CN111116634A - Imide-terminated mercaptosilane coupling agent and synthesis method and application thereof - Google Patents
Imide-terminated mercaptosilane coupling agent and synthesis method and application thereof Download PDFInfo
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- CN111116634A CN111116634A CN201911305562.6A CN201911305562A CN111116634A CN 111116634 A CN111116634 A CN 111116634A CN 201911305562 A CN201911305562 A CN 201911305562A CN 111116634 A CN111116634 A CN 111116634A
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- 239000007822 coupling agent Substances 0.000 title claims abstract description 47
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- 229920001971 elastomer Polymers 0.000 claims abstract description 69
- 239000005060 rubber Substances 0.000 claims abstract description 69
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000945 filler Substances 0.000 claims abstract description 31
- 230000003993 interaction Effects 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims description 73
- 238000006243 chemical reaction Methods 0.000 claims description 47
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 238000012545 processing Methods 0.000 claims description 17
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims description 14
- -1 imide salt Chemical class 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- 238000004440 column chromatography Methods 0.000 claims description 12
- 238000010828 elution Methods 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000000741 silica gel Substances 0.000 claims description 12
- 229910002027 silica gel Inorganic materials 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000005062 Polybutadiene Substances 0.000 claims description 8
- 229920003049 isoprene rubber Polymers 0.000 claims description 8
- 150000003949 imides Chemical class 0.000 claims description 7
- 229920002857 polybutadiene Polymers 0.000 claims description 7
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 238000013040 rubber vulcanization Methods 0.000 claims description 3
- 239000004636 vulcanized rubber Substances 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- 238000010058 rubber compounding Methods 0.000 claims 1
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 45
- 239000006229 carbon black Substances 0.000 abstract description 26
- 229920000642 polymer Polymers 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 14
- 230000020169 heat generation Effects 0.000 abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 238000010057 rubber processing Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 40
- 239000000463 material Substances 0.000 description 37
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 238000004513 sizing Methods 0.000 description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 238000004073 vulcanization Methods 0.000 description 17
- 238000001514 detection method Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 239000005457 ice water Substances 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 238000004896 high resolution mass spectrometry Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- IHMCIQQFJOAERW-UHFFFAOYSA-N 3-triethoxysilylpropyl thiohypochlorite Chemical compound CCO[Si](OCC)(OCC)CCCSCl IHMCIQQFJOAERW-UHFFFAOYSA-N 0.000 description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 description 6
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 6
- 238000007906 compression Methods 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- FYRHIOVKTDQVFC-UHFFFAOYSA-M potassium phthalimide Chemical compound [K+].C1=CC=C2C(=O)[N-]C(=O)C2=C1 FYRHIOVKTDQVFC-UHFFFAOYSA-M 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000003139 buffering effect Effects 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 125000005462 imide group Chemical group 0.000 description 3
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 125000005371 silicon functional group Chemical group 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- ZSBDPRIWBYHIAF-UHFFFAOYSA-N n-acetylacetamide Chemical compound CC(=O)NC(C)=O ZSBDPRIWBYHIAF-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- WLDMPODMCFGWAA-UHFFFAOYSA-N 3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione Chemical compound C1CCCC2C(=O)NC(=O)C21 WLDMPODMCFGWAA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- KNCYXPMJDCCGSJ-UHFFFAOYSA-N piperidine-2,6-dione Chemical compound O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention belongs to a silane coupling agent, and particularly relates to an imide-terminated mercapto silane coupling agent, and a synthesis method and application thereof. The imide-group-terminated mercaptosilane coupling agent has a structure shown in a formula (I). The imide-group-terminated mercaptosilane coupling agent shown in the formula (I) can obviously enhance the interaction between a polymer and a filler, reduce the hysteresis loss of rubber, reduce heat generation, reduce the Payne effect of the rubber and improve the dispersibility of white carbon black, thereby reducing the content of the white carbon blackThe oil consumption and the emission of carbon dioxide in the running process of the tire enhance the wear resistance of the tire, and simultaneously can prolong the scorching time of rubber and improve the safety of rubber processing.
Description
Technical Field
The invention relates to a silane coupling agent, in particular to an imide-terminated mercapto silane coupling agent, a synthetic method and application thereof.
Background
White carbon black is an inorganic filler, which is the most important inorganic reinforcing filler following carbon black because of its excellent reinforcing property, and exhibits strong polarity and high surface energy because its surface is covered with a large amount of silicon hydroxyl groups. The rubber molecules are nonpolar as alkyl chains, and when the two are blended, phase interface separation is easy to generate due to thermodynamic incompatibility.
The silane coupling agent is a silane containing two groups with different chemical properties simultaneously, including an organic functional group and a hydrolyzable silicon functional group, and the general formula of the silane coupling agent can be expressed as Y-R-SiX3. Because the silane coupling agent molecules simultaneously have two functional groups which are organophilic and organophilic, the silane coupling agent can play a role of a molecular bridge, connect rubber molecules and white carbon black on an interface, increase the compatibility of the rubber molecules and the white carbon black, improve the dispersibility of the white carbon black, enhance the interaction of the white carbon black and the rubber, and achieve the purposes of improving the processability, the physical property and the dynamic property of the rubber. Silane coupling agents have been developed to date in the middle of the last century and are quite diverse, with hundreds of known structures. Silane coupling agents of novel structure have also been developed and reported as in recent years, such as the oligomer-type silane coupling agent Rheinfiat 1715 from Rheinchemie Rheinau, Germany; an oligomer silane coupling agent developed by Nippon shoku rubber company, having an average molecular weight of about 800; the subject group of the university of south China's Jade & Min professor grafts the silicon functional group and other functional groups of the rubber auxiliary agent segment together, and synthesizes the multifunctional silane coupling agent; several macromolecular silane coupling agents are combined on the subject of the Zhuqing increase professor of Shandong university in China and are used for improving the interaction between the silicon rubber and the white carbon black. Although development and research of novel silane coupling agents have been ongoing, only over twenty types of silane coupling agents are currently distributed in the market from the viewpoint of significance to actual industrial production, and the types of silane coupling agents that can be applied to different industrial fields are rare.
Sulfur-containing silane coupling agents are the most important class in the tire rubber industry, and can be roughly classified into three classes, namely mercaptoalkoxysilane coupling agents; one is bis (polysulfur-chain silane coupling agents) such as Si69, Si 75; still another class is thiocarboxylate-based silane coupling agents (also known as hindered mercaptosilane coupling agents NXT). The mercapto alkoxy silane coupling agent is easy to generate scorch in the processing process due to the high reactivity of the end mercapto group, so that the higher viscosity is caused, the processing and the forming are not favorable, and the application of the silane coupling agent is limited due to the unpleasant smell of the mercapto alkoxy silane coupling agent; due to higher atom economy, proper mixing temperature and final rubber viscosity of the bis (polysulfide chain silane coupling agent), the bis (polysulfide chain silane coupling agent) is the most widely used silane coupling agent at present, for example, Si69 exclusively takes the role of chelating head in the silane coupling agent for tires for a long time, the bis (polysulfide chain silane coupling agent) has multiple functions of a coupling agent, a vulcanizing agent, a lubricant, an anti-vulcanization reversion agent and the like, a longer and softer vulcanization crosslinking bond can improve the dynamic mechanical property of tire rubber, but Si69 easily causes rubber scorching in use; thiocarboxylate silane coupling agents were first discovered in the 21 st century, hydrogen on original mercapto group was replaced by carbonyl, reduced the reactivity of mercapto group, the mercapto group that is blocked is in the sub-active state, the group of blocking mercapto group can be taken off while sulfurizing, thus show the characteristic (US20040210001) that mercapto group participates in the rubber vulcanization, such as NXT can reach better effects compared with Si69 and Si75, such as reducing the sizing material viscosity, reduce the number of mixing stages, lower costs, improve the processing property of sizing material, improve the filler dispersion, improve the dynamic mechanical properties of sizing material, it is the better silane coupling agent for tire at present.
The thiocarboxylate silane coupling agent NXT can be regarded as that carbonyl carries out end capping treatment on the mercapto silane coupling agent at the end position, the silicon functional group of the coupling agent reacts with white carbon black in the mixing process to change the surface polarity of the white carbon black, the driving force of the agglomeration of the filler white carbon black is reduced, the filler-filler interaction is reduced, the filler agglomeration is inhibited, and the dispersibility of the filler is improved. However, the existing coupling agent can not show advantages in improving the interaction force between the filler and the polymer, for example, the C-S bond energy of the common alkyl group is about 305KJ/mol, the C-S bond energy of (C ═ O) -S in NXT is about 320.1KJ/mol, the N-S bond energy of the common alkyl group is similar to the data of the common C-S bond energy, so that the C-S bond and the N-S bond are not easy to open under the mixing condition, the silane coupling agent is not easy to interact with the polymer, and the interaction force between the polymer and the filler is relatively weak. Therefore, in order to better enhance the interaction force between the polymer and the filler and simultaneously have no obvious damage to the processing performance of the rubber material, finally improve the dispersibility of the white carbon black in the rubber material, achieve the purposes of reducing the hysteresis loss of rubber and reducing the heat generation and energy loss in the running process of a tire, conceptionally design a plurality of high-activity end-capping functional groups, and graft the end-capping functional groups and the mercaptosilane coupling agent together to synthesize the novel silane coupling agent so as to improve the interaction force between the polymer and the filler, and the method has important significance.
Disclosure of Invention
In order to solve the problem that the silane coupling agent in the prior art cannot well improve the interaction between a polymer and a filler, the invention provides an imide-group-terminated mercaptosilane coupling agent.
In order to solve the technical problems, the invention adopts the following technical scheme:
an imide-group-terminated mercaptosilane coupling agent has a structure shown in formula (I):
wherein, R is1Is selected from C1-C18An alkyl, aryl, cycloalkyl, alkenyl or alkynyl group of (a); the R is2、R3、R4At least one is hydrolyzable chlorine, bromine, alkoxy or ester group, the others are selected from hydrogen, alkyl, aryl or cycloalkyl; the R is5Selected from hydrogen, C1-C18The alkyl group of (1), substituted or unsubstituted aryl group, substituted or unsubstituted cycloalkyl group.
Preferably, the coupling agent is selected from
Having only one thiogenThe silane coupling agent of the subgroup plays a role of reinforcing polymer-filler interaction, and can only break an N-S bond or a C-S bond to generate a sulfur radical, for example, the C-S bond energy of (C ═ O) -S in NXT which is most commonly used is about 320.1KJ/mol, and the C-S bond or general N-S bond is difficult to open under mixing conditions, so that the silane coupling agent is not easy to interact with the polymer, and the interaction force between the polymer and the filler is relatively weak. During the development process, the inventor wants to design a coupling agent capable of enhancing the interaction between a polymer and a filler under the mixing condition, finally screens out the coupling agent with N-S bonds with a specific structure by synthesizing and screening a plurality of compounds, and finally finds out that a characteristic structure (C ═ O) exists in a silane coupling agent along with the progress of experiments2The N-S is characterized in that two carbonyl groups in the characteristic structure are strong electron groups, so that the N-S bond can be polarized more easily, the N-S bond can be broken more easily, more active sulfur free radicals can exist under the mixing condition, the sulfur free radicals and a polymer form chemical bonds in the mixing process, and the polar hydrolysis end of a coupling agent and a filler form chemical bonds, so that the interaction between the polymer and the filler is enhanced, the dispersion of the filler is promoted, the agglomeration of the filler is inhibited, the hysteresis loss of rubber is reduced, the energy loss generated by continuous breaking and reconstruction of a filler network structure is reduced, and the energy loss of a tire in the driving process can be reduced.
Moreover, the coupling agent provided by the invention can influence the scorching characteristics of the rubber material through the chemical reaction characteristics of the end-capping functional groups, prolong the scorching time of the rubber material, improve the processing safety of the rubber material, and finally reflect the processing performance, physical and mechanical properties and dynamic properties of the rubber material.
The invention also aims to provide a synthesis method of the imide-terminated mercaptosilane coupling agent shown in the formula (I), wherein the imide-terminated mercaptosilane coupling agent can be prepared by reacting halogenated imide or imide salt or imide compounds with mercaptoalkylsilane compounds or corresponding sulfenyl chloride compounds of mercaptoalkylsilane.
Preferably, the molar ratio of the halogenated imide or imide salt or imide-like compound to the corresponding sulfenyl chloride compound of mercaptoalkylsilane compound or mercaptoalkylsilane is from 1:1.0 to 1.2.
The invention provides a synthesis method of imide-group-terminated mercapto silane coupling agent shown in formula (I), which comprises the following steps of dissolving halogenated imide or imide salt or imide compound in an organic solvent in an inert gas atmosphere to prepare a reaction solution with the concentration of 0.4-0.8mol/L, and adding an acid-binding agent if acid is generated; the mercaptoalkyl silane compound or the sulfenyl chloride compound corresponding to the mercaptoalkyl silane is dripped into the reaction solution to react at room temperature, the rotating speed of the magneton is 500-800r/min, and the reaction time is 3-12 h.
Preferably, after the reaction is finished, removing the solvent of the reaction system, and then performing column chromatography separation by using 400-mesh silica gel powder, wherein the eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 20:1-6:1, thereby finally obtaining the compound imido group-blocked mercaptosilane coupling agent.
Finally, the invention also provides the application of the imide group end-capping mercapto silane coupling agent shown in the formula (I) in rubber mixing or vulcanization, which is used for improving the interaction force between rubber and filler, reducing the hysteresis loss, prolonging the scorching time of rubber materials and improving the processing safety of the rubber materials.
The invention provides an imide-group-terminated mercapto silane coupling agent shown as a formula (I), which can remarkably enhance the interaction between a polymer and a filler, reduce the hysteresis loss of a rubber material, reduce heat generation, reduce the Payne effect of the rubber material and improve the dispersibility of white carbon black, thereby reducing the oil consumption and the emission of carbon dioxide in the running process of a tire and enhancing the wear resistance of the tire; meanwhile, the imide group end-capped mercaptosilane coupling agent provided by the invention can prolong the scorching time of rubber materials and improve the processing safety of the rubber materials, and the synthesis of the novel imide group end-capped mercaptosilane coupling agent is realized for the first time by adopting the nucleophilic substitution reaction of imide or imide salt to sulfenyl chloride.
Detailed Description
The invention discloses an imido-terminated mercaptosilane coupling agent, a synthesis method and application thereof, and can be realized by appropriately improving process parameters by referring to the content. It is expressly intended that all such similar substitutes and modifications which would be obvious to those skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The following detailed description of the invention refers to specific embodiments thereof for better understanding by those skilled in the art.
Comparative example 1
Under the atmosphere of inert gas and nitrogen, 10.64g (0.125mol) of 2-pyrrolidone is dissolved in 250mL of toluene in a 500mL Schlenk bottle to prepare a solution with the concentration of 0.5mol/L, 26mL (0.188mol) of triethylamine is added, then the solution is placed in an ice water bath (0 ℃), 40.94g (0.15mol) of triethoxysilylpropyl sulfenyl chloride is dropwise added into the solution system, the solution is placed at room temperature after the dropwise addition, the molar ratio is 1.2:1, the rotation speed of magnetons is 800r/min, the reaction time is 8h, and the reaction progress is followed by TLC detection. After the reaction is finished, filtering to remove triethylamine hydrochloride, removing a solvent by using a rotary evaporator, and then performing column chromatography separation by using 400-mesh silica gel powder, wherein an eluent system is petroleum ether and ethyl acetate, the gradient elution polarity selection range is 6: 1-3: 1, 25g of a compound (shown as a structure in the specification) is obtained, and the data are represented by a nuclear magnetic resonance spectrum and a high-resolution mass spectrum, and are as follows:1H NMR(600MHz,CDCl3)δ3.80(q,J＝7.0Hz,6H),3.59(t,J＝7.1Hz,2H),2.85-2.78(m,2H),2.41(t,J＝8.1Hz,2H),2.09–2.01(m,2H),＝1.74-1.66(m,2H),1.21(t,J＝7.0Hz,9H),0.80–0.73(m,2H).13C NMR(150MHz,CDCl3) δ 177.96,58.56,53.10,40.18,30.42,22.13,19.03,18.43,9.70 ESI-MS:344.1321, calculated as (M + Na): 344.1328.
example 1
16.8g (0.126mol) of N-bromosuccinimide (NCS) is dissolved in 315mL of dichloromethane in a 500mL Schlenk bottle under the atmosphere of inert gas nitrogen to prepare a solution with the concentration of 0.4mol/L, and then the solution is placed in an ice water bath (0 ℃), 29.04mL (0.12mol) of mercaptopropyltriethoxysilane is dripped into the NCS solution system, the molar ratio is 1:1.05, the magneton rotating speed is 800r/min, and the reaction is carried out for 30min at room temperature. Then, 18.4mL (0.132mol) of triethylamine was further dissolved in 50mL of dichloromethane and added dropwise to the reaction system for 3 hours, and the progress of the reaction was followed by TLC detection. And after the reaction is finished, filtering to remove triethylamine hydrochloride, removing the solvent by using a rotary evaporator, and performing column chromatography separation by using 400-mesh silica gel powder, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 6: 1-3: 1, so that 25g of the compound is obtained. The compounds were characterized using nuclear magnetic resonance spectroscopy and high resolution mass spectroscopy with the following data:1H NMR(600MHz,CDCl3)δ3.64(q,J＝7.0Hz,6H),2.71(t,J＝7.3Hz,2H),2.68(s,4H),1.54–1.44(m,2H),1.05(t,J＝7.0Hz,9H),0.65–0.56(m,2H).13C NMR(150MHz,CDCl3) δ 176.96,58.17,40.18,28.43,21.69,18.08,9.12.ESI-MS:358.1120, calculated as (M + Na): 358.1120. the reaction formula of the above reaction is shown below:
the performance of the coupling agent prepared in comparative example 1 and example 1 was tested:
the coupling agent prepared in comparative example 1 and example 1, bis- (gamma-propyltriethoxysilane) tetrasulfide (Si69) and 3-thio caprylate-1-propyltriethoxysilane (NXT) are applied to raw rubber isoprene rubber, and the raw rubber isoprene rubber is subjected to mixing and vulcanization by adopting a conventional mixing method and a formula (table 1), and the performance of the corresponding rubber compound is detected, wherein the detection results are shown in table 2.
The common mixing process is carried out by three sections, wherein one section is to keep the temperature of the raw rubber isoprene rubber, the white carbon black and the silane coupling agent at 150 ℃ for 2 min; in the second stage, stearic acid, zinc oxide, protective wax and an anti-aging agent are added into the first-stage rubber compound to carry out mixing reaction, and the mixture is heated to 150 ℃; mixing the accelerant, the sulfur and the second-stage rubber compound to obtain final rubber compound in the third stage;
vulcanizing the final rubber on a flat vulcanizing machine, wherein the vulcanization temperature is 150 ℃, and the vulcanization time of a tensile and tearing test sample is (tc90+5) min; the vulcanization time of the elasticity, hardness and compression heat generation test specimens was (tc90+10) min.
Table 1: IR mixing formula detail
The structures of the Si69 and the NXT are as follows:
TABLE 2 elastomeric compound/vulcanizate Properties measurements
Injecting: the Si69 stock data were all set to 100, and the other stock data were percentages of their true data to the Si69 true data.
the tan delta value can be used for representing the hysteresis loss of the rubber material, the smaller the tan delta value is, the lower the hysteresis loss is, and the data in table 2 show that the imide-group-terminated mercaptosilane coupling agent obtained in the embodiment can obviously improve the hysteresis loss of the isoprene rubber.
ΔG'(0.1％-25％)The value represents the Payne effect of the sizing material, and further reflects the dispersibility of the white carbon black in the sizing material, delta G'(0.1％-25％)The smaller the value is, the smaller the Payne effect is, and the better the dispersibility of the white carbon black is; TABLE 2 numbersIt is shown to be from Δ G'(0.1％-25％)The value data show that the imide-group-terminated mercaptosilane coupling agent obtained in the embodiment can obviously reduce Payne effect of the sizing material and improve the dispersibility of white carbon black in the sizing material; from the compression heat generation Δ T values, it can be seen that example 1 can reduce the heat generation of the compound, thereby reducing the energy loss during tire running.
300 stretch/100 stretch, the bound gum content can characterize the polymer-filler interaction to a certain extent, generally speaking, the greater the 300 stretch/100 stretch, the higher the bound gum content, the stronger the polymer-filler interaction; the data in table 2 show that the imide-terminated mercaptosilane coupling agent obtained in this example can enhance the polymer-filler interaction and, to a certain extent, the wear resistance of the tire.
Mooney viscosity values can be used to characterize the processability of the compound, with larger Mooney viscosity values being more detrimental to the processing of the compound. It can therefore be seen from the Mooney @100 ℃ value data that the compound prepared in example 1 does not increase the Mooney viscosity value of the compound and does little to impair the processability of the compound.
The scorch time t5 can be used to characterize the safety of the compound processing, the greater the t5 value, the higher the safety of the compound processing. Therefore, it can be seen from the t5 value data that the compound obtained in example 1 can prolong the scorching time of the sizing material and improve the safety of sizing material processing, because the pKa value of succinimide N-H is 14.7, has certain acidity, and can have certain buffering effect on the alkaline accelerator.
In addition, the compounds obtained in comparative example 1 and example 1, bis- (gamma-propyltriethoxysilane) tetrasulfide (Si69) and 3-thiooctanoate-1-propyltriethoxysilane (NXT) were applied to raw butylbenzene/butadiene rubber, and the mixture was kneaded and vulcanized by a conventional kneading method and formulation (detailed in table 3), and the corresponding rubber compound was tested for properties, and the test results are shown in table 4.
The mixing process is carried out in three stages, and in the first stage, raw rubber butylbenzene/butadiene rubber, white carbon black, a silane coupling agent, stearic acid, zinc oxide, protective wax and an anti-aging agent are subjected to heat preservation for 2min at the temperature of 150 ℃; in the second stage, the first-stage rubber compound is thermally treated to 150 ℃; mixing the accelerant, the sulfur and the second-stage rubber compound to obtain final rubber compound in the third stage;
vulcanizing the final rubber on a flat vulcanizing machine, wherein the vulcanization temperature is 165 ℃, and the vulcanization time of a tensile and tearing test sample is (tc90+5) min; the vulcanization time of the elasticity, hardness and compression heat generation test specimens was (tc90+10) min.
TABLE 3 SBR/BR compounding recipe
TABLE 4 elastomeric compound/vulcanizate Properties measurements
Injecting: the Si69 stock data were all set to 100, and the other stock data were percentages of their true data to the Si69 true data.
The data in Table 4 show that tan delta values can be used to characterize the hysteresis loss of the compound, with lower tan delta values giving lower hysteresis losses. It can be seen from the tan δ value data that example 1 can improve the hysteresis loss of butylbenzene/butadiene rubber.
ΔG'(0.1％-25％)The value represents the Payne effect of the sizing material, and further reflects the dispersibility of the white carbon black in the sizing material, delta G'(0.1％-25％)The smaller the value, the smaller the Payne effect, the better the white carbon black dispersibility, from G'(0.1％-25％)The value data show that the imide-group-terminated mercaptosilane coupling agent obtained in the embodiment can reduce Payne effect of the sizing material and improve the dispersibility of white carbon black in the sizing material.
The 300/100 elongation, bound gel content in the data of Table 4, characterizes the interaction of polymer and filler to some extent, in general, the greater the 300/100 elongation, the higher the bound gel content, and the stronger the interaction of polymer and filler; therefore, the two data show that the imide-group-terminated mercaptosilane coupling agent obtained by the implementation can better enhance the interaction between the polymer and the filler and enhance the wear resistance of the tire to a certain extent.
Mooney viscosity values can be used to characterize the processability of the compound, with higher Mooney viscosity values being more detrimental to the processing of the compound; therefore, it can be seen from the Mooney viscosity @100 ℃ data that the compound prepared in example 1 does not increase the Mooney viscosity of the compound and does not impair the processability of the compound.
Example 2
In a 250mL Schlenk bottle, 13.89g (0.075mol) of phthalimide potassium salt is dissolved in 150mL of tetrahydrofuran under the atmosphere of inert gas and nitrogen to prepare a solution with the concentration of 0.5mol/L, then the solution is placed in an ice water bath (0 ℃), 24.57g (0.09mol) of triethoxysilylpropyl sulfenyl chloride is dripped into the solution system, the solution is placed at room temperature after the dripping, the reaction is carried out for 8 hours at the room temperature, and the reaction progress is tracked through TLC detection, wherein the molar ratio is 1.2:1, the magneton rotation speed is 600 r/min. After the reaction is finished, filtering to remove potassium chloride, removing the solvent by using a rotary evaporator, and then carrying out column chromatography separation by using a 400-mesh silica gel powder column, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 10: 1-8: 1, so as to obtain 17g of the compound. The compounds were characterized using nuclear magnetic resonance spectroscopy and high resolution mass spectroscopy with the following data:1H NMR(600MHz,CDCl3)δ7.89(dd,J＝5.5,3.1Hz,2H),7.75(dd,J＝5.5,3.1Hz,2H),3.76(q,J＝7.0Hz,6H),2.89(t,J＝7.3Hz,2H),1.74-1.63(m,2H),1.15(t,J＝7.0Hz,9H),0.80-0.74(m,2H).13C NMR(150MHz,CDCl3) δ 168.54,134.61,132.21,123.87,58.48,41.52,22.08,18.34,9.43.ESI-MS:406.1139, calculated as (M + Na): 406.1120, respectively; the reaction formula is shown as follows:
the performance of the coupling agent prepared in comparative example 1 and example 2 was tested:
the coupling agent prepared in comparative example 1 and example 2, bis- (gamma-propyltriethoxysilane) tetrasulfide (Si69) and 3-thio caprylate-1-propyltriethoxysilane (NXT) are applied to raw rubber isoprene rubber, the conventional mixing method and formula (the same as table 1) are adopted for mixing and vulcanization, and the corresponding rubber materials are subjected to performance detection, wherein the detection results are shown in table 5;
the common mixing process is carried out by three sections, wherein one section is to keep the temperature of the raw rubber isoprene rubber, the white carbon black and the silane coupling agent at 150 ℃ for 2 min; in the second stage, stearic acid, zinc oxide, protective wax and an anti-aging agent are added into the first-stage rubber compound to carry out mixing reaction, and the mixture is heated to 150 ℃; mixing the accelerant, the sulfur and the second-stage rubber compound to obtain final rubber compound in the third stage;
vulcanizing the final rubber on a flat vulcanizing machine, wherein the vulcanization temperature is 150 ℃, and the vulcanization time of a tensile and tearing test sample is (tc90+5) min; the vulcanization time of the elasticity, hardness and compression heat generation test specimens was (tc90+10) min.
In addition, the compounds obtained in comparative example 1 and example 1, bis- (gamma-propyltriethoxysilane) tetrasulfide (Si69) and 3-thiooctanoate-1-propyltriethoxysilane (NXT) were applied to raw butylbenzene/butadiene rubber, and they were subjected to mixing and vulcanization by the conventional mixing method and formulation (same as in table 3), and the corresponding rubber compounds were subjected to property detection, and the detection results are shown in table 6.
The mixing process is carried out in three stages, and in the first stage, raw rubber butylbenzene/butadiene rubber, white carbon black, a silane coupling agent, stearic acid, zinc oxide, protective wax and an anti-aging agent are subjected to heat preservation for 2min at the temperature of 150 ℃; in the second stage, the first-stage rubber compound is thermally treated to 150 ℃; mixing the accelerant, the sulfur and the second-stage rubber compound to obtain final rubber compound in the third stage;
vulcanizing the final rubber on a flat vulcanizing machine, wherein the vulcanization temperature is 165 ℃, and the vulcanization time of a tensile and tearing test sample is (tc90+5) min; the vulcanization time of the elasticity, hardness and compression heat generation test specimens was (tc90+10) min.
Table 5: detection of mixed rubber/vulcanized rubber performance
The data in table 5 show that the coupling agent compound obtained in example 2 can significantly improve the hysteresis loss of isoprene rubber; as can be seen from the data of Δ G' (0.1% -25%), the compound obtained in example 2 can significantly reduce the Payne effect of the sizing material and improve the dispersibility of white carbon black in the sizing material; from the data of 300 stretch/100 stretch and the content of the bound rubber, it can be seen that the compound obtained in example 2 can significantly enhance the polymer-filler interaction and enhance the wear resistance of the tire to a certain extent; from the t5 value data, it can be seen that the scorch time of the rubber compound can be prolonged and the safety of rubber compound processing can be improved in example 2, because the pKa value of phthalimide N-H is 8.3, and the phthalimide N-H has certain acidity and can have a certain buffering effect on the alkaline accelerator.
Table 6: detection of mixed rubber/vulcanized rubber performance
The data in table 6 show that the tan δ value shows that the coupling agent compound obtained in example 2 can improve the hysteresis loss of butylbenzene/butadiene rubber; from Δ G'(0.1％-25％)The value data shows that the coupling agent obtained in the embodiment 2 can obviously reduce Payne effect of the sizing material and improve the dispersibility of the white carbon black in the sizing material; from the data of 300 stretch/100 stretch and the content of the bound rubber, it can be seen that the coupling agent obtained in example 2 can significantly enhance the interaction of the polymer and the filler, and enhance the wear resistance of the tire to a certain extent; it can be seen from the t5 value data that the coupling agent obtained in example 2 can prolong the scorching time of the sizing material and improve the safety of sizing material processing, because the pKa value of phthalimide N-H is 8.3, has certain acidity, and can have certain buffering effect on the alkaline accelerator.
Example 3
18.52g (0.1mol) of potassium phthalimide was dissolved in 125mL of N, N-dimethylformamide in a 250mL Schlenk flask under an inert gas argon atmosphere to prepare a 0.8mol/L solution, which was then placed in an ice-water bath (0 ℃ C.), and the temperature was 3 ℃ C0.02g (0.11mol) of triethoxysilylpropylsulfenyl chloride is dripped into the solution system, the solution system is placed at room temperature after the dripping, the molar ratio is 1.1:1, the rotation speed of magnetons is 700r/min, the reaction time is 12h, and the reaction process is tracked by TLC detection. After the reaction is finished, filtering to remove potassium chloride, removing the solvent by using a rotary evaporator, and then performing column chromatography separation by using 400-mesh silica gel powder, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 10: 1-8: 1, so that 23g of the compound is obtained. The compounds were characterized using nuclear magnetic resonance spectroscopy and high resolution mass spectroscopy with the following data:1H NMR(600MHz,CDCl3)δ7.89(dd,J＝5.5,3.1Hz,2H),7.75(dd,J＝5.5,3.1Hz,2H),3.76(q,J＝7.0Hz,6H),2.89(t,J＝7.3Hz,2H),1.74-1.63(m,2H),1.15(t,J＝7.0Hz,9H),0.80-0.74(m,2H).13C NMR(150MHz,CDCl3) δ 168.54,134.61,132.21,123.87,58.48,41.52,22.08,18.34,9.43.ESI-MS:406.1139, calculated as (M + Na): 406.1120, respectively; the reaction formula is shown as follows:
example 4
Under the atmosphere of inert gas and nitrogen, 5.56g (0.03mol) of phthalimide potassium salt is dissolved in 60mL of dichloromethane in a 250mL Schlenk bottle to prepare a solution with the concentration of 0.5mol/L, then the solution is placed in an ice-water bath (0 ℃), 9.01g (0.033mol) of triethoxysilylpropylsulfenyl chloride is dripped into the solution system, the solution is placed at room temperature after the dripping, the molar ratio is 1.1:1, the magneton rotating speed is 500r/min, the reaction time is 6h, and the reaction progress is tracked by TLC detection. After the reaction is finished, filtering to remove potassium chloride, removing the solvent by using a rotary evaporator, and then performing column chromatography separation by using 400-mesh silica gel powder, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 10: 1-8: 1, so as to obtain 5g of the compound. The compounds were characterized using nuclear magnetic resonance spectroscopy and high resolution mass spectroscopy with the following data:1H NMR(600MHz,CDCl3)δ7.89(dd,J＝5.5,3.1Hz,2H),7.75(dd,J＝5.5,3.1Hz,2H),3.76(q,J＝7.0Hz,6H),2.89(t,J＝7.3Hz,2H),1.74–1.63(m,2H),1.15(t,J＝7.0Hz,9H),0.80–0.74(m,2H).13C NMR(150MHz,CDCl3) δ 168.54,134.61,132.21,123.87,58.48,41.52,22.08,18.34,9.43.ESI-MS:406.1139, calculated as (M + Na): 406.1120, respectively; the reaction formula is shown as follows:
example 5
Under the atmosphere of inert gas and nitrogen, 5.56g (0.03mol) of phthalimide potassium salt is dissolved in 50mL of acetonitrile in a 250mL Schlenk bottle to prepare a solution with the concentration of 0.6mol/L, then the solution is placed in an ice water bath (0 ℃), 9.83g (0.036mol) of triethoxysilylpropyl sulfenyl chloride is dripped into the solution system, the solution is placed at room temperature after the dripping, the molar ratio is 1.2:1, the magneton rotating speed is 600r/min, the reaction time is 10h, and the reaction progress is tracked by TLC detection. After the reaction is finished, filtering to remove potassium chloride, removing the solvent by using a rotary evaporator, and then performing column chromatography separation by using 400-mesh silica gel powder, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 10: 1-8: 1, so that 3.5g of the compound is obtained. The compounds were characterized using nuclear magnetic resonance spectroscopy and high resolution mass spectroscopy with the following data:1H NMR(600MHz,CDCl3)δ7.89(dd,J＝5.5,3.1Hz,2H),7.75(dd,J＝5.5,3.1Hz,2H),3.76(q,J＝7.0Hz,6H),2.89(t,J＝7.3Hz,2H),1.74–1.63(m,2H),1.15(t,J＝7.0Hz,9H),0.80–0.74(m,2H).13C NMR(150MHz,CDCl3) δ 168.54,134.61,132.21,123.87,58.48,41.52,22.08,18.34,9.43.ESI-MS:406.1139, calculated as (M + Na): 406.1120, respectively; the reaction formula of the above reaction is shown below:
example 6
11.31g (0.1mol) of glutarimide was dissolved in 125mL of methylene chloride in a 250mL Schlenk flask under an inert gas nitrogen atmosphere to prepare a solution having a concentration of 0.8mol/L, 20.85mL (0.15mol) of triethylamine was added, and the solution was placed in an ice-water bath (0 ℃ C.), and 32.75g (0.12mol) of triethoxysilylpropylmethanesulfonyl chloride was addedDropwise adding into the solution system, standing to room temperature after dropwise adding, wherein the molar ratio is 1.2:1, the magneton rotation speed is 600r/min, the reaction time is 12h, and detecting and tracking the reaction process by TLC. After the reaction is finished, filtering to remove triethylamine hydrochloride, removing a solvent by using a rotary evaporator, and then performing column chromatography separation by using 400-mesh silica gel powder, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 8: 1-4: 1, so that 18.5g of the compound is obtained. Compounds were characterized by nmr spectroscopy and high resolution mass spectroscopy with the following data:1H NMR(600MHz,CDCl3)δ3.63(q,J＝7.0Hz,6H),2.69(t,J＝7.3Hz,2H),2.44–2.22(m,4H),2.20–2.05(m,2H),1.53–1.41(m,2H),1.04(t,J＝7.0Hz,9H),0.63–0.55(m,2H).13C NMR(150MHz,CDCl3) δ 175.18,58.14,40.12,32.14,21.65,19.15,18.05,9.10 ESI-MS:372.1271, calculated as (M + Na): 372.1277, respectively; the reaction formula of the above reaction is shown below:
example 7
Under the atmosphere of inert gas nitrogen, 15.32g (0.1mol) of hexahydrophthalimide is dissolved in 150mL of dichloromethane in a 500mL Schlenk bottle to prepare a solution with the concentration of 0.67mol/L, 20.85mL (0.15mol) of triethylamine is added, then the solution is placed in an ice water bath (0 ℃), 32.75g (0.12mol) of triethoxysilylpropyl sulfenyl chloride is dropwise added into the solution system, the solution is placed at room temperature after the dropwise addition, the molar ratio is 1.2:1, the rotation speed of magnetons is 700r/min, the reaction time is 10h, and the reaction progress is tracked through TLC detection. And after the reaction is finished, filtering to remove triethylamine hydrochloride, removing the solvent by using a rotary evaporator, and performing column chromatography separation by using 400-mesh silica gel powder, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 10: 1-5: 1, so that 19g of the compound is obtained. Compounds were characterized by nmr spectroscopy and high resolution mass spectroscopy with the following data:1H NMR(600MHz,CDCl3)δ3.62(q,J＝7.0Hz,6H),2.80–2.70(m,2H),2.68(t,J＝7.3Hz,2H),1.65–1.30(m,10H),1.03(t,J＝7.0Hz,9H),0.63–0.53(m,2H).13C NMR(150MHz,CDCl3)δ178.85,58.12,42.05,40.10,24.38,23.13,21.64,18.04,9.10.ESI-MS:412.1581, calculated as (M + Na): 412.1590, respectively; the reaction formula is shown as follows:
example 8
Under the atmosphere of inert gas and nitrogen, 17.52g (0.1mol) of 4, 7-dimethyl phthalimide is dissolved in 200mL of dichloromethane to prepare a solution with the concentration of 0.5mol/L in a 500mL Schlenk bottle, 20.85mL (0.15mol) of triethylamine is added, then the solution is placed in an ice water bath (0 ℃), 32.75g (0.12mol) of triethoxysilylpropyl sulfenyl chloride is dropwise added into the solution system, the solution is placed at room temperature after the dropwise addition, the molar ratio is 1.2:1, the rotation speed of magnetons is 800r/min, the reaction time is 12h, and the reaction progress is followed by TLC detection. And after the reaction is finished, filtering to remove triethylamine hydrochloride, removing the solvent by using a rotary evaporator, and performing column chromatography separation by using 400-mesh silica gel powder, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 12: 1-8: 1, so as to obtain 16g of the compound. The compounds were characterized using nuclear magnetic resonance spectroscopy and high resolution mass spectroscopy with the following data:1H NMR(600MHz,CDCl3)δ7.62(d,J＝5.6Hz,2H),3.74(q,J＝7.0Hz,6H),2.86(t,J＝7.3Hz,2H),2.53(s,6H),1.69–1.61(m,2H),1.13(t,J＝7.0Hz,9H),0.78–0.68(m,2H).13CNMR(150MHz,CDCl3) δ 167.86,148.12,137.34,135.69,58.44,41.45,22.03,20.13,18.31,9.40.ESI-MS:434.1430, calculated as (M + Na): 434.1433, respectively; the reaction formula is shown as follows:
example 9
5.06g (0.05mol) of diacetylamine was dissolved in 80mL of dichloromethane in a 250mL Schlenk flask under an inert gas nitrogen atmosphere to prepare a solution having a concentration of 0.63mol/L, 10.43mL (0.075mol) of triethylamine was added, and the solution was placed in an ice-water bath (0 ℃ C.), and 16.38g (0.06mol) of triethoxysilylpropylsulfenyl chloride was droppedAdding into solution system, standing to room temperature after dripping, the molar ratio is 1.2:1, the magneton rotation speed is 600r/min, the reaction time is 10h, and detecting and tracking the reaction process by TLC. And after the reaction is finished, filtering to remove triethylamine hydrochloride, removing the solvent by using a rotary evaporator, and performing column chromatography separation by using 400-mesh silica gel powder, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 15: 1-6:1, so as to obtain 10g of the compound. The compounds were characterized using nuclear magnetic resonance spectroscopy and high resolution mass spectroscopy with the following data:1H NMR(600MHz,CDCl3)δ3.60(q,J＝7.0Hz,6H),2.68(t,J＝7.3Hz,2H),2.42(s,6H),1.52-1.41(m,2H),1.03(t,J＝7.1Hz,9H),0.65-0.54(m,2H).13C NMR(150MHz,CDCl3) δ 174.67,58.15,40.13,27.26,21.67,18.07,9.11.ESI-MS:360.1273, calculated as (M + Na): 360.1277, respectively; the reaction formula is shown as follows:
the coupling agent compound obtained in the embodiments 6 to 9 can enhance the interaction between the polymer and the filler, reduce the hysteresis loss of the rubber material, reduce the heat generation, reduce the Payne effect of the rubber material, and improve the dispersibility of the white carbon black, thereby reducing the oil consumption and the emission of carbon dioxide in the running process of the tire and enhancing the wear resistance of the tire; meanwhile, the imide-terminated mercaptosilane coupling agent provided by the invention can prolong the scorching time of the rubber material and improve the processing safety of the rubber material, and the effect data are not repeated.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. An imide-group-terminated mercaptosilane coupling agent has a structure shown in formula (I):
wherein, R is1Is selected from C1-C18An alkyl, aryl, cycloalkyl, alkenyl or alkynyl group of (a); the R is2、R3、R4At least one is hydrolyzable chlorine, bromine, alkoxy or ester group, the others are selected from hydrogen, alkyl, aryl or cycloalkyl; the R is5Selected from hydrogen, C1-C18The alkyl group of (1), substituted or unsubstituted aryl group, substituted or unsubstituted cycloalkyl group.
2. The imido-terminated mercaptosilane coupling agent of claim 1, wherein said coupling agent is selected from the group consisting of
3. The method for synthesizing the imido-terminated mercaptosilane coupling agent according to claim 1 or 2, wherein the imido-terminated mercaptosilane coupling agent is prepared by reacting a halogenated imide or an imide salt or an imide-based compound with a mercaptoalkylsilane compound or a corresponding sulfenyl chloride compound of mercaptoalkylsilane.
4. The method of claim 3, wherein the molar ratio of the haloimide or imide salt or imide-like compound to the mercaptoalkylsilane compound or the corresponding sulfenyl chloride compound of the mercaptoalkylsilane is from 1:1.0 to 1.2.
5. The method as claimed in claim 3, wherein the reaction is carried out by dissolving halogenated imide or imide salt or imide compound in organic solvent under inert gas atmosphere to obtain reaction solution with concentration of 0.4-0.8mol/L, dropping mercaptoalkylsilane compound or mercaptoalkylsilane corresponding sulfenyl chloride compound into the reaction solution, reacting at room temperature with magneton rotation speed of 500-800r/min and reaction time of 3-12 h.
6. The synthetic method of claim 3 or 5, wherein after the reaction is finished, the solvent of the reaction system is removed, and then column chromatography separation is carried out by using 400-mesh silica gel powder, the eluant system is petroleum ether and ethyl acetate, the gradient elution polarity selection range is 20:1-6:1, and finally the compound imido group-terminated mercaptosilane coupling agent is obtained.
7. The use of the imido-terminated mercaptosilane coupling agent of claim 1 in rubber compounding or vulcanization to increase the interaction force between rubber and filler, reduce hysteresis loss, extend scorch time of the compound, and increase safety of compound processing.
8. The use of claim 7, wherein: and (3) applying the imide-terminated mercaptosilane coupling agent to raw rubber isoprene rubber or butylbenzene/butadiene rubber, mixing, and vulcanizing to obtain vulcanized rubber.
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| CN114213728A (en) * | 2021-12-28 | 2022-03-22 | 青岛双星轮胎工业有限公司 | Preparation method of tire tread rubber composition and rubber composition |
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| CN114213728A (en) * | 2021-12-28 | 2022-03-22 | 青岛双星轮胎工业有限公司 | Preparation method of tire tread rubber composition and rubber composition |
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