CN111153871A - Substituted anilino-benzothiazole-2-thioketone compound and preparation method and application thereof - Google Patents
Substituted anilino-benzothiazole-2-thioketone compound and preparation method and application thereof Download PDFInfo
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- CN111153871A CN111153871A CN202010057172.8A CN202010057172A CN111153871A CN 111153871 A CN111153871 A CN 111153871A CN 202010057172 A CN202010057172 A CN 202010057172A CN 111153871 A CN111153871 A CN 111153871A
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- Prior art keywords
- benzothiazole
- formula
- compound
- thione
- reaction
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 72
- 229920001971 elastomer Polymers 0.000 claims abstract description 42
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 86
- 238000006243 chemical reaction Methods 0.000 claims description 46
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 36
- 229910052717 sulfur Inorganic materials 0.000 claims description 35
- 239000011593 sulfur Substances 0.000 claims description 35
- 230000003712 anti-aging effect Effects 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 238000004073 vulcanization Methods 0.000 claims description 9
- -1 anilino-benzothiazole-2-thione compound Chemical class 0.000 claims description 8
- 238000006482 condensation reaction Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- MDKKCKGBEGNWIA-UHFFFAOYSA-N 6-(2-methylanilino)-3H-1,3-benzothiazole-2-thione Chemical compound C=1(C(=CC=CC1)NC1=CC2=C(NC(S2)=S)C=C1)C MDKKCKGBEGNWIA-UHFFFAOYSA-N 0.000 claims description 7
- UBWVGJGJHFGROR-UHFFFAOYSA-N 6-(3-methylanilino)-3H-1,3-benzothiazole-2-thione Chemical compound C1(=CC(=CC=C1)NC1=CC2=C(NC(S2)=S)C=C1)C UBWVGJGJHFGROR-UHFFFAOYSA-N 0.000 claims description 7
- WAFUGLPXYWCCKG-UHFFFAOYSA-N 6-(4-ethylanilino)-3H-1,3-benzothiazole-2-thione Chemical compound C(C)C1=CC=C(NC2=CC3=C(NC(S3)=S)C=C2)C=C1 WAFUGLPXYWCCKG-UHFFFAOYSA-N 0.000 claims description 7
- PFXMHGFTFKGCNZ-UHFFFAOYSA-N 6-(4-methylanilino)-3H-1,3-benzothiazole-2-thione Chemical compound N(C1=CC=C(C=C1)C)C1=CC2=C(NC(S2)=S)C=C1 PFXMHGFTFKGCNZ-UHFFFAOYSA-N 0.000 claims description 7
- FAQNMDREGDKUGZ-UHFFFAOYSA-N 6-(4-propan-2-ylanilino)-3H-1,3-benzothiazole-2-thione Chemical compound C(C)(C)C1=CC=C(C=C1)NC1=CC2=C(NC(S2)=S)C=C1 FAQNMDREGDKUGZ-UHFFFAOYSA-N 0.000 claims description 7
- UVCOBSXCPMCSMX-UHFFFAOYSA-N 6-(4-propylanilino)-3H-1,3-benzothiazole-2-thione Chemical compound CCCC1=CC=C(C=C1)NC2=CC3=C(C=C2)NC(=S)S3 UVCOBSXCPMCSMX-UHFFFAOYSA-N 0.000 claims description 7
- XKPSFOJLWVRGGO-UHFFFAOYSA-N 6-anilino-3H-1,3-benzothiazole-2-thione Chemical compound N(C1=CC=CC=C1)C1=CC2=C(NC(S2)=S)C=C1 XKPSFOJLWVRGGO-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000013040 rubber vulcanization Methods 0.000 abstract description 7
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 238000000034 method Methods 0.000 description 33
- 239000000203 mixture Substances 0.000 description 29
- 238000004949 mass spectrometry Methods 0.000 description 23
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 22
- 238000005160 1H NMR spectroscopy Methods 0.000 description 21
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 20
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- 239000003795 chemical substances by application Substances 0.000 description 15
- 239000000706 filtrate Substances 0.000 description 15
- 239000002244 precipitate Substances 0.000 description 15
- 239000007858 starting material Substances 0.000 description 15
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003444 phase transfer catalyst Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 3
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- YFEJFIBZPXJRSI-UHFFFAOYSA-N 4-(2-methylanilino)phenol Chemical compound CC1=CC=CC=C1NC1=CC=C(O)C=C1 YFEJFIBZPXJRSI-UHFFFAOYSA-N 0.000 description 2
- PJCNSVHWHHVSMK-UHFFFAOYSA-N 4-(4-methylanilino)phenol Chemical compound C1=CC(C)=CC=C1NC1=CC=C(O)C=C1 PJCNSVHWHHVSMK-UHFFFAOYSA-N 0.000 description 2
- PRCYIOGBFOYIEI-UHFFFAOYSA-N 4-ethyl-n-(4-nitrophenyl)aniline Chemical compound C1=CC(CC)=CC=C1NC1=CC=C([N+]([O-])=O)C=C1 PRCYIOGBFOYIEI-UHFFFAOYSA-N 0.000 description 2
- JTTMYKSFKOOQLP-UHFFFAOYSA-N 4-hydroxydiphenylamine Chemical compound C1=CC(O)=CC=C1NC1=CC=CC=C1 JTTMYKSFKOOQLP-UHFFFAOYSA-N 0.000 description 2
- AMAHTMJTDVOIFX-UHFFFAOYSA-N 4-methyl-n-(4-nitrophenyl)aniline Chemical compound C1=CC(C)=CC=C1NC1=CC=C([N+]([O-])=O)C=C1 AMAHTMJTDVOIFX-UHFFFAOYSA-N 0.000 description 2
- XXYMSQQCBUKFHE-UHFFFAOYSA-N 4-nitro-n-phenylaniline Chemical compound C1=CC([N+](=O)[O-])=CC=C1NC1=CC=CC=C1 XXYMSQQCBUKFHE-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- OFLWZDHLKWQOJP-UHFFFAOYSA-N N-(4-nitrophenyl)-4-propylaniline Chemical compound C(CC)C1=CC=C(NC2=CC=C(C=C2)[N+](=O)[O-])C=C1 OFLWZDHLKWQOJP-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
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- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- TYAIENOHMWQMKI-UHFFFAOYSA-N n-(4-nitrophenyl)-4-propan-2-ylaniline Chemical compound C1=CC(C(C)C)=CC=C1NC1=CC=C([N+]([O-])=O)C=C1 TYAIENOHMWQMKI-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
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- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
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- HAEQAUJYNHQVHV-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylbenzamide Chemical group NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NC2=CC=CC=C2)C=CC=1 HAEQAUJYNHQVHV-UHFFFAOYSA-N 0.000 description 1
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- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- UBFFOJPWISNVKE-UHFFFAOYSA-N N-(4-nitrosophenyl)-4-propan-2-ylaniline Chemical compound C1=CC(C(C)C)=CC=C1NC1=CC=C(N=O)C=C1 UBFFOJPWISNVKE-UHFFFAOYSA-N 0.000 description 1
- VAWYWLYQQHAEIB-UHFFFAOYSA-N N-(4-nitrosophenyl)-4-propylaniline Chemical compound C(CC)C1=CC=C(NC2=CC=C(C=C2)N=O)C=C1 VAWYWLYQQHAEIB-UHFFFAOYSA-N 0.000 description 1
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- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IJRVQAXSAHHCNH-UHFFFAOYSA-M butyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](C)(C)C IJRVQAXSAHHCNH-UHFFFAOYSA-M 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
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- SKOLWUPSYHWYAM-UHFFFAOYSA-N carbonodithioic O,S-acid Chemical compound SC(S)=O SKOLWUPSYHWYAM-UHFFFAOYSA-N 0.000 description 1
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- 229940125904 compound 1 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- KTDMLSMSWDJKGA-UHFFFAOYSA-M methyl(tripropyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](C)(CCC)CCC KTDMLSMSWDJKGA-UHFFFAOYSA-M 0.000 description 1
- 230000001617 migratory effect Effects 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000005002 naphthylamines Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- OIJHFHYPXWSVPF-UHFFFAOYSA-N para-Nitrosodiphenylamine Chemical compound C1=CC(N=O)=CC=C1NC1=CC=CC=C1 OIJHFHYPXWSVPF-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical group C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- QVOFCQBZXGLNAA-UHFFFAOYSA-M tributyl(methyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](C)(CCCC)CCCC QVOFCQBZXGLNAA-UHFFFAOYSA-M 0.000 description 1
- JAJRRCSBKZOLPA-UHFFFAOYSA-M triethyl(methyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(CC)CC JAJRRCSBKZOLPA-UHFFFAOYSA-M 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a substituted anilino-benzothiazole-2-thioketone compound and a preparation method thereof. Furthermore, the compounds are also related to the use in rubber articles. The substituted anilino-benzothiazole-2-thioketone compound can promote rubber vulcanization and prolong the service life of rubber products.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a substituted anilino-benzothiazole-2-thioketone compound, a preparation method thereof and application thereof in production of rubber products.
Background
The rubber auxiliary agent mainly comprises an anti-aging agent and an accelerator, and also comprises other processing auxiliary agents with various varieties. They are an indispensable important part in the rubber industry, and play an important role in improving the rubber performance, reducing the production cost and prolonging the service life of products.
The rubber accelerator is a rubber vulcanization accelerator and plays a very important role in the rubber vulcanization process. Rubber vulcanization is mainly performed using sulfur, but sulfur reacts with rubber relatively slowly, and therefore a vulcanization accelerator is produced at the same time. The accelerator is added into the rubber material to promote the activation of the vulcanizing agent, so that the crosslinking reaction of the vulcanizing agent and rubber molecules is accelerated, and the effects of shortening the vulcanizing time and reducing the vulcanizing temperature are achieved. Accelerators can be classified into sulfenamides, thiazoles, thiurams, guanidines, thioureas, and dithiocarbamates according to their chemical structure. The thiazole has good vulcanization activity, can endow vulcanized rubber with good aging resistance and fatigue resistance, and is widely applied, especially the accelerator M (2-mercaptobenzothiazole).
The rubber anti-aging agent is a chemical substance which is added in the rubber production process and can delay the rubber aging and prolong the service life of the rubber. The anti-aging agents can be classified into naphthylamines, phenols, quinolines, diphenylamines and p-phenylenediamines according to chemical structures. The age resister with excellent performance and most widely applied is p-phenylenediamine, especially PPD series, but the age resister of the type has the problems of easy migration and easy exudation, which causes the concentration of the effective age resister in rubber products to be reduced, thereby affecting the aging resistance effect of the age resister.
In order to improve the performance of rubber products and prolong the service life of the rubber products, a rubber accelerator and an anti-aging agent are generally compounded, and the functions of the accelerator and the anti-aging agent are exerted to the maximum extent by utilizing the synergistic effect of the components. So far, no matter which has the effects of both an anti-aging agent and a promoter exists.
Disclosure of Invention
Aiming at the problem that a rubber anti-aging agent in the prior art is easy to migrate, the invention aims to provide a compound which can prolong the service life of a rubber product and promote rubber vulcanization, in particular to a substituted anilino-benzothiazole-2-thioketone compound.
Another object of the present invention is to provide a method for preparing substituted anilino-benzothiazole-2-thione compounds.
The third purpose of the invention is to provide the application of the substituted anilino-benzothiazole-2-thioketone compound, in particular to the application of the compound as a rubber anti-aging and vulcanization accelerator in the production of rubber products, especially in the production of tires.
The invention relates to a rubber product, in particular to a rubber product with a structure containing p-phenylenediamine and benzothiazole, which is characterized in that a structure of a substituted anilino-benzothiazole-2-thioketone compound contains both the structure of p-phenylenediamine and the structure of benzothiazole, so that the compound is chemically reacted with rubber in the vulcanization process of the rubber, is combined in a network of vulcanized rubber in a chemical bond manner, has non-migratory property, and can further prolong the service life of the rubber product.
Therefore, the substituted anilino-benzothiazole-2-thioketone compound provided by the invention can promote rubber vulcanization and prolong the service life of rubber products. The structure of the compound is represented by a general formula (I):
wherein R represents a substituent attached to the benzene ring and is selected from hydrogen or lower alkyl.
The compounds of formula (I) may also be tautomers corresponding to formula (Ia) and have the structures shown below:
for better understanding, the present invention collectively represents the structure of the above-mentioned compounds as "thioketone" represented by formula (I).
The lower alkyl group in the compound of formula (I) of the present invention means a chain aliphatic hydrocarbon group having 1 to 6 carbon atoms, preferably a chain aliphatic hydrocarbon group having 1 to 3 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, etc., preferably methyl.
In the compounds of formula (I) according to the invention, R is preferably hydrogen.
Compounds of formula (I) of the present invention include, but are not limited to:
in another aspect of the present invention, there is provided a process for the preparation of a compound of this type (hereinafter referred to as "process 1" of the present invention) which comprises condensation of a compound of formula (II) with carbon disulphide and sulphur to give a compound of formula (I). The reaction formula is as follows:
in the compounds of formula (II) R is as defined for formula (I).
In the method 1, a mixture of a compound shown as a formula (II), sulfur and carbon disulfide is heated to over 170 ℃, preferably 230-260 ℃ in a closed tank; the pressure is 0 to 16MPa, preferably 7 to 10 MPa. The reaction time is controlled within 2-7 h, and the reaction can be completed within 3-4 h.
In the method 1 of the present invention, the feeding molar ratio of the compound of formula (II) to sulfur is preferably 1:1.1 to 2.0, more preferably 1:1.3 to 1.5.
In the method 1 of the present invention, the feeding molar ratio of the compound of formula (II) to the carbon disulfide is preferably 1:1.2 to 2.0, and more preferably 1:1.3 to 1.6.
In the process 1 according to the invention, the reaction-finished material is treated with an alkaline hydroxide solution, for example sodium hydroxide, and filtered to remove the tarry substance. Then, an acid such as dilute hydrochloric acid is added to neutralize the precipitate. The precipitate was separated and washed with water. The precipitate is dried and recrystallized by adding an alkyl halide such as dichloroethane, dichloromethane, chloroform, etc. The product after recrystallization is a substituted anilino-benzothiazole-2-thioketone compound.
The invention also provides another preparation method of the compound (hereinafter referred to as the method 2 of the invention), which comprises the steps of carrying out condensation reaction on the compound of the formula (II), the compound of the formula (III), carbon disulfide and sulfur to obtain the compound of the formula (I). The reaction formula is as follows:
r in the compounds of formula (III) is as defined for formula (I).
The compound of formula (II) is the same as the compound of formula (III) in that R is attached to the benzene ring, and R is the same.
In the method 2, the compound of the formula (II), the compound of the formula (III), the mixture of sulfur and carbon disulfide are heated to over 170 ℃, preferably 230-260 ℃ in a closed tank; the pressure is 0 to 16MPa, preferably 7 to 10 MPa. The reaction time is controlled within 2-7 h, and the reaction can be completed within 3-4 h.
In the method 2 of the present invention, the feeding molar ratio of the compound of formula (II) to the compound of formula (III) is preferably 1:0 to 1:0.66, more preferably 1:0.2 to 1: 0.5.
In the method 2 of the present invention, the molar ratio of the total amount of the compounds of formula (II) and (III) to the sulfur charge is 1:1.1 to 2.0, and more preferably 1:1.3 to 1.5.
In the method 2 of the present invention, the molar ratio of the total amount of the compounds of formula (II) and (III) to the carbon disulfide is preferably 1:1.2 to 2.0, more preferably 1:1.3 to 1.6.
The invention also provides a third preparation method of the compound (hereinafter referred to as the method 3) of the invention, which comprises the steps of carrying out condensation reaction on the compound of the formula (II), the compound of the formula (III) and the compound of the formula (IV) with carbon disulfide and sulfur to obtain the compound of the formula (I). The reaction formula is as follows:
the compounds of formula (IV) wherein R is as defined for formula (I).
The compound of formula (II), the compound of formula (III) and the compound of formula (IV) have the same position where R is bonded to the benzene ring, and R is the same.
In the method 3, the compound of the formula (II), the compound of the formula (III) and the mixture of the compound of the formula (IV) and sulfur and carbon disulfide are heated to over 170 ℃, preferably 230-260 ℃ in a closed tank; the pressure is 0 to 16MPa, preferably 7 to 10 MPa. The reaction time is controlled within 2-7 h, and the reaction can be completed within 3-4 h.
In the method 3 of the present invention, the feeding molar ratio of the compound of formula (III) to the compound of formula (IV) is preferably 1:1 to 1:20, and more preferably 1:3 to 1: 10.
In the method 3 of the present invention, the charging molar ratio of the compound of formula (II) to the total amount of the compounds of formula (III) and formula (IV) is 1:0 to 1:0.66, and more preferably 1:0.2 to 1: 0.5.
In the method 3 of the present invention, the feeding molar ratio of the total amount of the compounds of the formula (II), the formula (III) and the formula (IV) to sulfur is preferably 1:1.1 to 2.0, more preferably 1:1.3 to 1.5.
In the method 3 of the present invention, the feeding molar ratio of the total amount of the compounds of formula (II), formula (III) and formula (IV) to the carbon disulfide is preferably 1:1.2 to 2.0, and more preferably 1:1.3 to 1.6.
The compounds of formula (II) may be commercially available products or intermediates obtained by synthesis according to known literature references, see for example US4326080, the relevant contents of which are incorporated herein by reference.
In some embodiments, the compound of formula (ii) may be achieved according to the following procedure: in the presence of catalyst gamma-Al2O3In the presence of (A), carrying out condensation reaction on hydroquinone and alkylaniline or aniline; then in the same catalyst gamma-Al2O3In the presence of ammonia, reacting the product obtained after the above reaction with ammonia to obtain the compound of formula (II).
Further, the molar ratio of hydroquinone to alkylaniline or aniline is in a stoichiometric ratio where the chemical reaction is completely carried out, but in actual practice, the alkylaniline or aniline is used in excess. For example, 1 to 10 moles of alkylaniline or aniline is used for 1 mole of hydroquinone, and 1.05 to 8 moles of alkylaniline or aniline is preferably used.
Further, in the above-mentioned amination reaction, an excess amount of ammonia is usually used, for example, 1 mole of hydroquinone, 10 to 40 moles of ammonia, preferably 15 to 30 moles of ammonia are used.
Further, the catalyst is gamma-Al2O3The amount of the gamma-alumina is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 1 part by weight of hydroquinone.
Further, the reaction temperature of hydroquinone with alkylaniline or aniline is preferably 200 to 350 ℃, more preferably 220 to 300 ℃. The temperature of the ammoniation reaction is preferably 300 ℃ to 450 ℃, and is preferably 320 ℃ to 400 ℃.
Further, the pressure is 0.1 to 40MPa, preferably 1 to 35 MPa.
In some embodiments, the compounds of formula (ii) may also be prepared using the following methods. In an organic solvent, under the action of alkali and a phase transfer catalyst, nitrobenzene and alkylaniline or aniline undergo a condensation dehydration reaction to obtain a mixture of nitrosodiphenylamine and nitrodiphenylamine; then hydrogenation reaction is carried out to obtain the compound shown in the formula (II).
Further, the phase transfer catalyst is tetraalkylamine hydroxide. The phase transfer catalyst is selected from one or a combination of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltributylammonium hydroxide, methyltripropylammonium hydroxide, methyltriethylammonium hydroxide, trimethylbutylammonium hydroxide and-N-phenyltrimethylammonium hydroxide, preferably tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide, more preferably tetramethylammonium hydroxide.
Further, the base is an alkali metal, an alkali metal hydride, an alkali metal oxide, an alkoxide of an alkali metal, an alkaline earth metal hydride, an alkaline earth metal oxide, an alkaline earth metal hydroxide, an alkoxide of an alkaline earth metal. The alkali is selected from Na, K, Rb, Cs, Mg, Ca, NaH and CaH2、Na2O、K2O、MgO、CaO、NaOH、KOH、RbOH、CsOH、Mg(OH)2、Ca(OH)2One or a combination of sodium methoxide, sodium ethoxide and potassium tert-butoxide, preferably NaOH and KOH, more preferably NaOH.
Further, the organic solvent is selected from one or a combination of benzene, toluene, tetrahydrofuran, N-methylpyrrolidone, ethylene glycol dimethyl ether, dioxane and N, N-dimethylformamide, preferably toluene and ethylene glycol dimethyl ether, and more preferably ethylene glycol dimethyl ether.
Furthermore, the feeding molar ratio of nitrobenzene to aniline in the condensation reaction is 1: 1-1: 15, and the preferable molar ratio is 1: 4-1: 10. The reaction temperature is 20-120 deg.C, preferably 75-85 deg.C. The vacuum degree of the dehydration reaction is 0.1-0.09 MPa, preferably 0.098-0.092 MPa.
Further, the molar ratio of the phase transfer catalyst to the aniline is 1: 1-1: 5, and preferably 1: 1-1: 2.
The reaction time of the condensation step is controlled to be 2-4 hours.
Further, the catalyst for the hydrogenation reaction is a group VIII metal comprising a support. The metal is preferably palladium, rhodium and ruthenium, more preferably palladium. The support is a carbonaceous support such as coke, graphite, carbon black or activated carbon, preferably activated carbon. The amount of the hydrogenation catalyst is 0.01 to 50% by weight, preferably 0.1 to 10% by weight of the condensation reaction mixture.
The solvent of the hydrogenation reaction is an alcohol solvent, and is selected from one or the combination of methanol, ethanol and isopropanol.
The reaction temperature of the hydrogenation reaction is 50-100 ℃, and the reaction pressure is 0.2-3.0 MPa. The time of the hydrogenation reaction is 2 to 7 hours.
The "alkyl group" in the alkylaniline in the invention means a chain aliphatic hydrocarbon group having 1 to 6 carbon atoms.
The compound of formula (III) may be a commercially available product or an intermediate product synthesized according to known literature references, for example, see ARKIVOC,2011, vol.2011, No.10, p.118-126.
The compounds of formula (IV) may be commercially available products or intermediates synthesized according to known literature procedures, for example, see Journal of Organic Chemistry,1967, vol.32, p.158-162.
The invention also provides a substituted anilino-benzothiazole-2-thioketone compound which is used as a rubber anti-aging and vulcanization accelerator and applied to the production of rubber products, in particular to the production of tires.
Compared with the traditional anti-aging agent, the substituted anilino-benzothiazole-2-thioketone compound synthesized by the invention has the following advantages: the compound contains a benzothiazole structure, and can perform chemical reaction with rubber in the rubber vulcanization process, play the role of an accelerator, be combined in a rubber macromolecular grid in a chemical bond form, and have non-migration property, so that the service life of a rubber product can be further prolonged. The compound prepared by the invention is applied to rubber products, and can endow the rubber products with good heat resistance and aging resistance and good mechanical properties.
Detailed Description
The structure of the compounds is determined by Nuclear Magnetic Resonance (NMR) or/and Mass Spectrometry (MS). NMR shift (. delta.) of 10-6The units in (ppm) are given. NMR was measured using a Brucker AVANCE-400 nuclear magnetic spectrometer using deuterated chloroform (CDCl)3) Internal standard is Tetramethylsilane (TMS).
MS was measured using a FINNIGAN LCQAD (ESI) mass spectrometer (manufacturer: Thermo, model: FINNIGAN LCQAdvantage MAX).
High Performance Liquid Chromatography (HPLC) analysis an Agilent HPLC 1200DAD high performance liquid chromatograph was used.
The% in the embodiment of the present invention means mass percentage.
Example 1 (preparation of 4-aminodiphenylamine)
In a 700ml steel autoclave, 110g (1.0mol) of hydroquinone, 108g of a crushed gamma-alumina catalyst and 186g (2.0mol) of aniline were charged into the autoclave under a nitrogen atmosphere, and the reaction temperature was 270 ℃ and the pressure was 2MPa for 4 hours. The obtained reaction product was extracted with methylene chloride, and the filtrate after the extraction was distilled under reduced pressure to obtain 157.3g of 4-hydroxydiphenylamine in a yield of 85%.
In a 700ml steel autoclave, 44.4g (0.24mol) of 4-hydroxydiphenylamine, 88g of gamma-alumina catalyst and 120g (7.0mol) of ammonia were charged into the autoclave under a nitrogen atmosphere at a reaction temperature of 350 ℃ and a pressure of 3.5MPa for a reaction time of 2 hours. The obtained reaction product was extracted with dimethylformamide, and then the filtrate after extraction was subjected to distillation under reduced pressure to obtain 36.21g of 4-aminodiphenylamine with a yield of 82.1%.
Example 2 preparation of 4-amino-2' -methyldiphenylamine
In a 700ml steel autoclave, 110g (1.0mol) of hydroquinone, 108g of a crushed γ -alumina catalyst and 214g (2.0mol) of o-toluidine were charged into the autoclave under a nitrogen atmosphere, and the reaction temperature was 270 ℃ and the pressure was 0.6MPa, and the reaction time was 3 hours. The obtained reaction product was extracted with methylene chloride, and the filtrate after the extraction was distilled under reduced pressure to obtain 163.2g of 4-hydroxy-2' -methyldiphenylamine in a yield of 82%.
In a 700ml steel autoclave, 47.8g (0.24mol) of 4-hydroxy-2' -methyldiphenylamine, 88g of gamma-alumina catalyst and 85g (5.0mol) of ammonia were charged into the autoclave under a nitrogen atmosphere at a reaction temperature of 350 ℃ and a pressure of 27MPa for a reaction time of 2 hours. The obtained reaction product was extracted with dimethylformamide, and then the filtrate after extraction was subjected to distillation under reduced pressure to obtain 40.39g of 4-amino-2' -methyldiphenylamine with a yield of 85.0%.
Example 3 preparation of 4-amino-3' -methyldiphenylamine
In a 700ml steel autoclave, 110g (1.0mol) of hydroquinone, 108g of a pulverized γ -alumina catalyst and 214g (2.0mol) of m-toluidine were charged into the autoclave under a nitrogen atmosphere, and the reaction temperature was 270 ℃ and the pressure was 2MPa, and the reaction time was 3 hours. The obtained reaction product was extracted with methylene chloride, and the filtrate after the extraction was subjected to distillation under reduced pressure to obtain 165.2g of 4-hydroxy-3' -methyldiphenylamine with a yield of 83%.
In a 700ml steel autoclave, 47.8g (0.24mol) of 4-hydroxy-3' -methyldiphenylamine, 88g of gamma-alumina catalyst and 85g (5.0mol) of ammonia were charged into the autoclave under a nitrogen atmosphere at a reaction temperature of 350 ℃ and a pressure of 26MPa for a reaction time of 2 hours. The obtained reaction product was extracted with dimethylformamide, and then the filtrate after extraction was subjected to distillation under reduced pressure to obtain 40.87g of 4-amino-3' -methyldiphenylamine with a yield of 86.0%.
Example 4 preparation of 4-amino-4' -methyldiphenylamine
In a 700ml steel autoclave, 110g (1.0mol) of hydroquinone, 108g of a pulverized γ -alumina catalyst and 214g (2.0mol) of p-toluidine were charged into a reaction vessel under a nitrogen atmosphere at a reaction temperature of 270 ℃ under a pressure of 2MPa for a reaction time of 3 hours. The obtained reaction product was extracted with methylene chloride, and the filtrate after the extraction was subjected to distillation under reduced pressure to obtain 169.2g of 4-hydroxy-4' -methyldiphenylamine in a yield of 85%.
In a 700ml steel autoclave, 47.8g (0.24mol) of 4-hydroxy-4' -methyldiphenylamine, 88g of gamma-alumina catalyst and 85g (5.0mol) of ammonia were charged into the autoclave under a nitrogen atmosphere at a reaction temperature of 350 ℃ and a pressure of 26MPa for a reaction time of 2 hours. The obtained reaction product was extracted with dimethylformamide, and then the filtrate after extraction was subjected to distillation under reduced pressure to obtain 40.87g of 4-amino-4' -methyldiphenylamine with a yield of 86.0%.
Example 5 preparation of 4-aminodiphenylamine
200mL of ethylene glycol dimethyl ether is added into a 500mL four-neck flask which is provided with a mechanical stirrer, a thermometer, a condenser and a constant pressure dropping funnel, then 111.6g (1.2mol) of aniline, 109.2g (1.2mol) of tetramethylammonium hydroxide and 48g (1.2mol) of sodium hydroxide are added, then 36.9g (0.3mol) of nitrobenzene is gradually dropped into the flask, the feeding time is controlled to be 1 hour, the condensation dehydration reaction temperature is 60-80 ℃, the dehydration vacuum degree is 0.093MPa, the temperature is reduced after the dehydration reaction is finished, the condensation liquid is added into a high pressure reaction kettle, 100mL of ethanol is added, 5g of Pd/C catalyst is added, hydrogen is introduced, the heating temperature is raised to 80 ℃, and the pressure is controlled to be 1 MPa. After the reaction, the Pd/C catalyst is filtered out, the obtained filtrate is subjected to layering recovery of the quaternary ammonium base catalyst in the water phase, and the organic phase is subjected to reduced pressure distillation to obtain 49.7g of 4-aminodiphenylamine with the yield of 90%.
Example 6 preparation of (6- (anilino) -benzothiazole-2 (3H) -thione)
In a closed steel tank, a mixture of 9.2g (0.05mol) of 4-aminodiphenylamine, 2.08g (0.065mol) of powdered sulfur and 4ml of carbon disulfide (0.065mol) is heated to 260 ℃, reacted for 1 hour under the pressure of 7MPa, the temperature is kept for 3 hours, and after the reaction is finished, pressure is released and the temperature is reduced. The reaction melt is treated while hot with 100ml of 5% sodium hydroxide solution and filtered to remove the tarry substance. Dilute hydrochloric acid was then added dropwise to the filtrate, resulting in precipitation. The precipitate was separated, washed with water and dried. The dried precipitate was refluxed with 400ml of dichloroethane, and the mixture was hot filtered. This was cooled to give 10.97g of 6- (anilino) -benzothiazole-2 (3H) -thione in 85% yield.
1HNMR(400MHz，CDCl3):δ7.20～7.28(m，4H)，7.00(s，1H)，6.81(m，1H)，6.16～6.22(m，2H)，4.0(s，2H)。
MS m/z(ESI):259[M+1]
Example 7 preparation of (6- (o-toluidino) -benzothiazole-2 (3H) -thione)
In a closed steel pot, a mixture of 9.9g (0.05mol) of 4-amino-2' -methyldiphenylamine, 2.4g (0.075mol) of powdered sulfur and 4ml of carbon disulfide (0.065mol) is heated to 230 ℃, the pressure is 10MPa, the reaction is carried out for 1 hour, the temperature is kept for 3 hours, and the pressure is released and the temperature is reduced after the reaction is finished. The reaction melt is treated while hot with 100ml of 5% sodium hydroxide solution and filtered to remove the tarry substance. Dilute hydrochloric acid was then added dropwise to the filtrate, resulting in precipitation. The precipitate was separated, washed with water and dried. The dried precipitate was refluxed with 400ml of dichloroethane, and the mixture was hot filtered. This was cooled to give 11.97g of 6- (o-toluidino) -benzothiazole-2 (3H) -thione in 88% yield.
1HNMR(400MHz，CDCl3):δ7.15(d，1H)，7.01(m，2H)，6.69(t，1H)，6.51(d，1H)，6.16～6.22(m，2H)，4.0(s，2H)，2.12(s，3H)。
MS m/z(ESI):273[M+1]
Example 8 preparation of (6- (m-toluidino) -benzothiazole-2 (3H) -thione)
In a closed steel tank, a mixture of 9.9g (0.05mol) of 4-amino-3' -methyldiphenylamine, 2.08g (0.065mol) of powdered sulfur and 4.8ml of carbon disulfide (0.079mol) is heated to 260 ℃ and the pressure is 7MPa, the reaction is carried out for 1 hour, the temperature is kept for 3 hours, and the pressure is released and the temperature is reduced after the reaction is finished. The reaction melt is treated while hot with 100ml of 5% sodium hydroxide solution and filtered to remove the tarry substance. Dilute hydrochloric acid was then added dropwise to the filtrate, resulting in precipitation. The precipitate was separated, washed with water and dried. The dried precipitate was refluxed with 400ml of dichloroethane, and the mixture was hot filtered. This was cooled to give 11.70g of 6- (m-toluidino) -benzothiazole-2 (3H) -thione in 86% yield.
1HNMR(400MHz，CDCl3):δ7.47(m，2H)，7.08(m，1H)，7.00(s，1H)，6.59(m，1H)，6.16～6.22(m，2H)，4.0(s，2H)，2.34(s，3H)。
MS m/z(ESI):273[M+1]
Example 9 preparation of (6- (p-toluidinyl) -benzothiazole-2 (3H) -thione)
In a closed steel tank, a mixture of 9.9g (0.05mol) of 4-amino-4' -methyldiphenylamine, 2.06g (0.065mol) of powdered sulfur and 4ml of carbon disulfide (0.065mol) is heated to 230 ℃, the pressure is 10MPa, the reaction is carried out for 1 hour, the temperature is kept for 3 hours, and the pressure is released and the temperature is reduced after the reaction is finished. The reaction melt is treated while hot with 100ml of 5% sodium hydroxide solution and filtered to remove the tarry substance. Dilute hydrochloric acid was then added dropwise to the filtrate, resulting in precipitation. The precipitate was separated, washed with water and dried. The dried precipitate was refluxed with 400ml of dichloroethane, and the mixture was hot filtered. This was cooled to give 12.10g of 6- (p-toluidinyl) -benzothiazole-2 (3H) -thione in 89% yield.
1HNMR(400MHz，CDCl3):δ7.33(d，2H)，7.24(d，2H)，7.00(s，1H)，6.16～6.22(m，2H)，4.0(s，2H)，2.34(s，3H)。
MS m/z(ESI):273[M+1]
EXAMPLE 10 preparation of (6- (4-ethylanilino) -benzothiazole-2 (3H) -thione)
The starting materials were 10.6g (0.05mol) of 4-ethylphenyl-1, 4-diphenylamine, 2.4g (0.075mol) of powdery sulfur and 4.8ml (0.079mol) of carbon disulfide, and the same operation as in example 6 was conducted. 12.30g of 6- (4-ethylanilino) -benzothiazole-2 (3H) -thione was obtained with a yield of 86%.
1HNMR(400MHz，CDCl3):δ7.40(m，2H)，7.04(m，3H)，6.16～6.22(m，2H)，4.0(s，2H)，2.61(q，2H)，1.25(t，3H)。
MS m/z(ESI):287[M+1]
EXAMPLE 11 preparation of (6- (4-Propylanilino) -benzothiazole-2 (3H) -thione)
The same procedures as in example 6 were repeated except that the starting materials used were 11.3g (0.05mol) of 4-propylphenyl-1, 4-diphenylamine, 2.06g (0.065mol) of powdery sulfur and 4ml (0.065mol) of carbon disulfide. 13.20g of 6- (4-propylanilino) -benzothiazole-2 (3H) -thione were obtained in a yield of 88%.
1HNMR(400MHz，CDCl3):δ7.40(m，2H)，7.04(m，3H)，6.16～6.22(m，2H)，4.0(s，2H)，2.62(t，2H)，1.65(m，2H)，0.90(t，3H)。
MS m/z(ESI):301[M+1]
EXAMPLE 12 preparation of (6- (4-isopropylphenylamino) -benzothiazole-2 (3H) -thione)
The same procedures as in example 6 were repeated except that the starting materials were 11.3g (0.05mol) of 4-isopropylphenyl-1, 4-diphenylamine, 2.06g (0.065mol) of powdery sulfur and 4.8ml (0.079mol) of carbon disulfide. 13.50g of 6- (4-isopropylphenylamino) -benzothiazole-2 (3H) -thione were obtained in a yield of 90%.
1HNMR(400MHz，CDCl3):δ7.37(m，2H)，7.00～7.05(m，3H)，6.16～6.22(m，2H)，4.0(s，2H)，2.87(m，1H)，1.20(d，6H)。
MS m/z(ESI):301[M+1]
Example 13 preparation of (6- (anilino) -benzothiazole-2 (3H) -thione)
In a closed steel tank, a mixture of 5.52g (0.03mol) of 4-aminodiphenylamine, 4.28g (0.02mol) of 4-nitrodiphenylamine, 2.06g (0.065mol) of powdered sulfur and 4ml of carbon disulfide (0.065mol) is heated to 250 ℃ for reaction for 1 hour under the pressure of 8MPa, the temperature is kept for 3 hours, and the pressure is released and the temperature is reduced after the reaction is finished. The reaction melt is treated while hot with 100ml of 5% sodium hydroxide solution and filtered to remove the tarry substance. Dilute hydrochloric acid was then added dropwise to the filtrate, resulting in precipitation. The precipitate was separated, washed with water and dried. The dried precipitate was refluxed with 400ml of dichloroethane, and the mixture was hot filtered. This was cooled to give 10.97g of 6- (anilino) -benzothiazole-2 (3H) -thione in 85% yield.
1HNMR(400MHz，CDCl3):δ7.20～7.28(m，4H)，7.00(s，1H)，6.81(m，1H)，6.16～6.22(m，2H)，4.0(s，2H)。
MS m/z(ESI):259[M+1]
Example 14 preparation of (6- (o-toluidino) -benzothiazole-2 (3H) -thione)
The same procedures as in example 13 were repeated except that the starting materials were 5.94g (0.03mol) of 4-amino-2 '-methyldiphenylamine, 1.37g (0.006mol) of 4-nitro-2' -methyldiphenylamine, 1.73g (0.054mol) of sulfur and 3.47ml (0.058mol) of carbon disulfide. 8.81g of 6- (o-toluidino) -benzothiazole-2 (3H) -thione were obtained in a yield of 90%.
1HNMR(400MHz，CDCl3):δ7.15(d，1H)，7.01(m，2H)，6.69(t，1H)，6.51(d，1H)，6.16～6.22(m，2H)，4.0(s，2H)，2.12(s，3H)。
MS m/z(ESI):273[M+1]
Example 15 preparation of (6- (m-toluidino) -benzothiazole-2 (3H) -thione)
The same procedure as in example 13 was repeated except that the starting materials were 5.94g (0.03mol) of 4-amino-3 '-methyldiphenylamine, 3.42 g (0.015mol) of 4-nitro-3' -methyldiphenylamine, 1.86g (0.058mol) of sulfur and 4.34ml (0.072mol) of carbon disulfide. 11.26g of 6- (m-toluidino) -benzothiazole-2 (3H) -thione were obtained in a yield of 92%.
1HNMR(400MHz，CDCl3):δ7.47(m，2H)，7.08(m，1H)，7.00(s，1H)，6.59(m，1H)，6.16～6.22(m，2H)，4.0(s，2H)，2.34(s，3H)。
MS m/z(ESI):273[M+1]
EXAMPLE 16 preparation of (6- (p-toluidinyl) -benzothiazole-2 (3H) -thione)
The same procedures as in example 13 were repeated except that the starting materials were 4-amino-4 '-methyldiphenylamine 5.94g (0.03mol), 4-nitro-4' -methyldiphenylamine 2.05g (0.009mol), sulfur 1.86g (0.058mol) and carbon disulfide 3.08ml (0.051 mol). 9.97g of 6- (p-toluidinyl) -benzothiazole-2 (3H) -thione was obtained in a yield of 94%.
1HNMR(400MHz，CDCl3):δ7.33(d，2H)，7.24(d，2H)，7.00(s，1H)，6.16～6.22(m，2H)，4.0(s，2H)，2.34(s，3H)。
MS m/z(ESI):273[M+1]
EXAMPLE 17 preparation of (6- (4-ethylanilino) -benzothiazole-2 (3H) -thione)
The starting materials were 6.36g (0.03mol) of 4-ethylphenyl-1, 4-diphenylamine, 3.63g (0.015mol) of 4-ethyl-N- (4-nitrophenyl) aniline, 1.86g (0.058mol) of sulfur and 4.34ml (0.072mol) of carbon disulfide, and the operation was identical to that of example 13. 11.84g of 6- (4-ethylanilino) -benzothiazole-2 (3H) -thione was obtained with a yield of 92%.
1HNMR(400MHz，CDCl3):δ7.40(m，2H)，7.04(m，3H)，6.16～6.22(m，2H)，4.0(s，2H)，2.61(q，2H)，1.25(t，3H)。
MS m/z(ESI):287[M+1]
EXAMPLE 18 preparation of (6- (4-Propylanilino) -benzothiazole-2 (3H) -thione)
The same procedures as in example 13 were repeated except that 6.78g (0.03mol) of 4-propylphenyl-1, 4-diphenylamine, 5.12g (0.02mol) of 4-propyl-N- (4-nitrophenyl) aniline, 2.06g (0.065mol) of sulfur and 4ml (0.065mol) of carbon disulfide were used as starting materials. 14.10g of 6- (4-propylanilino) -benzothiazole-2 (3H) -thione were obtained in a yield of 94%.
1HNMR(400MHz，CDCl3):δ7.40(m，2H)，7.04(m，3H)，6.16～6.22(m，2H)，4.0(s，2H)，2.62(t，2H)，1.65(m，2H)，0.90(t，3H)。
MS m/z(ESI):301[M+1]
Example 19 preparation of (6- (4-isopropylphenylamino) -benzothiazole-2 (3H) -thione)
The same procedures as in example 13 were repeated except that 6.78g (0.03mol) of 4-isopropylphenyl-1, 4-diphenylamine, 3.84g (0.015mol) of 4-isopropyl-N- (4-nitrophenyl) aniline, 1.86g (0.058mol) of sulfur and 3.47ml (0.058mol) of carbon disulfide were used as starting materials. 12.83g of 6- (4-isopropylphenylamino) -benzothiazole-2 (3H) -thione were obtained in a yield of 95%.
1HNMR(400MHz，CDCl3):δ7.37(m，2H)，7.00～7.05(m，3H)，6.16～6.22(m，2H)，4.0(s，2H)，2.87(m，1H)，1.20(d，6H)。
MS m/z(ESI):301[M+1]
EXAMPLE 20 preparation of (6- (anilino) -benzothiazole-2 (3H) -thione)
In a closed steel pot, a mixture of 5.52g (0.03mol) of 4-aminodiphenylamine, 0.86g (0.004mol) of 4-nitrodiphenylamine, 3.17g (0.016mol) of 4-nitrosodiphenylamine, 2.06g (0.065mol) of powdered sulfur and 4ml of carbon disulfide (0.065mol) is heated to 250 ℃ for reaction for 1 hour under the pressure of 8MPa, the temperature is kept for 3 hours, and the pressure is released and the temperature is reduced after the reaction is finished. The reaction melt is treated while hot with 100ml of 5% sodium hydroxide solution and filtered to remove the tarry substance. Dilute hydrochloric acid was then added dropwise to the filtrate, resulting in precipitation. The precipitate was separated, washed with water and dried. The dried precipitate was refluxed with 400ml of dichloroethane, and the mixture was hot filtered. This was cooled to give 11.35g of 6- (anilino) -benzothiazole-2 (3H) -thione in 88% yield.
1HNMR(400MHz，CDCl3):δ7.20～7.28(m，4H)，7.00(s，1H)，6.81(m，1H)，6.16～6.22(m，2H)，4.0(s，2H)。
MS m/z(ESI):259[M+1]
Example 21 preparation of (6- (o-toluidino) -benzothiazole-2 (3H) -thione)
The same procedures as in example 20 were repeated except that the starting materials used were 4-amino-2 ' -methyldiphenylamine 5.94g (0.03mol), 4-nitro-2 ' -methyldiphenylamine 0.91g (0.004mol), 4-nitroso-2 ' -methyldiphenylamine 3.18g (0.015mol), sulfur 2.34g (0.073mol) and carbon disulfide 4ml (0.065 mol). 12.13g of 6- (o-toluidino) -benzothiazole-2 (3H) -thione were obtained in a yield of 91%.
1HNMR(400MHz，CDCl3):δ7.15(d，1H)，7.01(m，2H)，6.69(t，1H)，6.51(d，1H)，6.16～6.22(m，2H)，4.0(s，2H)，2.12(s，3H)。
MS m/z(ESI):273[M+1]
EXAMPLE 22 preparation of (6- (m-toluidino) -benzothiazole-2 (3H) -thione)
The same procedures as in example 20 were repeated except that the starting materials used were 4-amino-3 ' -methyldiphenylamine 5.94g (0.03mol), 4-nitro-3 ' -methyldiphenylamine 0.91g (0.004mol), 4-nitroso-3 ' -methyldiphenylamine 3.39g (0.016mol), sulfur 2.06g (0.065mol) and carbon disulfide 4ml (0.065 mol). 12.24g of 6- (m-toluidino) -benzothiazole-2 (3H) -thione were obtained in a yield of 90%.
1HNMR(400MHz，CDCl3):δ7.47(m，2H)，7.08(m，1H)，7.00(s，1H)，6.59(m，1H)，6.16～6.22(m，2H)，4.0(s，2H)，2.34(s，3H)。
MS m/z(ESI):273[M+1]
EXAMPLE 23 preparation of (6- (p-toluidinyl) -benzothiazole-2 (3H) -thione)
The same procedures as in example 20 were repeated except that the starting materials were 4-amino-4 ' -methyldiphenylamine 5.94g (0.03mol), 4-nitro-4 ' -methyldiphenylamine 0.91g (0.004mol), 4-nitroso-4 ' -methyldiphenylamine 3.07g (0.0145mol), sulfur 2.02g (0.063mol) and carbon disulfide 4.68ml (0.077 mol). 12.40g of 6- (p-toluidinyl) -benzothiazole-2 (3H) -thione were obtained in a yield of 94%.
1HNMR(400MHz，CDCl3):δ7.33(d，2H)，7.24(d，2H)，7.00(s，1H)，6.16～6.22(m，2H)，4.0(s，2H)，2.34(s，3H)。
MS m/z(ESI):273[M+1]
EXAMPLE 24 preparation of (6- (4-ethylanilino) -benzothiazole-2 (3H) -thione)
The starting materials were 6.36g (0.03mol) of 4-ethylphenyl-1, 4-diphenylamine, 0.97g (0.004mol) of 4-ethyl-N- (4-nitrophenyl) aniline, 3.39g (0.015mol) of 4-ethyl-N- (4-nitrosophenyl) aniline, 2.05g (0.064mol) of sulfur and 4.70ml (0.078mol) of carbon disulfide, and the same operation as in example 20 was carried out. 12.89g of 6- (4-ethylanilino) -benzothiazole-2 (3H) -thione was obtained in a yield of 92%.
1HNMR(400MHz，CDCl3):δ7.40(m，2H)，7.04(m，3H)，6.16～6.22(m，2H)，4.0(s，2H)，2.61(q，2H)，1.25(t，3H)。
MS m/z(ESI):287[M+1]
EXAMPLE 25 preparation of (6- (4-Propylanilino) -benzothiazole-2 (3H) -thione)
The same procedures used in example 20 were repeated except for using 6.78g (0.03mol) of 4-propylphenyl-1, 4-diphenylamine, 1.02g (0.004mol) of 4-propyl-N- (4-nitrophenyl) aniline, 3.84g (0.016mol) of 4-propyl-N- (4-nitrosophenyl) aniline, 2.4g (0.075mol) of sulfur and 4ml (0.065mol) of carbon disulfide as starting materials. 14.10g of 6- (4-propylanilino) -benzothiazole-2 (3H) -thione were obtained in a yield of 94%.
1HNMR(400MHz，CDCl3):δ7.40(m，2H)，7.04(m，3H)，6.16～6.22(m，2H)，4.0(s，2H)，2.62(t，2H)，1.65(m，2H)，0.90(t，3H)。
MS m/z(ESI):301[M+1]
Example 26 preparation of (6- (4-isopropylphenylamino) -benzothiazole-2 (3H) -thione)
The starting materials were 6.78g (0.03mol) of 4-isopropylphenyl-1, 4-diphenylamine, 1.02g (0.004mol) of 4-isopropyl-N- (4-nitrophenyl) aniline, 3.36g (0.014mol) of 4-isopropyl-N- (4-nitrosophenyl) aniline, 2.3g (0.072mol) of sulfur and 3.74ml (0.062mol) of carbon disulfide, and the same operation as in example 20 was carried out. 13.68g of 6- (4-isopropylphenylamino) -benzothiazole-2 (3H) -thione were obtained in a yield of 95%.
1HNMR(400MHz，CDCl3):δ7.37(m，2H)，7.00～7.05(m，3H)，6.16～6.22(m，2H)，4.0(s，2H)，2.87(m，1H)，1.20(d，6H)。
MS m/z(ESI):301[M+1]
Performance testing
1. The sample formula (weight portions) is based on 100 weight portions of natural rubber, 5 weight portions of zinc oxide, 2 weight portions of sulfur, 2 weight portions of stearic acid, 40 weight portions of white carbon black and 2 weight portions of anti-aging agent. When the anti-aging agent is a compound 1-7, no accelerator is added; when the anti-aging agent is 6PPD and IPPD, the addition amount of the accelerator CZ is 1 weight part. The specific formulation is shown in table 1.
Wherein the natural rubber is a natural high molecular compound with cis-1, 4-polyisoprene as a main component; promoter CZ refers to N-cyclohexyl-2-benzothiazolesulfenamide; the anti-aging agent is a compound 1 to 7, and 6PPD (N- (1, 3-dimethylbutyl) -N '-phenyl-p-phenylenediamine) and IPPD (N-isopropyl-N' -phenyl-p-phenylenediamine).
2. Sample preparation: and (3) mixing the raw materials on an internal mixer by a conventional method according to the sample formula to obtain the rubber compound. And tabletting the mixed rubber on an open mill, standing for 1 day, and finally vulcanizing on a flat vulcanizing machine at the temperature of 150 ℃ to obtain a vulcanized rubber sample.
3. Aging test: the vulcanizate samples were placed in an ageing oven (model GT-7017-ELU type ageing oven, high-speed rail testing apparatus (Dongguan) Co., Ltd.) at a temperature of 100 ℃ for 72 hours and the tensile strength and elongation at break were determined (in accordance with GB/T528-2009). The tensile strength and elongation at break before and after aging are shown in Table 2.
Tensile Strength Change ═ (tensile Strength after aging of the sample-tensile Strength before aging of the sample)/(tensile Strength before aging of the sample X100%
The change in elongation at break is (elongation at break after sample aging-elongation at break before sample aging) ÷ elongation at break before sample aging × 100%.
The results of the tensile strength change rate and the elongation at break change rate calculated according to the above formulas are shown in table 3.
Table 1 the components in the formulation are parts by weight and the units are omitted from the table.
Table 2:
TABLE 3
| Sample formulation | Tensile Strength Change Rate (%) | Elongation at Break Change (%) |
| Formulation 1 | 1.67 | 2.17 |
| Formulation 2 | 9.37 | 3.41 |
| Formulation 3 | 5.56 | 3.22 |
| Formulation 4 | 7.08 | 3.00 |
| Formulation 5 | 6.92 | 4.26 |
| Formulation 6 | 8.89 | 3.39 |
| Formulation 7 | 8.90 | 3.78 |
| Formulation 8 | 14.29 | 6.25 |
| Formulation 9 | 14.0 | 6.28 |
As can be seen from Table 3, compared with a rubber sample prepared by using 6PPD and IPPD (added with a vulcanization accelerator CZ) as an anti-aging agent and using a substituted anilino-benzothiazole-2-thioketone compound as an anti-aging and vulcanization accelerator (not additionally added with a vulcanization accelerator), the mechanical property of the rubber sample is slowly reduced in an air heat aging test, and the thermal aging resistance of the rubber sample is good. In particular, the rubber samples made according to formulation 1 had the best resistance to thermal aging.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the invention is not limited to the embodiments described above, which are described in the specification only to illustrate the principles of the invention. The invention also includes insubstantial variations and modifications of the invention as would be understood by those skilled in the art without departing from the spirit of the invention as disclosed in the claims.
Claims (10)
1. The structure of the substituted anilino-benzothiazole-2-thioketone compound is represented by the general formula (I):
wherein R represents a substituent attached to the benzene ring and is selected from hydrogen or lower alkyl.
2. The substituted anilino-benzothiazole-2-thione compound of claim 1, wherein R is hydrogen.
3. The substituted anilino-benzothiazole-2-thione compound according to claim 1, wherein R represents a lower alkyl group bonded to a benzene ring, and has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.
4. The substituted anilino-benzothiazole-2-thione compound of claim 3, wherein R represents a methyl group, an ethyl group, a propyl group or an isopropyl group bonded to a benzene ring.
5. The substituted anilino-benzothiazole-2-thione compound of claim 3, wherein R represents a methyl group bonded to a benzene ring.
6. A substituted anilino-benzothiazole-2-thione according to claim 1, selected from the group consisting of:
6- (anilino) -benzothiazole-2 (3H) -thione, 6- (o-toluidino) -benzothiazole-2 (3H) -thione, 6- (m-toluidino) -benzothiazole-2 (3H) -thione, 6- (p-toluidino) -benzothiazole-2 (3H) -thione, 6- (4-ethylanilino) -benzothiazole-2 (3H) -thione, 6- (4-propylanilino) -benzothiazole-2 (3H) -thione, 6- (4-isopropylphenylamino) -benzothiazole-2 (3H) -thione.
7. A preparation method of a substituted anilino-benzothiazole-2-thioketone compound comprises the step of carrying out condensation reaction on a compound with a formula (II), carbon disulfide and sulfur to obtain a compound with a formula (I), wherein the reaction formula is as follows:
wherein R is as defined in claim 1.
8. A preparation method of a substituted anilino-benzothiazole-2-thioketone compound comprises the following steps of carrying out condensation reaction on a compound shown in a formula (II) and a compound shown in a formula (III), carbon disulfide and sulfur to obtain a compound shown in a formula (I), wherein the reaction formula is as follows:
wherein R is as defined in claim 1, the compound of formula (II) is the same as the compound of formula (III) wherein R is attached to the phenyl ring, and R is the same.
9. A preparation method of a substituted anilino-benzothiazole-2-thioketone compound comprises the following steps of carrying out condensation reaction on a compound shown in a formula (II), a compound shown in a formula (III) and a compound shown in a formula (IV), carbon disulfide and sulfur to obtain a compound shown in a formula (I), wherein the reaction formula is as follows:
wherein R is as defined in claim 1, and the position at which R is attached to the benzene ring in the compounds of formula (II), formula (III), and formula (IV) are the same, and R is the same.
10. The substituted anilino-benzothiazole-2-thioketone compound as set forth in any one of claims 1 to 6 can be used as a rubber anti-aging and vulcanization accelerator in the production of rubber products, especially in the production of tires.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022048565A1 (en) * | 2020-09-01 | 2022-03-10 | 圣奥化学科技有限公司 | Preparation method for asymmetric diaryl substituted p-phenylenediamine compound |
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