CN108218911A - Silane of one kind structure containing benzothiazole and preparation method thereof - Google Patents
Silane of one kind structure containing benzothiazole and preparation method thereof Download PDFInfo
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- CN108218911A CN108218911A CN201711483700.0A CN201711483700A CN108218911A CN 108218911 A CN108218911 A CN 108218911A CN 201711483700 A CN201711483700 A CN 201711483700A CN 108218911 A CN108218911 A CN 108218911A
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- China
- Prior art keywords
- benzothiazole
- silane
- preparation
- methyl
- mercaptobenzothiazole
- Prior art date
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- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 title claims abstract description 79
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 20
- -1 methylene, ethylidene Chemical group 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- BZGWZLIKWOCPLN-UHFFFAOYSA-N 1,3-benzothiazole;quinoline Chemical compound C1=CC=C2SC=NC2=C1.N1=CC=CC2=CC=CC=C21 BZGWZLIKWOCPLN-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 4
- JACGKHGTBZGVMW-UHFFFAOYSA-N 4-methyl-3h-1,3-benzothiazole-2-thione Chemical compound CC1=CC=CC2=C1N=C(S)S2 JACGKHGTBZGVMW-UHFFFAOYSA-N 0.000 claims description 4
- FFQWZJULSCUVRK-UHFFFAOYSA-N 5,6-dimethyl-3h-1,3-benzothiazole-2-thione Chemical compound C1=C(C)C(C)=CC2=C1SC(=S)N2 FFQWZJULSCUVRK-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000011085 pressure filtration Methods 0.000 claims description 4
- 125000000335 thiazolyl group Chemical group 0.000 claims description 4
- JJNKKYPHNWIYFW-UHFFFAOYSA-N 4,6-dimethyl-1,3-benzothiazol-2-amine Chemical compound CC1=CC(C)=C2N=C(N)SC2=C1 JJNKKYPHNWIYFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- ZDOBWJOCPDIBRZ-UHFFFAOYSA-N chloromethyl(triethoxy)silane Chemical compound CCO[Si](CCl)(OCC)OCC ZDOBWJOCPDIBRZ-UHFFFAOYSA-N 0.000 claims description 2
- FPOSCXQHGOVVPD-UHFFFAOYSA-N chloromethyl(trimethoxy)silane Chemical compound CO[Si](CCl)(OC)OC FPOSCXQHGOVVPD-UHFFFAOYSA-N 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- DXYYSGDWQCSKKO-UHFFFAOYSA-N 2-methylbenzothiazole Chemical compound C1=CC=C2SC(C)=NC2=C1 DXYYSGDWQCSKKO-UHFFFAOYSA-N 0.000 claims 2
- ILDUPWKUQLPLKK-UHFFFAOYSA-N 5-methyl-3h-1,3-benzothiazole-2-thione Chemical compound CC1=CC=C2SC(S)=NC2=C1 ILDUPWKUQLPLKK-UHFFFAOYSA-N 0.000 claims 2
- KECHYAFVYLLNCH-UHFFFAOYSA-N 6-methyl-3h-1,3-benzothiazole-2-thione Chemical compound CC1=CC=C2N=C(S)SC2=C1 KECHYAFVYLLNCH-UHFFFAOYSA-N 0.000 claims 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 claims 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 1
- ZMYXZXUHYAGGKG-UHFFFAOYSA-N propoxysilane Chemical compound CCCO[SiH3] ZMYXZXUHYAGGKG-UHFFFAOYSA-N 0.000 claims 1
- 239000012312 sodium hydride Substances 0.000 claims 1
- 229910000104 sodium hydride Inorganic materials 0.000 claims 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical group SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 239000000945 filler Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000002787 reinforcement Effects 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 238000004381 surface treatment Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000003973 paint Substances 0.000 abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 239000002657 fibrous material Substances 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 150000004756 silanes Chemical class 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 230000008719 thickening Effects 0.000 abstract description 2
- 238000004073 vulcanization Methods 0.000 abstract description 2
- MTKPOFJUULWZNU-UHFFFAOYSA-N ethoxysilicon Chemical compound CCO[Si] MTKPOFJUULWZNU-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical group C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RABBMOYULJIAFU-UHFFFAOYSA-N 1h-pyrrole;thiophene Chemical class C=1C=CNC=1.C=1C=CSC=1 RABBMOYULJIAFU-UHFFFAOYSA-N 0.000 description 1
- HQULYFAKUZDRPB-UHFFFAOYSA-N 6-bromo-2-[4-(trifluoromethoxy)phenoxy]-1,3-benzothiazole Chemical compound BrC1=CC2=C(N=C(S2)OC2=CC=C(C=C2)OC(F)(F)F)C=C1 HQULYFAKUZDRPB-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 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
- 239000003607 modifier Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention belongs to silane of organosilan technical field more particularly to a kind of structure containing benzothiazole and preparation method thereof.The silane of the structure containing benzothiazole of the present invention provides more reactive silicon alkoxies, more efficient for the interface processing of material；There is good compatibility with big multi-polymer material, when using epoxyhydrocarbyl silanes preparation method, due to introducing the aliphatic chain of epoxyhydrocarbyl, will further improve applicability of the product in polymer material modifying process；It is environmentally protective directly using solvent-free process；Product of the present invention contains N, S element, and interfacial adhesion property, adjustment vulcanization of rubber property for improving material etc. has certain effect；The present invention product involved in coating/paint to pigment/filler decentralized processing, the surface treatment of various inorganic powder/fibrous materials, the functional modification of plastics and its enhancing crosslinking, gum filler reinforcement when interface processing, thickening etc. be respectively provided with significant benefit.
Description
Technical field
The invention belongs to the silane and its preparation side of organosilan technical field more particularly to a kind of structure containing benzothiazole
Method.
Background technology
Silane can react with a variety of organic and inorganic materials, and due to its unique structure and performance, being recognized can
As applications such as coupling agent, crosslinking agent, surface and interface modifiers in each field, and in growing trend.From interface
Adhesive is stated to, from paint to coating, from cross-linked polyolefin to resin base fiberglass reinforced is compound and white carbon reinforcement tire
The fields of grade, the application of silane compound all play the role of highly important.
With the silane of various organosilicon functionalization and the Persisting exploitation of silane coupling agent, up to the present commodity
The silane and silane coupling agent of change is not 40 kinds lower, and main function and purposes are very extensive.Adhesion promoting component is used as in binding material
Adhesion strength is remarkably improved, the glue-joint strength of material interface can be improved in the interface processing of reinforcing fiber, it is compound in rubber-based
Timber-used is remarkably improved peel strength as interface treating agent and inorganic material surface processing is remarkably improved itself and organic polymer
Compatibility of object etc..
Application publication number be respectively CN101445620A, CN103923115A, CN102344462A and
The Chinese patent of CN104045664A discloses several multifunctional silicone alkanes auxiliary agents, their collection plasticising, dispersion, promotion, reinforcement are more
Kind function is integrated, and structure is shown in general formula I II III IV, and the silane of formula of II III IV has relatively low volatility.
There are one being contained only on silicon atom in general formula I, II molecule or two alkoxies, alkoxy group content are low；General formula III, IV point
The two long-chain alkoxy bases connected on silicon atom in son, reactivity are low.Therefore, material is carried out using such multi-functional silane adjuvant
Material surface treatment or during rubber vulcanization, while assigning material there are benzothiazole sulfenyl silane based structures, there is also with it is white
The deficiency that the surface hydroxyl reaction efficiencies of the fillers such as carbon black, clay, calcium carbonate, galapectite, magnesium hydroxide is low, activity is low.
Invention content
The technical problem to be solved by the invention is to provide the silane of one kind structure containing benzothiazole, benzothiazole parents
It is upper to contain more substituted hydrocarbon radical and siloxy structure, in the surface treatment for carrying out the fillers such as white carbon, silicate, carbonate
When have higher efficiency, can also improve its compatibility with polymer phase.
The technical solution that the present invention solves above-mentioned technical problem is as follows：The silane of one kind structure containing benzothiazole, structure
General formula is as follows：
Wherein, R1For C1-C8Alkyl or substituted hydrocarbon radical；
R2For methyl or ethyl；
R3、R4It is each independently H or C1-C4Alkyl；
Y is-S- or-NH-.
Preferably, R1Propoxypropyl-the CH replaced for methylene, ethylidene, propylidene, hydroxyl2-CH(OH)-CH2-O-
(CH2)3Or cyclohexyl-ethyl of hydroxyl substitution
R3、R4It is each independently H or methyl.
Second object of the present invention is to provide the silane preparation method of the above-mentioned structure containing benzothiazole, by benzothiazole
Class monomer carries out removing hcl reaction with chloro hydrocarbyl si lanes or benzothiazole class monomer and epoxyhydrocarbyl silane is carried out ring
Oxygen ring-opening reaction is made.
Wherein, according to the molar ratio control of active hydrogen in benzothiazole class monomer and chloro hydrocarbyl si lanes/epoxyhydrocarbyl silane
The dosage of the benzothiazole class monomer is made, wherein active hydrogen is-NH2Or-SH ,-NH2According to an active hydrogen reaction meter.
When active hydrogen is-NH2When, active hydrogen and chloro hydrocarbyl si lanes/epoxyhydrocarbyl silane in benzothiazole class monomer
Molar ratio is 1: 1.05；When active hydrogen is-SH, active hydrogen and chloro hydrocarbyl si lanes/epoxyhydrocarbyl in benzothiazole class monomer
The molar ratio of silane is 1: (1-1.5).
Further, the preparation that benzothiazole class monomer is reacted with chloro hydrocarbyl si lanes, step are as follows：
(1) organic solvent of chloro hydrocarbyl si lanes He 1-3 times of its volume is put into dry reactor, adds chlorine
For the alkaline matter of hydrocarbyl si lanes weight 1-5%, under nitrogen protection, 10-30min is stirred under the conditions of 50-65 DEG C；
(2) benzothiazole class monomer is taken to be dissolved in the organic solvent of 1-3 times of its volume, benzene a pair of horses going side by side thiophene of organic solvent will be dissolved in
Azole monomer solution is added drop-wise in the chloro hydrocarbyl si lanes solution of step (1), and controlling reaction temperature reacts 3-6h at 65-110 DEG C；
(3) by the reaction solution of step (2) through negative pressure filtration, with organic solvent washing filter cake, gained filtrate decompression has been evaporated off
To get to target product after solvent and unreacted monomer.
Wherein, the benzothiazole class monomer is 2-mercaptobenzothiazole, 4- methyl -2-mercaptobenzothiazole, 6- first
Base -2-mercaptobenzothiazole, 5,6- dimethyl -2-mercaptobenzothiazole, 6- amino-2-mercapto phenyl formics benzothiazole, 5- methyl -2- mercaptos
Base benzothiazole, 2- methylbenzene a pair of horses going side by side thiazolyl -6- amine, 2- amino -4,6- dimethyl benzothiazole or benzothiazole quinoline；
The organic solvent is chloroform, ethyl alcohol, tetrahydrofuran, benzene, toluene, n-hexane, hexamethylene or petroleum ether；
The alkaline matter is lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, hydrogen
Change the mixing of one or more of sodium or sodium ethoxide；
The chloro hydrocarbyl si lanes are chloromethyl trimethoxy silane, chloromethyl triethoxysilane, β-chloroethyl three
Ethoxysilane, γ-r-chloropropyl trimethoxyl silane or γ-chloropropyl triethoxysilane.
Further, the preparation of benzothiazole class monomer and epoxyhydrocarbyl silane reaction, step are as follows：
(1) benzothiazole class monomer and epoxyhydrocarbyl silane are taken, after being thoroughly mixed uniformly under nitrogen protection, is heated to
80-130 DEG C of reaction 2-5h；
(2) reaction solution is detached through distillation, obtains target product.
Wherein, the benzothiazole class monomer is 2-mercaptobenzothiazole, 4- methyl -2-mercaptobenzothiazole, 6- first
Base -2-mercaptobenzothiazole, 5,6- dimethyl -2-mercaptobenzothiazole, 6- amino-2-mercapto phenyl formics benzothiazole, 5- methyl -2- mercaptos
Base benzothiazole, 2- methylbenzene a pair of horses going side by side thiazolyl -6- amine, 2- amino -4,6- dimethyl benzothiazole or benzothiazole quinoline；
The epoxyhydrocarbyl silane is β-(3,4- epoxycyclohexyls) ethyl trimethoxy silane, β-(3,4- epoxide rings
Hexyl) ethyl triethoxysilane, γ-(the third oxygen of 2,3- epoxies) propyl trimethoxy silicane or γ-(the third oxygen of 2,3- epoxies) third
Ethyl triethoxy silicane alkane.
The beneficial effects of the invention are as follows：
(1) silane of the structure containing benzothiazole of the invention provides more reactive silicon alkoxies, for material
Interface processing is more efficient；
(2) silane of the structure containing benzothiazole of the invention has good compatibility with big multi-polymer material, when adopting
During with epoxyhydrocarbyl silanes preparation method, due to introducing the aliphatic chain of epoxyhydrocarbyl, such is will further improve containing benzene a pair of horses going side by side
Applicability of the silane of thiazole structure in polymer material modifying process；It is environmentally protective directly using solvent-free process；
(3) silane of the structure containing benzothiazole of the invention contains N, S element, for improve material interfacial adhesion property,
Adjustment vulcanization of rubber property etc. has certain effect；
(4) silane of the structure containing benzothiazole of the invention is at the pigment/filler dispersion arrived involved in coating/paint
Reason, the surface treatment of various inorganic powder/fibrous materials, the functional modification of plastics and its enhancing crosslinking, gum filler reinforcement
When interface processing, thickening etc. be respectively provided with significant benefit.
Description of the drawings
Fig. 1 is the infrared spectrum of the embodiment of the present invention 1；
Fig. 2 is the nuclear magnetic resonance spectroscopy of the embodiment of the present invention 1.
Specific embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, and a pair of horses going side by side is non-to be used to limit
Determine the scope of the present invention.
Embodiment 1
A kind of silane of structure containing benzothiazole, molecular structural formula are as follows：
The preparation method of above-mentioned silane is：
23.42g (0.14mol) 2- thiol benzothiazoles are added in reactor, pipette 33.13mL (0.147mol,
1.07g/mL, 98%) γ-(2,3- the third oxygen of epoxy)-propyl-triethoxysilicane is added directly into reactor, nitrogen protection
Under, it is uniformly mixed a pair of horses going side by side and is gradually heated to 90 DEG C, product becomes homogeneous yellow transparent oily liquids after reacting 3h, and reaction terminates
Remove unreacted components, product yield 98.2%.
Products therefrom is 1- ((benzothiazole -2- bases) is thio) -3- (3- (three ethoxy silicon substrates) propoxyl group) propane -2- alcohol,
The infrared spectrum (FT-IR) of the compound see attached drawing 1, nuclear magnetic resonance spectroscopy (1H NMR) see attached drawing 2, synthesized product is above-mentioned
The target product of molecular structural formula.
Embodiment 2
A kind of silane of structure containing benzothiazole, molecular structural formula are as follows：
The preparation method of above-mentioned silane is：
19.18g (0.14mol) benzothiazole quinoline is added in reactor, pipettes 33.1ml (0.147mol, 1.07g/
ML, 98%) γ-(2,3- the third oxygen of epoxy)-propyl-triethoxysilicane is added directly into reactor, under nitrogen protection, stirring
Uniformly mixed a pair of horses going side by side is gradually heated to 85 DEG C, and product becomes homogeneous pale yellow transparent oily liquids after reacting 2h, and reaction terminates, removing
Unreacted components, product yield 98.8%.
Products therefrom be 1- (benzothiazole quinoline base) -3- (3- (three ethoxy silicon substrates) propoxyl group) propane -2- alcohol, infrared light
Spectrum, elemental analysis and nuclear magnetic resonance result show synthesized by target product of the product for above-mentioned molecular structure.
Embodiment 3
A kind of silane of structure containing benzothiazole, molecular structural formula are as follows：
The preparation method of above-mentioned silane is：
Equipped with thermometer, reflux, constant pressure funnel drying three-necked flask in, add in 129mL
(0.525mol, 1.00g/mL, content 98%) γ-chloropropyl triethoxysilane, 130mL tetrahydrofurans and 8.0g sodium hydrides,
It under nitrogen protection, stirs, be heated to 55 DEG C of maintenance 0.5h；68.5g (0.50mol) benzothiazole quinoline/150mL tetrahydrochysenes are slowly added dropwise
Tetrahydrofuran solution, stirring, controlling reaction temperature are after 65-67 DEG C, back flow reaction 4.5h, negative pressure filtration while hot, obtained organic liquor
Rotary distillation is mutually carried out, after detaching solvent and unreacted monomer, obtains pale yellow transparent oily liquids silane product, yield
97.3%.
Products therefrom be 3- (3- (three ethoxy silicon substrates) propyl) -2,3- benzothiazole quinolines, infrared spectrum, elemental analysis and core
Magnetic resonance results show synthesized by product be above-mentioned molecular structure target product.
Embodiment 4
A kind of silane of structure containing benzothiazole, molecular structural formula are as follows：
The preparation method of above-mentioned silane is：
Equipped with thermometer, reflux, constant pressure funnel drying three-necked flask in, add in 129mL
(0.525mol, 1.0g/mL, content 98%) γ-chloropropyl triethoxysilane, 130mL toluene and 8.0g sodium hydrides, nitrogen are protected
It under shield, stirs, be heated to 55 DEG C of maintenance 0.5h；Be slowly added dropwise 45.5g (0.25mol) 6- amino-2-mercapto phenyl formics benzothiazole/
100mL toluene solutions, stirring, controlling reaction temperature are after 110 DEG C, back flow reaction 5h, negative pressure filtration while hot, obtained organic liquor
Rotary distillation is mutually carried out, after detaching solvent and unreacted monomer, obtains dark yellow transparent oily liquid silane product, yield
98.1%.
Products therefrom is N- (3- (three ethoxy silicon substrates) propyl) -2- ((3- (three ethoxy silicon substrates) propyl) is thio) benzene a pair of horses going side by side thiophene
Azoles -6- amine, infrared spectrum, elemental analysis and nuclear magnetic resonance result show synthesized by product for above-mentioned molecular structure target produce
Object.
The foregoing is merely presently preferred embodiments of the present invention, a pair of horses going side by side not to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (10)
1. the silane of a kind of structure containing benzothiazole, which is characterized in that its general structure is as follows：
Wherein, R1For C1-C8Alkyl or substituted hydrocarbon radical；
R2For methyl or ethyl；
R3、R4It is each independently H or C1-C4Alkyl；
Y is-S- or-NH-.
2. the silane of the structure according to claim 1 containing benzothiazole, which is characterized in that R1For methylene, ethylidene, Asia
Propyl, the propoxypropyl-CH of hydroxyl substitution2-CH(OH)-CH2-O-(CH2)3Or cyclohexyl-ethyl of hydroxyl substitution
R3、R4It is each independently H or methyl.
3. the silane preparation method of the structure containing benzothiazole described in a kind of claims 1 or 2, which is characterized in that by benzothiazole
Class monomer carries out removing hcl reaction with chloro hydrocarbyl si lanes or benzothiazole class monomer and epoxyhydrocarbyl silane is carried out ring
Oxygen ring-opening reaction is made.
4. preparation method according to claim 3, which is characterized in that step is as follows：
(1) organic solvent of chloro hydrocarbyl si lanes He 1-3 times of its volume is put into dry reactor, adds chlorohydrocarbon
The alkaline matter of base silane weight 1-5% under nitrogen protection, stirs 10-30min under the conditions of 50-65 DEG C；
(2) benzothiazole class monomer is taken to be dissolved in the organic solvent of 1-3 times of its volume, the benzothiazole class of organic solvent will be dissolved in
Monomer solution is added drop-wise in the chloro hydrocarbyl si lanes solution of step (1), and controlling reaction temperature reacts 3-6h at 65-110 DEG C；
(3) by the reaction solution of step (2) through negative pressure filtration, with organic solvent washing filter cake, gained filtrate decompression is evaporated off organic molten
To get to target product after agent and unreacted monomer.
5. preparation method according to claim 3, which is characterized in that step is as follows：
(1) benzothiazole class monomer and epoxyhydrocarbyl silane are taken, after being thoroughly mixed uniformly under nitrogen protection, is heated to 80-
130 DEG C of reaction 2-5h；
(2) reaction solution is detached through distillation, obtains target product.
6. preparation method according to claim 4 or 5, which is characterized in that according to active hydrogen in benzothiazole class monomer with
The molar ratio of chloro hydrocarbyl si lanes/epoxyhydrocarbyl silane controls the dosage of the benzothiazole class monomer, wherein active hydrogen for-
NH2Or-SH ,-NH2According to an active hydrogen reaction meter.
7. preparation method according to claim 6, which is characterized in that active hydrogen is-NH2When, it is living in benzothiazole class monomer
The molar ratio for sprinkling hydrogen and chloro hydrocarbyl si lanes/epoxyhydrocarbyl silane is 1: 1.05.
8. preparation method according to claim 6, which is characterized in that living in benzothiazole class monomer when active hydrogen is-SH
The molar ratio for sprinkling hydrogen and chloro hydrocarbyl si lanes/epoxyhydrocarbyl silane is 1: (1-1.5).
9. preparation method according to claim 4, which is characterized in that the benzothiazole class monomer is 2- sulfydryls benzene a pair of horses going side by side
Thiazole, 4- methyl -2-mercaptobenzothiazole, 6- methyl -2-mercaptobenzothiazole, 5,6- dimethyl -2-mercaptobenzothiazole, 6-
Amino-2-mercapto phenyl formic benzothiazole, 5- methyl -2-mercaptobenzothiazole, 2- methylbenzene a pair of horses going side by side thiazolyl -6- amine, 2- amino -4,6- two
Methyl benzothiazole or benzothiazole quinoline；
The organic solvent is chloroform, ethyl alcohol, tetrahydrofuran, benzene, toluene, n-hexane, hexamethylene or petroleum ether；
The alkaline matter is lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydride
Or one or more of sodium ethoxide mixing；
The chloro hydrocarbyl si lanes are chloromethyl trimethoxy silane, chloromethyl triethoxysilane, three ethoxy of β-chloroethyl
Base silane, γ-r-chloropropyl trimethoxyl silane or γ-chloropropyl triethoxysilane.
10. preparation method according to claim 5, which is characterized in that the benzothiazole class monomer is 2- sulfydryl benzene
Parallel thiazole, 4- methyl -2-mercaptobenzothiazole, 6- methyl -2-mercaptobenzothiazole, 5,6- dimethyl -2-mercaptobenzothiazole,
6- amino-2-mercapto phenyl formics benzothiazole, 5- methyl -2-mercaptobenzothiazole, 2- methylbenzene a pair of horses going side by side thiazolyl -6- amine, 2- amino -4,6-
Dimethyl benzothiazole or benzothiazole quinoline；
The epoxyhydrocarbyl silane is β-(3,4- epoxycyclohexyls) ethyl trimethoxy silane, β-(3,4- epoxycyclohexyls)
Ethyl triethoxysilane, γ-(the third oxygen of 2,3- epoxies) propyl trimethoxy silicane or γ-three second of (the third oxygen of 2,3- epoxies) propyl
Oxysilane.
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| CN110092801A (en) * | 2019-01-07 | 2019-08-06 | 青岛科技大学 | A kind of novel promotion silane coupling agent and preparation method thereof |
| CN112321633A (en) * | 2020-11-05 | 2021-02-05 | 湖北新蓝天新材料股份有限公司 | Double-silicon type coupling agent and preparation method and application thereof |
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| CN112321633B (en) * | 2020-11-05 | 2023-10-03 | 湖北新蓝天新材料股份有限公司 | Double-silicon coupling agent and preparation method and application thereof |
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