CN109320542A - Double kettles series connection synthetic method of the silane coupling agent of the propyl containing mercapto - Google Patents
Double kettles series connection synthetic method of the silane coupling agent of the propyl containing mercapto Download PDFInfo
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- CN109320542A CN109320542A CN201811344626.9A CN201811344626A CN109320542A CN 109320542 A CN109320542 A CN 109320542A CN 201811344626 A CN201811344626 A CN 201811344626A CN 109320542 A CN109320542 A CN 109320542A
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- reaction kettle
- coupling agent
- silane coupling
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- propyl
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- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 24
- 238000010189 synthetic method Methods 0.000 title claims abstract description 19
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 title claims abstract description 18
- 125000003396 thiol group Chemical class [H]S* 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 127
- 239000007788 liquid Substances 0.000 claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000007789 gas Substances 0.000 claims abstract description 39
- 235000019441 ethanol Nutrition 0.000 claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 13
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- -1 γ-chloropropyl Chemical group 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000077 silane Inorganic materials 0.000 claims abstract description 5
- 239000012530 fluid Substances 0.000 claims description 17
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 14
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 10
- 239000000112 cooling gas Substances 0.000 claims description 9
- DTOOTUYZFDDTBD-UHFFFAOYSA-N 3-chloropropylsilane Chemical compound [SiH3]CCCCl DTOOTUYZFDDTBD-UHFFFAOYSA-N 0.000 claims description 8
- AOAUDAYOMHDUEU-UHFFFAOYSA-N 3-silylpropane-1-thiol Chemical compound [SiH3]CCCS AOAUDAYOMHDUEU-UHFFFAOYSA-N 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 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 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 abstract description 3
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- 238000004821 distillation Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 7
- 239000007822 coupling agent Substances 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 4
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 4
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 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
Double kettles series connection synthetic method of the silane coupling agent of the propyl containing mercapto, it is related to the synthetic method of silane coupling agent.The technical issues of it is the method production cycle length that solve the silane coupling agent of existing synthesis propyl containing mercapto, low yield, pollution environment.This method: one, be equipped with synthesizer: the device includes two reaction kettles being connected in series by circulator, two sets of circulator and a filter；Two, vulcanized sodium and ethyl alcohol are added in first reaction kettle, and are passed through hydrogen chloride gas precursor reactant；Three, the silane containing γ-chloropropyl is added into reaction kettle to be synthesized；Four, that the gas in first reaction kettle is squeezed into second reaction kettle is spare；Five, liquid in first reaction kettle is squeezed into filter again and is filtered；Six, it is produced using second reaction kettle using operation identical with first reaction kettle；Seven, distillation is after filtrate adjusts pH value to get product.The product purity is 99.2%~99.5%, and yield is 89~91%.
Description
Technical field
The present invention relates to the synthetic methods of silane coupling agent.
Background technique
The silane coupling agent of the propyl containing mercapto in epoxy resin, polyurethane, polyester, butadiene-styrene rubber and natural rubber, to
The performance for improving the composite material as made from them can be used for glass fibre, deep-seated oil additionally as reinforcement and crosslinking accelerator
Ink, glue and sealing material.By taking gamma-mercaptopropyltriethoxysilane as an example, silane coupling agent is served not only as, it can be with
Can be with unsaturated bond addition reaction using sulfydryl the characteristics of, for developing silicone resin and some new rubbers with light-cured performance
Glue product.
The synthetic method of the silane coupling agent of the propyl containing mercapto has Thiourea-uv Method, NaHS synthetic method and bis- (alkoxies at present
Silicon substrate organic group) polysulfide cracking process.As disclosed in the Chinese patent application No. is 200710132081.0, pass through γ-
Chloropropyl triethoxysilane and thiocarbamide are in alcohol solvent, and using iodide as catalyst, ethylenediamine is that acid binding agent is synthesized
The silane coupling agent of mercapto propyl.This method is the disadvantage is that the reaction time is long, low yield, stink is big, pollutes environment.It is many in recent years to learn
Person is improved in above-mentioned technique, such as selects different catalyst and acid binding agent, although product purity and yield after improving
It increased, but not change the shortcomings that technique production cycle is long, solid waste is more, stink is big, pollution environment.Patent No.
The United States Patent (USP) of US3849471 proposes the ethylenediamine salt using hydrogen sulfide and reacting ethylenediamine synthesis hydrogen sulfide, in ethanol
With γ-chloropropyl triethoxysilane reaction synthesis gamma-mercaptopropyltriethoxysilane synthetic method.The disadvantage is that solid waste
More, safe operation requires height, operating environment poor.The Chinese patent of Patent No. 201510359710.8, with NaHS water
Solution is under phase transfer catalyst and γ-chloropropyl triethoxysilane reaction synthesizes the conjunction of gamma-mercaptopropyltriethoxysilane
At method.Although these reactions have it is easy to operate, they the shortcomings that all clearly: (1) it is used in the synthesis process
Raw material γ-chloropropyl triethoxysilane and product gamma-mercaptopropyltriethoxysilane can all have in water phase generation hydrolysis,
The reaction such as polymerization, reduces the utilization rate and product yield of raw material；(2) rate-determining steps are cumbersome in reaction process, the operating time compared with
Length needs multiple sampling and testing, is unfavorable for process control；(3) product purity and yield is all relatively low, stability is poor；(4) it can produce
Raw a large amount of waste water, environmental pollution are big.
Summary of the invention
The present invention is to solve the production cycle of the synthetic method of the silane coupling agent of the existing propyl containing mercapto length, yield
It is low, pollution environment the technical issues of, and provide the propyl containing mercapto silane coupling agent double kettles series connection synthetic method.
Double kettles series connection synthetic method of the silane coupling agent of the propyl containing mercapto of the invention, sequentially includes the following steps:
One, be equipped with synthesizer: the synthesizer includes two reaction kettles, two sets of circulator and a filter；
The upper end of first reaction kettle is provided with feed opening, liquid inlet opening, exhaust outlet, sample tap；In the side wall of reaction kettle
Lower end is provided with air inlet, and the bottom of reaction kettle 1 is provided with leakage fluid dram；Liquid is provided on the pipeline connecting with liquid inlet opening
Body inlet valve and liquid feedstock flowmeter；Cooling gas check valve and control valve are provided on the pipeline connecting with air inlet；
The structure of second reaction kettle is identical as the structure of the first reaction kettle, that is, the upper end of the second reaction kettle is provided with charging
Mouth, liquid inlet opening, exhaust outlet, sample tap；The side wall lower ends of reaction kettle are provided with air inlet, are arranged in the bottom of reaction kettle
There is leakage fluid dram；Liquid feedstock valve and liquid feedstock flowmeter are provided on the pipeline connecting with liquid inlet opening；Connect with air inlet
Cooling gas check valve and control valve are provided on the pipeline connect；
First circulation device is made of gas circulator and circulation control valve；Second circulation device and first circulation device phase
Together, that is, second circulation device is made of gas circulator and circulation control valve；
The exhaust outlet of first reaction kettle is connected by gas circulator and circulation control valve with the air inlet of the second reaction kettle；
The exhaust outlet of second reaction kettle is connected by gas circulator and circulation control valve with the air inlet of the first reaction kettle；
The top of filter is provided with feed inlet, and lower part is provided with discharge port, and top is additionally provided with equilibrated valve；
The feed inlet connection of the leakage fluid dram and filter of two reaction kettles；
Two, according to anhydrous sodium sulfide and ethyl alcohol mass ratio 1:(9~10) ratio be made into anhydrous sodium sulfide ethanol solution, so
Afterwards by feed opening 2 be added the first reaction kettle 1 in, after being warming up to 50~65 DEG C of 25~30min of uniform stirring, through air inlet 6 to
In first reaction kettle 1 with the speed of (4.5~5) g/min be passed through hydrogen chloride gas until kettle in the pH value of solution reach 8~9,
Stopping is passed through hydrogen chloride gas；
Three, after the temperature that the first reaction kettle 1 is warming up to solution being reached 80~90 DEG C, under agitation, through liquid into
Material mouth 3 is added dropwise containing γ-chloropropyl silane；After being added dropwise, it is further heated up to 90~93 DEG C to be reacted, from sample tap 5
Sample detection, when the mass percentage of the silane containing γ-chloropropyl in sample is less than 2% and containing γ-mercapto propyl silane idol
Join agent mass percentage >=95% when stop reaction, be cooled to room temperature；
It is wherein γ-chloropropyl triethoxysilane or γ-r-chloropropyl trimethoxyl silane containing γ-chloropropyl silane；
Four, the gas circulator 12 and circulation control valve 13 for opening first circulation device, by the gas in the first reaction kettle 1
It squeezes into spare in the second reaction kettle 1 '；
Five, the leakage fluid dram 7 for opening the first reaction kettle 1, the liquid in the first reaction kettle 1 is put into filter 14 and is filtered；
Six, the second reaction kettle 1 ' and second circulation device is recycled to repeat step 2 to step 5, two covering devices are alternately given birth to
It produces；
Seven, after being adjusted to neutrality the pH value of filtrate obtained in filter 14, ethyl alcohol is evaporated off in first normal pressure, then depressurizes steaming
It evaporates, obtains containing γ-mercapto propyl silane coupling agent.
Reaction principle of the invention is described as follows for synthesizing γ-chloropropyl triethoxysilane: utilizing γ-chlorine third
The removing of group (- Cl) in ethyl triethoxy silicane alkane and the substitution reaction of mercapto groups (- HS), essence are negatively charged originals
Son group replaces halogen atom.Its reaction equation is as follows:
Advantages of the present invention is as follows:
1, the suck-back that cooling gas check valve feed pipe prevents reaction solution is provided in novel reaction device；Pass through anhydrous sulphur
Change sodium and HCl gas reacts in ethanol solution, so that anhydrous sodium sulfide is converted into anhydrous sodium hydrosulfide to the maximum extent, pass through
Suitable material is arranged, and when reaction temperature and time, conversion ratio should reach 98.5% or more；
2, concatenated reaction kettle can utilize reaction raw materials hydrogen chloride to a greater extent；
3, what organic method synthesized generates without waste water, safety and environmental protection；
4, sour gas hydrogen sulfide used can be recycled after collecting when producing anhydrous sodium hydrosulfide；
5, at low cost, product purity is up to 99.2%~99.5%, and product yield is yield 89~91%, while product matter
Amount is stablized.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of synthesizer of the invention.
Specific embodiment
The synthetic method specific embodiment 1: double kettles of the silane coupling agent of the propyl containing mercapto of present embodiment are connected, is pressed
Following steps carry out:
One, be equipped with synthesizer: the synthesizer includes two reaction kettles, two sets of circulator and a filter；
The upper end of first reaction kettle 1 is provided with feed opening 2, liquid inlet opening 3, exhaust outlet 4, sample tap 5；In reaction kettle 1
Side wall lower ends be provided with air inlet 6, the bottom of reaction kettle 1 is provided with leakage fluid dram 7；
Liquid feedstock valve 8 and liquid feedstock flowmeter 9 are provided on the pipeline connecting with liquid inlet opening 3；
Cooling gas check valve 10 and control valve 11 are provided on the pipeline connecting with air inlet 6；
The structure of second reaction kettle is identical as the first reaction kettle, that is, the upper end of the second reaction kettle 1 ' be provided with feed opening 2 ',
Liquid inlet opening 3 ', exhaust outlet 4 ', sample tap 5 '；The side wall lower ends of reaction kettle 1 ' are provided with air inlet 6 ', in reaction kettle 1 '
Bottom be provided with leakage fluid dram 7 '；
Liquid feedstock valve 8 ' and liquid feedstock flowmeter 9 ' are provided on the pipeline connecting with liquid inlet opening 3 '；
Cooling gas check valve 10 ' and control valve 11 ' are provided on the pipeline connecting with air inlet 6 '；
First circulation device is made of gas circulator 12 and circulation control valve 13；Second circulation device and first circulation fill
It sets identical, that is, second circulation device is made of gas circulator 12 ' and circulation control valve 13 '；
The exhaust outlet 4 of first reaction kettle 1 by gas circulator 12 and circulation control valve 13 and the second reaction kettle 1 ' into
Port 6 ' is connected；
The exhaust outlet 4 ' of second reaction kettle 1 ' passes through gas circulator 12 ' and circulation control valve 13 ' and the first reaction kettle 1
Air inlet 6 is connected；
The top of filter 14 is provided with feed inlet 15, and lower part is provided with discharge port 16, and top is additionally provided with pressure balance
Valve 17；
The connection of feed inlet 15 of the leakage fluid dram and filter of two reaction kettles；
Two, according to anhydrous sodium sulfide and ethyl alcohol mass ratio 1:(9~10) ratio be made into anhydrous sodium sulfide ethanol solution, so
Afterwards by feed opening 2 be added the first reaction kettle 1 in, after being warming up to 50~65 DEG C of 25~30min of uniform stirring, through air inlet 6 to
In first reaction kettle 1 with the speed of 4.5~5g/min be passed through hydrogen chloride gas until kettle in the pH value of solution reach 8~9, stop
Only it is passed through hydrogen chloride gas；
Three, after the temperature that the first reaction kettle 1 is warming up to solution being reached 80~90 DEG C, under agitation, through liquid into
Material mouth 3 is added dropwise containing γ-chloropropyl silane；After being added dropwise, it is further heated up to 90~93 DEG C to be reacted, from sample tap 5
Sample detection, when mass percentage≤2% of the silane containing γ-chloropropyl in sample and containing γ-mercapto propyl it is silane coupled
Stop reaction when the mass percentage of agent >=95%, is cooled to room temperature；
Four, the gas circulator 12 and circulation control valve 13 for opening first circulation device, by the gas in the first reaction kettle 1
It squeezes into spare in the second reaction kettle 1 '；
Five, the leakage fluid dram 7 for opening the first reaction kettle 1, the liquid in the first reaction kettle 1 is put into filter 14 and is filtered；
Six, the second reaction kettle 1 ' and second circulation device is recycled to repeat step 2 to step 5, two covering devices are alternately given birth to
It produces；
Seven, after being adjusted to neutrality the pH value of filtrate obtained in filter 14, ethyl alcohol is evaporated off in first normal pressure, then depressurizes steaming
It evaporates, obtains containing γ-mercapto propyl silane coupling agent.
Specific embodiment 2: the present embodiment is different from the first embodiment in that in step 1, the first reaction kettle 1
Exhaust outlet 4 at be arranged exhaust-valve；Exhaust-valve is arranged in the 4 ' place of exhaust outlet of second reaction kettle 1 '.Other and specific embodiment one
It is identical.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that wherein described in step 2
Containing γ-chloropropyl silane be γ-chloropropyl triethoxysilane or γ-r-chloropropyl trimethoxyl silane.It is other with it is specific
Embodiment one or two is identical.
Specific embodiment 4: being added dropwise in step 2 unlike one of present embodiment and specific embodiment one to three
The molar ratio containing anhydrous sodium sulfide in γ-chloropropyl silane and step 1 be 1:(1~1.1).Other and specific embodiment party
One of formula one to three is identical.
Specific embodiment 5: unlike one of present embodiment and specific embodiment one to four described in step 7
Vacuum distillation be to be carried out under conditions of vacuum degree -0.095~-0.085MPa, temperature are 130~133 DEG C.It is other with
One of specific embodiment one to four is identical.
Beneficial effects of the present invention are verified with the following examples:
Embodiment 1: double kettles of the silane coupling agent of the propyl containing mercapto of the present embodiment are connected synthetic method, according to the following steps into
Row:
One, be equipped with synthesizer: the synthesizer includes two reaction kettles, two sets of circulator and a filter；
The upper end of first reaction kettle 1 is provided with feed opening 2, liquid inlet opening 3, exhaust outlet 4, sample tap 5；In reaction kettle 1
Side wall lower ends be provided with air inlet 6, the bottom of reaction kettle 1 is provided with leakage fluid dram 7；
Liquid feedstock valve 8 and liquid feedstock flowmeter 9 are provided on the pipeline connecting with liquid inlet opening 3；
Cooling gas check valve 10 and control valve 11 are provided on the pipeline connecting with air inlet 6；
The structure of second reaction kettle is identical as the first reaction kettle, that is, the upper end of the second reaction kettle 1 ' be provided with feed opening 2 ',
Liquid inlet opening 3 ', exhaust outlet 4 ', sample tap 5 '；The side wall lower ends of reaction kettle 1 ' are provided with air inlet 6 ', in reaction kettle 1 '
Bottom be provided with leakage fluid dram 7 '；
Liquid feedstock valve 8 ' and liquid feedstock flowmeter 9 ' are provided on the pipeline connecting with liquid inlet opening 3 '；
Cooling gas check valve 10 ' and control valve 11 ' are provided on the pipeline connecting with air inlet 6 '；
First circulation device is made of gas circulator 12 and circulation control valve 13；Second circulation device and first circulation fill
It sets identical, that is, second circulation device is made of gas circulator 12 ' and circulation control valve 13 '；
The exhaust outlet 4 of first reaction kettle 1 by gas circulator 12 and circulation control valve 13 and the second reaction kettle 1 ' into
Port 6 ' is connected；
The exhaust outlet 4 ' of second reaction kettle 1 ' passes through gas circulator 12 ' and circulation control valve 13 ' and the first reaction kettle 1
Air inlet 6 is connected；
The top of filter 14 is provided with feed inlet 15, and lower part is provided with discharge port 16, and top is additionally provided with pressure balance
Valve 17；
The connection of feed inlet 15 of the leakage fluid dram and filter of two reaction kettles；
Two, it is made into anhydrous sodium sulfide ethanol solution according to the ratio of anhydrous sodium sulfide and ethyl alcohol mass ratio 1:10, then led to
It crosses feed opening 2 to be added in the first reaction kettle 1, after being warming up to 50 DEG C of uniform stirring 30min, through air inlet 6 into the first reaction kettle 1
With the speed of 5g/min be passed through hydrogen chloride gas until kettle in the pH value of solution reach 8, stopping is passed through hydrogen chloride gas；
Three, after the temperature that the first reaction kettle 1 is warming up to solution being reached 80 DEG C, under agitation, through liquid inlet opening 3
γ-chloropropyl triethoxysilane is added dropwise；Wherein the molar ratio of γ-chloropropyl triethoxysilane and anhydrous sodium sulfide is 1:1；
After being added dropwise, it is further heated up to 92 DEG C to be reacted, and after reaction 3 hours, is sampled by sample tap 5, γ-in test sample
The mass percentage of chloropropyl triethoxysilane is the quality percentage of 2% and gamma-mercaptopropyltriethoxysilane coupling agent
Content is 95.5%, stops reaction, is cooled to room temperature；
Four, the gas circulator 12 and circulation control valve 13 for opening first circulation device, by the gas in the first reaction kettle 1
It squeezes into spare in the second reaction kettle 1 '；
Five, the leakage fluid dram 7 for opening the first reaction kettle 1, the liquid in the first reaction kettle 1 is put into filter 14 and is filtered；
Six, the second reaction kettle 1 ' and second circulation device is recycled to repeat step 2 to step 5, two covering devices are alternately given birth to
It produces；
Seven, after being adjusted to neutrality the pH value of filtrate obtained in filter 14, ethyl alcohol is evaporated off in first normal pressure, then in vacuum degree
It is evaporated under reduced pressure under conditions of being 133 DEG C for -0.095MPa, temperature, obtains gamma-mercaptopropyltriethoxysilane coupling agent.
The purity 99.5% of gamma-mercaptopropyltriethoxysilane coupling agent manufactured in the present embodiment；Yield 89.2%.
Embodiment 2: double kettles of the silane coupling agent of the propyl containing mercapto of the present embodiment are connected synthetic method, according to the following steps into
Row:
One, be equipped with synthesizer: the synthesizer is same as Example 1；
Two, it is made into anhydrous sodium sulfide ethanol solution according to the ratio of anhydrous sodium sulfide and ethyl alcohol mass ratio 1:10, then led to
It crosses feed opening 2 to be added in the first reaction kettle 1, after being warming up to 55 DEG C of uniform stirring 25min, through air inlet 6 into the first reaction kettle 1
With the speed of 4.5g/min be passed through hydrogen chloride gas until kettle in the pH value of solution reach 9, stopping is passed through hydrogen chloride gas；
Three, after the temperature that the first reaction kettle 1 is warming up to solution being reached 86 DEG C, under agitation, through liquid inlet opening 3
γ-r-chloropropyl trimethoxyl silane is added dropwise；Wherein the molar ratio of γ-r-chloropropyl trimethoxyl silane and vulcanized sodium is 1:1；It is added dropwise
After, it is further heated up to 93 DEG C to be reacted, and after reaction 3 hours, from 5 sample detection of sample tap, measures γ-chlorine in sample
The mass percentage of propyl trimethoxy silicane is the quality percentage of 1.8% and γ-mercaptopropyl trimethoxysilane coupling agent
Content is 99.5%, stops reaction, is cooled to room temperature；
Four, the gas circulator 12 and circulation control valve 13 for opening first circulation device, by the gas in the first reaction kettle 1
It squeezes into spare in the second reaction kettle 1 '；
Five, the leakage fluid dram 7 for opening the first reaction kettle 1, the liquid in the first reaction kettle 1 is put into filter 14 and is filtered；
Six, the second reaction kettle 1 ' and second circulation device is recycled to repeat step 2 to step 5, two covering devices are alternately given birth to
It produces；
Seven, after being adjusted to neutrality the pH value of filtrate obtained in filter 14, ethyl alcohol is evaporated off in first normal pressure, then in vacuum degree
It is evaporated under reduced pressure, then is evaporated under reduced pressure under conditions of being 133 DEG C for -0.095MPa, temperature, obtain γ-mercaptopropyl trimethoxysilane
Coupling agent.
The purity 99.5% of γ-mercaptopropyl trimethoxysilane coupling agent manufactured in the present embodiment；Yield 92%.
Claims (5)
- The synthetic method 1. double-reactor of the silane coupling agent of the propyl containing mercapto is connected, it is characterised in that this method according to the following steps into Row:One, be equipped with synthesizer: the synthesizer includes two reaction kettles, two sets of circulator and a filter；The upper end of first reaction kettle (1) is provided with feed opening (2), liquid inlet opening (3), exhaust outlet (4), sample tap (5)；Anti- It answers the side wall lower ends of kettle (1) to be provided with air inlet (6), the bottom of reaction kettle (1) is provided with leakage fluid dram (7)；With liquid feedstock Liquid feedstock valve (8) and liquid feedstock flowmeter (9) are provided on the pipeline of mouth (3) connection；The pipeline being connect with air inlet (6) On be provided with cooling gas check valve (10) and control valve (11)；The structure of second reaction kettle is identical as the structure of the first reaction kettle, that is, the upper end of the second reaction kettle (1 ') is provided with charging Mouth (2 '), liquid inlet opening (3 '), exhaust outlet (4 '), sample tap (5 ')；The side wall lower ends of reaction kettle (1 ') are provided with air inlet Mouth (6 '), is provided with leakage fluid dram (7 ') in the bottom of reaction kettle (1 ')；It is provided on the pipeline being connect with liquid inlet opening (3 ') Liquid feedstock valve (8 ') and liquid feedstock flowmeter (9 ')；Cooling gas check valve is provided on the pipeline connecting with air inlet (6 ') (10 ') and control valve (11 ')；First circulation device is made of gas circulator (12) and circulation control valve (13)；Second circulation device and first circulation fill It sets identical, that is, second circulation device is made of gas circulator (12 ') and circulation control valve (13 ')；The exhaust outlet (4) of first reaction kettle (1) passes through gas circulator (12) and circulation control valve (13) and the second reaction kettle The air inlet (6 ') of (1 ') is connected；The exhaust outlet (4 ') of second reaction kettle (1 ') passes through gas circulator (12 ') and loop control Valve (13 ') is connected with the air inlet (6) of the first reaction kettle (1)；The top of filter (14) is provided with feed inlet (15), and lower part is provided with discharge port (16), and it is flat that top is additionally provided with pressure It weighs valve (17)；Feed inlet (15) connection of the leakage fluid dram and filter of two reaction kettles；Two, according to anhydrous sodium sulfide and ethyl alcohol mass ratio 1:(9~10) ratio be made into anhydrous sodium sulfide ethanol solution, then lead to It crosses feed opening (2) to be added in the first reaction kettle (1), after being warming up to 50~65 DEG C of 25~30min of uniform stirring, through air inlet (6) To in the first reaction kettle (1) with the speed of 4.5~5g/min be passed through hydrogen chloride gas until kettle in solution pH value reach 8~ 9, stopping is passed through hydrogen chloride gas；Three, after the temperature that the first reaction kettle (1) is warming up to solution being reached 80~90 DEG C, under agitation, through liquid feedstock Mouth (3) is added dropwise containing γ-chloropropyl silane；After being added dropwise, it is further heated up to 90~93 DEG C to be reacted, from sample tap (5) sample detection, when mass percentage≤2% of the silane containing γ-chloropropyl in sample and containing γ-mercapto propyl silane idol Join agent mass percentage >=95% when stop reaction, be cooled to room temperature；Four, the gas circulator (12) and circulation control valve (13) for opening first circulation device, by the gas in the first reaction kettle (1) Body is squeezed into spare in the second reaction kettle (1 ')；Five, the leakage fluid dram (7) for opening the first reaction kettle (1), is put into mistake in filter (14) for the liquid in the first reaction kettle (1) Filter；Six, the second reaction kettle (1 ') and second circulation device is recycled to repeat step 2 to step 5, two covering devices alternately produce；Seven, after being adjusted to neutrality the pH value of filtrate obtained in filter (14), ethyl alcohol is evaporated off in first normal pressure, then is evaporated under reduced pressure, It obtains containing γ-mercapto propyl silane coupling agent.
- The synthetic method 2. double-reactor of the silane coupling agent of the propyl according to claim 1 containing mercapto is connected, feature exist In step 1, exhaust-valve is set at the exhaust outlet (4) of the first reaction kettle (1)；At the exhaust outlet (4 ') of second reaction kettle (1 ') Exhaust-valve is set.
- The synthetic method 3. double-reactor of the silane coupling agent of the propyl according to claim 1 or 2 containing mercapto is connected, feature It is in step 2 that wherein described is γ-chloropropyl triethoxysilane or γ-chloropropyl front three containing γ-chloropropyl silane Oxysilane.
- The synthetic method 4. double-reactor of the silane coupling agent of the propyl according to claim 1 or 2 containing mercapto is connected, feature It is that the molar ratio containing anhydrous sodium sulfide in γ-chloropropyl silane and step 1 being added dropwise in step 2 is 1:(1~1.1).
- The synthetic method 5. double-reactor of the silane coupling agent of the propyl according to claim 1 or 2 containing mercapto is connected, feature It is that vacuum distillation described in step 7 is in the item that vacuum degree is -0.095~-0.085MPa, temperature is 130~133 DEG C It is carried out under part.
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| CN112569868A (en) * | 2020-12-08 | 2021-03-30 | 长江大学 | Semi-open type crude oil multi-step cracking gas generation device and method |
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