroxide into the flask, and stirring for 16 hours at room temperature; distilling under reduced pressure and washing with water for 2-3 times to obtain modified cashew nut oil e.
Example 5 (preparation of modified cashew oil f)
The synthetic route is as follows:
the method comprises the following specific steps:
s2, adding 300g of cashew nut oil and 25g of ethylene glycol into a flask, uniformly mixing, heating to 130 ℃, adding 5g of zinc perchlorate, and continuously reacting for 2.5 hours; and (3) distilling under reduced pressure to remove the generated water and the glycol which is not completely reacted to obtain the modified cashew nut oil f.
Example 6 (preparation of modified cashew oil g)
The synthetic route is as follows:
the method comprises the following specific steps:
s2: 500g cashew nut oil and 110g p-xylene glycol were added to the flask and mixedAfter homogenization, the mixture was heated to 125 ℃ and 6.5g AlCl was added3Continuously reacting for 3 hours; and carrying out reduced pressure distillation to obtain modified cashew nut oil g.
Example 7 (preparation of modified cashew oil h)
The synthetic route is as follows:
the method comprises the following specific steps:
s1: 380g of cashew nut oil and 205g of butyric anhydride are added into the flask, and the mixture is stirred uniformly at room temperature; then 5.8g of potassium hydroxide is added, and the mixture is continuously stirred for 18 hours at room temperature; distilling under reduced pressure to remove butyric acid to obtain hydroxy-terminated cardanol (intermediate);
s2 adding 220g of the hydroxyl-terminated cardanol (intermediate) and 80g of p-xylylene glycol into a flask, uniformly mixing, heating to 135 ℃, and adding 5g of AlCl3Continuously reacting for 3 hours; and (5) carrying out reduced pressure distillation to obtain the modified cashew nut oil h.
Example 8 (preparation of modified cashew oil i)
The synthetic route is as follows:
the method comprises the following specific steps:
s1, adding 440g of cashew nut oil and 160g of triethylamine into the flask, and uniformly stirring at room temperature; 160g of propionyl chloride is slowly dripped into the mixture by a constant-pressure dropping funnel, and the mixture is continuously stirred for 18 hours at room temperature after the dripping is finished; distilling under reduced pressure to remove residual propionyl chloride and hydrochloric acid, and washing with water for 2-3 times to obtain hydroxy-terminated cardanol (intermediate);
s2, adding 300g of the hydroxyl-terminated cardanol (intermediate) and 30g of ethylene glycol into a flask, uniformly mixing, heating to 140 ℃, adding 5g of p-toluenesulfonic acid, and continuously reacting for 2 hours; and (3) distilling under reduced pressure to remove generated water and unreacted ethylene glycol to obtain the modified cashew nut oil i.
Example 9 (preparation of modified cashew oil j)
The modified cashew nut oils c and f obtained in examples 2 and 5 were mixed in an equal mass ratio of 1:1 to obtain modified cashew nut oil j.
Example 10 (preparation of rubber plasticizer)
The preparation methods of the rubber plasticizer b-j are respectively the same as the preparation methods of the modified cashew nut oil b-j.
EXAMPLE 1 (testing and characterization of modified cashew oil)
Table 1 shows cashew oil a and the end-capping and cross-linking agents used in the preparation of modified cashew oils b-f, j. The viscosity, flash point and NMR spectra of comparative cashew oil a and modified cashew oils b-f, j of examples 1-5, 9 were respectively (1H NMR), the results are given in table 2 below.
Table 1.
TABLE 2 test results
Note: a-f, j in tables 1, 2 correspond to cashew oil a and modified cashew oil b-f, j, respectively.
From the above table, it can be seen that, compared with the unmodified cashew nut oil raw material, the viscosity and flash point of the product obtained by the invention are obviously changed, and the modified cashew nut oil b, d, f, j and other crosslinking modified products1H NMR can prove the success of the modification of each group of products.
EXAMPLE 2 polycyclic aromatic testing of modified cashew oil
Polycyclic aromatic hydrocarbons were tested on the cashew nut oil a of comparative example and the modified cashew nut oils b-f, j of examples 1-5, 9, and the results are shown in Table 3. from the test results, it can be seen that the raw materials and the preparation processes of examples 1-5 and 9 do not contain polycyclic aromatic hydrocarbons.
Table 3.
Note: a-f, j in table 3 correspond to cashew oil a and modified cashew oil b-f, j, respectively; according to AfPS (German product safety Committee) and the regulations of the European Union on polycyclic aromatic hydrocarbons, BaP means that the content of benzo (a) pyrene is less than 1ppm,8 items and less than 10 ppm. Item 8 and means: the total content of eight items including benzo (a) anthracene + chrysene + benzo (b) fluoranthene + benzo (k) fluoranthene + benzo (j) fluoranthene + benzo (e) pyrene + benzo (a) pyrene + dibenzo (a, h) anthracene.
EXAMPLE 3 (preparation of Tread rubber composition A, B, C, D, E, F, J)
The preparation of the tread rubber compositions was carried out according to the formulation in Table 4.
TABLE 4 Tread rubber composition formulation
Note: a-f, j in table 4 correspond to cashew oil a and modified cashew oil b-f, j, respectively.
Experimental example 4 (processability and mechanical Property test of Tread rubber composition)
The results of the processability and mechanical properties tests on the tread rubber composition prepared in experimental example 3 are shown in Table 5 below.
TABLE 5 processability test results of the rubber compositions
As can be seen from the results in Table 5, the scorch time and cure time for the unmodified cashew nut oil feedstock are very short, Mooney scorch (T)5) 11 minutes, scorch time (T)10) 0.82 min, vulcanization time (T)90) Is 12 minutes; the rubber plasticizer prepared by the invention can be obviously improvedGood processability of the rubber material, T5Can be prolonged to 18 minutes or even more than 1 hour, T10Can be prolonged to 1.28 min at most90The time can be prolonged to 19.69 minutes at most; more importantly, the invention has obvious adjustability on the sintering time and the vulcanizing time according to different selections of the types of the end-capping reagent and the cross-linking agent. In addition, the invention improves the processing performance and does not have obvious influence on the mechanical property of the sizing material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (11)
1. A rubber plasticizer characterized by comprising the following structural formula:
wherein R ═ C15H31-nN is 0, 2, 4 or 6,
R1is any one of methyl, ethyl, isopropyl, acetyl, propionyl, butyryl, acryloyl, epoxypropyl or isocyanate.
2. A modified cashew nut oil, comprising the following structural formula:
wherein R ═ C15H31-n，R2Is positioned at ortho-position or para-position of the benzene ring, n is 0, 2, 4 or 6, m is more than or equal to 2 and less than or equal to 6, and m is a positive integer;
R3is H, R2Is prepared from ethanediol, propanetriol, pentaerythritol, bornylene, ethylidene norbornene, dicyclopentadiene, coumarone resin, divinylbenzeneAnd a group obtained by removing one or two hydrogen atoms from any one compound of p-xylylene glycol or trimesic tritanol.
3. A modified cashew nut oil, comprising the following structural formula:
wherein R ═ C15H31-n，R2Is positioned at ortho-position or para-position of the benzene ring, n is 0, 2, 4 or 6, m is more than or equal to 2 and less than or equal to 6, and m is a positive integer;
R3is one of methyl, ethyl, isopropyl, acetyl, propionyl, butyryl or acryloyl; r2Is a group obtained by removing one or two hydrogen atoms from any one compound of formaldehyde, paraformaldehyde, ethylene glycol, glycerol, pentaerythritol, urotropine, bornylene, ethylidene norbornene, dicyclopentadiene, coumarone resin, hexamethoxy methyl melamine, furfural, divinylbenzene, p-xylene glycol or trimesic alcohol.
4. A rubber plasticizer characterized by being the modified cashew oil of claim 2 or 3.
5. A method for preparing a rubber plasticizer according to claim 1, comprising the steps of:
s1 mixing cashew nut oil and catalyst C1And mixing the cardanol with an end-capping reagent, and reacting at room temperature to obtain the hydroxy end-capped cardanol.
6. The method for preparing a rubber plasticizer according to claim 5, wherein in step S1, the end-capping agent is one or more of methyl iodide, methyl bromide, ethyl iodide, ethyl bromide, isopropyl iodide, isopropyl bromide, acetic anhydride, propionic anhydride, butyric anhydride, acetyl chloride, propionyl chloride, butyryl chloride, acryloyl chloride, methyl acetate, ethyl acetate, methyl propionate, ethyl butyrate, epichlorohydrin, and isocyanate.
7. The method for preparing a rubber plasticizer according to claim 5, wherein in step S1, catalyst C is added1Is one or more of inorganic acid, acidic inorganic salt, organic acid, solid acid, Lewis acid, organic base, inorganic base or basic inorganic salt.
8. A method of preparing the modified cashew nut oil of claim 2 or 3 or the rubber plasticizer of claim 4, comprising the steps of:
s2: the cardanol with the end capped by hydroxyl, a cross-linking agent and a catalyst C2Mixing and heating to react to obtain the rubber plasticizer.
9. The method according to claim 8, wherein in step S2, the crosslinking agent is one or more of formaldehyde, paraformaldehyde, ethylene glycol, glycerol, pentaerythritol, urotropin, bornene, ethylidene norbornene, dicyclopentadiene, coumarone resin, hexamethoxymethyl melamine, furfural, divinylbenzene, terephthalyl alcohol, or trimesic alcohol.
10. The method according to claim 8, wherein the catalyst C is used in step S22Is sulfuric acid, hydrochloric acid, phosphoric acid, oxalic acid, citric acid, p-toluenesulfonic acid, AlCl3、FeCl 3Or BF3One or more of (a).
11. Use of a rubber plasticizer according to any of claims 1 or 4 in tire rubber processing or use of a modified cashew oil according to any of claims 2 or 3 in tire rubber processing.
Priority Applications (1)
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| CN115368222A (en) * | 2022-08-17 | 2022-11-22 | 江苏麒祥高新材料有限公司 | Modified cashew nut oil, cashew nut oil rubber plasticizer, and preparation method and application thereof |
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