CN108997409A - A method of reducing ethyl alcohol in polysulfide silanes coupling agent - Google Patents
A method of reducing ethyl alcohol in polysulfide silanes coupling agent Download PDFInfo
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- CN108997409A CN108997409A CN201810990460.1A CN201810990460A CN108997409A CN 108997409 A CN108997409 A CN 108997409A CN 201810990460 A CN201810990460 A CN 201810990460A CN 108997409 A CN108997409 A CN 108997409A
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- coupling agent
- ethyl alcohol
- polysulfide silanes
- silanes coupling
- reducing
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229920001021 polysulfide Polymers 0.000 title claims abstract description 68
- 239000005077 polysulfide Substances 0.000 title claims abstract description 68
- 150000008117 polysulfides Polymers 0.000 title claims abstract description 68
- 150000004756 silanes Chemical class 0.000 title claims abstract description 64
- 235000019441 ethanol Nutrition 0.000 title claims abstract description 59
- 239000007822 coupling agent Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 239000003292 glue Substances 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 5
- 238000012805 post-processing Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 12
- 125000005909 ethyl alcohol group Chemical group 0.000 description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000000945 filler Substances 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000010074 rubber mixing Methods 0.000 description 2
- 239000000126 substance Substances 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- OGFYGJDCQZJOFN-UHFFFAOYSA-N [O].[Si].[Si] Chemical compound [O].[Si].[Si] OGFYGJDCQZJOFN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The present invention provides a kind of methods of ethyl alcohol in reduction polysulfide silanes coupling agent, first by polysulfide silanes coupling agent, C5‑C8Pure and mild supported alumina catalyst is reacted, to which the ethyl alcohol in polysulfide silanes coupling agent be steamed, be evaporated under reduced pressure after reaction to no fraction flow out, this part operation can by polysulfide silanes coupling agent remaining ethyl alcohol and unreacted C5‑C8Alcohol steams, and finally cools down, and filters to get the polysulfide silanes coupling agent of ethyl alcohol is excluded.In the above method, on the one hand, supported alumina catalyst can promote polysulfide silanes coupling agent and C5‑C8The reaction of alcohol, so that the ethyl alcohol in polysulfide silanes coupling agent is largely replaced, to can be reduced the ethanol content in polysulfide silanes coupling agent, simultaneously because supported alumina catalyst is solid type catalyst, post-processing need to only be filtered.
Description
Technical field
The present invention relates to the methods for reducing ethanol content in silane coupling agent, and in particular to a kind of reduction polysulfide silicon
The method of ethyl alcohol in alkane coupling agent.
Background technique
Polysulfide silanes coupling agent is in sealed compound, casting metals part, colorant, protective coating, adhesive, pitch
Mixture and rubber chemicals etc. have a wide range of applications.It can improve between rubber and filler (such as carbon black, white carbon black)
Compatibility, improve the comprehensive performance of rubber product, be a kind of common rubber chemicals.By taking automobile tire as an example, polysulfide
The addition of silane coupling agent can significantly improve the performances such as anti-slippery, wearability and the heat generation of tire.Currently, automotive wheels
In tire industry, most popular polysulfide silanes coupling agent is double-[3- (triethoxysilicane) propyl]-tetrasulfide, should
Polysulfide silanes coupling agent is also known as Si-69, and polysulfide bond therein can participate in the vulcanization of rubber, and siloxy can be with filler
Surface reacts and is bonded, and plays the role of " molecular bridge " between filler and rubber.The wide more vulcanizations of other application
Object silane coupling agent further includes gamma-mercaptopropyltriethoxysilane and double-[3- (triethoxysilicane) propyl]-disulphide, this
Two kinds of polysulfide silanes coupling agents can play Si-69 similar effect.To sum up, polysulfide silanes coupling agent not only may be used
To realize that inoganic particle modified and graft polymers use in conjunction achievees the effect that be modified polymeric matrix, and
Its polysulfide bond can participate in the vulcanization of rubber, to improve the dynamic bending performance of rubber, thus become the hot spot of research and development.
But due to usually containing 6 ethyl alcohol groups in polysulfide silanes coupling agent molecule, in rubber mixing process
In, the filler (such as: White Carbon black) in polysulfide silanes coupling agent molecule in ethyl alcohol group and rubber reacts, and forms silicon-
Oxygen-silicon bound, ethyl alcohol are released, these ethyl alcohol released can cause to protrude during the further processing of rubber
The technical issues of, as it can make the porosity of rubber increase and generate in rubber body bubble；In addition, the second released
Alcohol brings serious harm to safety, labour health and environmental protection.
For this purpose, Chinese patent literature CN101318971A discloses a kind of method for reducing ethyl alcohol in polysulfide silanes,
It is by by polysulfide silanes and C5-C8It is reacted under the conditions of alcohol is existing for the titanate catalyst, thus ethyl alcohol
It steams in real time.The above method can reduce the ethanol content in polysulfide silanes, but since catalyst Ti acid esters terminates in reaction
After can inevitably remain in polysulfide silanes, to influence the comprehensive performance of rubber.In consideration of it, how to existing
Method improve, to overcome the deficiencies of existing technologies, this is technology urgently to be resolved to those skilled in the art
Problem.
Summary of the invention
The technical problems to be solved by the invention are to overcome in existing reduction polysulfide silanes in the method for ethyl alcohol,
The defect that remaining catalyst has an impact the comprehensive performance of rubber, and then it is even to provide a kind of reduction polysulfide silanes
Join the method for ethyl alcohol in agent.
The present invention solves the technical solution that above-mentioned technical problem uses are as follows:
First aspect present invention provides a kind of method for reducing ethyl alcohol in polysulfide silanes coupling agent, including walks as follows
It is rapid:
(1) by polysulfide silanes coupling agent, C5-C8Pure and mild supported alumina catalyst is mixed to form reaction system simultaneously
It is reacted；
Wherein, the supported alumina catalyst the preparation method is as follows: prepare soluble metallic salt aqueous solution,
The aqueous solution is added in Aluminum sol, metal salt glue is obtained, and reducing agent water is added in the backward metal salt glue
Solution obtains active component precursor solution, using the active component precursor solution oxide impregnation aluminium ball type carrier, and
Dry afterwards, roasting, obtains the supported alumina catalyst.
(2) by the step (1) reaction system after reaction in -0.10~-0.01MPa, 90 DEG C~130 DEG C
At a temperature of vacuum distillation to no fraction flow out, be cooled to -15 DEG C~0 DEG C, filtering.
Preferably, in the step (1), the temperature of the reaction system is 70~85 DEG C, preferably 75~80 DEG C, when reaction
Between be 3~4h, preferably 3.5h；The polysulfide silanes coupling agent and the C5-C8The molar ratio of alcohol is 1:(3~5), preferably
1:(4~4.5)；The ethyl alcohol generated during the reaction is distilled out of at any time.
Preferably, in the step (1), the C5-C8Alcohol is 2-Ethylhexyl Alcohol, amylalcohol or hexanol.
In the preparation method of the supported alumina catalyst, the reducing agent is hydrazine hydrate or formaldehyde；The reduction
The mass concentration of reducing agent is 1g/L~30g/L, preferably 10~20g/L in agent aqueous solution；The soluble metallic salt with it is described
The molar ratio of reducing agent is 1:(1.5~2.5).
In the preparation method of the supported alumina catalyst, the aluminium oxide ball type carrier institute of unit mass part
The parts by volume of the active component precursor solution needed is 1~5, preferably 2~3；
The relationship of the mass parts and the parts by volume is g/mL.
In the preparation method of the supported alumina catalyst, the active component is calculated as platinum or palladium with metal.
In the preparation method of the supported alumina catalyst, the quality hundred of soluble metallic salt in the aqueous solution
Dividing content is 3~20%, preferably 8~15%.
In the preparation method of the supported alumina catalyst, the mass ratio of the aqueous solution and the Aluminum sol
For 1:(5~10), preferred 1:(6~9).
In the preparation method of the supported alumina catalyst, drying temperature be 70~95 DEG C, preferably 80~90 DEG C,
Time is 1~3h；Maturing temperature is 300~500 DEG C, and preferably 350~450 DEG C, the time is 2~4h.
Second aspect of the present invention provides a kind of above method in the use for reducing the ethyl alcohol in polysulfide silanes coupling agent
On the way.
Above-mentioned technical proposal of the invention has the advantages that
1, the method for the present invention for reducing ethyl alcohol in polysulfide silanes coupling agent, first by polysulfide silanes
Coupling agent, C5-C8Pure and mild supported alumina catalyst is reacted, so that the ethyl alcohol in polysulfide silanes coupling agent be steamed
Out, it is evaporated under reduced pressure to no fraction and is flowed out after reaction, this part operation can will be in polysulfide silanes coupling agent
Remaining ethyl alcohol and unreacted C5-C8Alcohol steams, and finally cools down, and filters to get the polysulfide silanes coupling of ethyl alcohol is excluded
Agent.In the above method, on the one hand, supported alumina catalyst can promote polysulfide silanes coupling agent and C5-C8Alcohol it is anti-
It answers, so that the ethyl alcohol in polysulfide silanes coupling agent is largely replaced, to can be reduced polysulfide silanes coupling agent
In ethanol content, simultaneously because supported alumina catalyst be solid type catalyst, post-processing only need to filter.Through
Measurement, the content more as little as 97% or more of the ethyl alcohol group through the method for the present invention treated polysulfide silanes coupling agent,
Ethyl alcohol is hardly released in rubber mixing process, is conducive to the health and environmental protection of operator, is improved rubber
The safety of glue calendering process；On the other hand, in precursor solution on the one hand the presence of Aluminum sol can prevent metal active constituent
It is spread to carrier inside, so that metal is as much as possible to be supported on carrier shell layer surface, and then improves the benefit of active component
With rate, the catalytic efficiency of catalyst is improved.
Specific embodiment
Technical solution of the present invention will be clearly and completely described below, it is clear that described embodiment is this
Invention a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
Every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.This
Outside, technical characteristic involved in invention described below different embodiments is as long as they do not conflict with each other
It can be combined with each other.
Embodiment 1
The method provided in this embodiment for reducing ethyl alcohol in polysulfide silanes coupling agent, includes the following steps:
The preparation of supported alumina catalyst:
The palladium nitrate aqueous solution that mass percentage is 20% is prepared, above-mentioned palladium nitrate aqueous solution is then added to aluminium
It is uniformly mixed in colloidal sol, obtains metal salt glue, and the hydrazine hydrate that mass concentration is 1g/L is added in the backward metal salt glue
Aqueous solution obtains active component precursor solution, wherein and the mass ratio of above-mentioned palladium nitrate aqueous solution and Aluminum sol is 1:5, on
The molar ratio for stating palladium nitrate and hydrazine hydrate is 1:2.5, obtains active component precursor solution；
It takes 10g aluminium oxide spherical shape carrier impregnation in the above-mentioned active component precursor solution of 10mL, impregnates 3 times, impregnate every time
Time is 1h, and naturally dry, through 300 DEG C of roasting 4h, obtains supported alumina catalyst after 70 DEG C of dry 1.0h；
Reduce ethyl alcohol in polysulfide silanes coupling agent
538g (1mol) bis- (triethoxies are added in the three-necked flask equipped with blender, thermometer and distiller condenser
Propyl) tetrasulfide, 650g (5.0mol) 2-Ethyl Hexanol and 1g supported alumina catalyst formation reaction system, by this
Reaction system reacts 3h at 85 DEG C, and the ethyl alcohol in reaction process is steamed at any time, stops reaction, then true in -0.01MPa
It is empty, be evaporated under reduced pressure to no fraction at a temperature of 130 DEG C and flowed out, be then cooled to -15 DEG C, stand overnight, filter, obtain
To the polysulfide silanes coupling agent for reducing ethanol content, through detecting, the content of ethyl alcohol group in polysulfide silanes coupling agent
Less 97%.
Embodiment 2
The method provided in this embodiment for reducing ethyl alcohol in polysulfide silanes coupling agent, includes the following steps:
The preparation of supported alumina catalyst:
The palladium nitrate aqueous solution that mass percentage is 3% is prepared, it is molten that above-mentioned palladium nitrate aqueous solution is then added to aluminium
It is uniformly mixed in glue, obtains metal salt glue, and the formalin that mass concentration is 30g/L is added in the backward metal salt glue
Solution obtains active component precursor solution, wherein the mass ratio of above-mentioned palladium nitrate aqueous solution and Aluminum sol is 1:10, above-mentioned
The molar ratio of palladium nitrate and formaldehyde is 1:1.5, obtains active component precursor solution；
It takes 10g aluminium oxide spherical shape carrier impregnation in the above-mentioned active component precursor solution of 50mL, impregnates 3 times, impregnate every time
Time is 1h, and naturally dry, through 500 DEG C of roasting 2h, obtains supported alumina catalyst after 95 DEG C of dry 1.0h；
Reduce ethyl alcohol in polysulfide silanes coupling agent
474g (1mol) bis- (triethoxies are added in the three-necked flask equipped with blender, thermometer and distiller condenser
Propyl) disulphide, 264g (3mol) amylalcohol and 1g supported alumina catalyst formation reaction system, by the reaction system
4h is reacted at 70 DEG C, the ethyl alcohol in reaction process is steamed at any time, stop reaction, then in -0.10MPa vacuum, 90 DEG C
At a temperature of be evaporated under reduced pressure to no fraction flow out, be then cooled to 0 DEG C, stand overnight, filter, be reduced ethyl alcohol and contain
The polysulfide silanes coupling agent of amount, through detecting, the content of ethyl alcohol group less 99% in polysulfide silanes coupling agent.
Embodiment 3
The method provided in this embodiment for reducing ethyl alcohol in polysulfide silanes coupling agent, includes the following steps:
The preparation of supported alumina catalyst:
The palladium nitrate aqueous solution that mass percentage is 8% is prepared, it is molten that above-mentioned palladium nitrate aqueous solution is then added to aluminium
It is uniformly mixed in glue, obtains metal salt glue, and the formalin that mass concentration is 20g/L is added in the backward metal salt glue
Solution obtains active component precursor solution, wherein the mass ratio of above-mentioned palladium nitrate aqueous solution and Aluminum sol is 1:9, above-mentioned
The molar ratio of palladium nitrate and formaldehyde is 1:2.0, obtains active component precursor solution；
It takes 10g aluminium oxide spherical shape carrier impregnation in the above-mentioned active component precursor solution of 20mL, impregnates 3 times, impregnate every time
Time is 1h, and naturally dry, through 450 DEG C of roasting 3h, obtains supported alumina catalyst after 80 DEG C of dry 2.0h；
Reduce ethyl alcohol in polysulfide silanes coupling agent
538g (1mol) bis- (triethoxies are added in the three-necked flask equipped with blender, thermometer and distiller condenser
Propyl) tetrasulfide, 219.7g (4.0mol) hexanol and 1g supported alumina catalyst formation reaction system, by the reaction
System reacts 3.5h at 75 DEG C, and the ethyl alcohol in reaction process is steamed at any time, stop reaction, then in -0.05MPa vacuum,
It is evaporated under reduced pressure at a temperature of 100 DEG C to no fraction and is flowed out, be cooled to -5 DEG C, stand overnight, filtered, be reduced second
The polysulfide silanes coupling agent of alcohol content, through detecting, the content of ethyl alcohol group is less in polysulfide silanes coupling agent
98%.
Embodiment 4
The method provided in this embodiment for reducing ethyl alcohol in polysulfide silanes coupling agent, includes the following steps:
The preparation of supported alumina catalyst:
The platinum nitrate aqueous solution that mass percentage is 15% is prepared, above-mentioned platinum nitrate aqueous solution is then added to aluminium
It is uniformly mixed in colloidal sol, obtains metal salt glue, and the hydration that mass concentration is 10g/L is added in the backward metal salt glue
Hydrazine aqueous solution obtains active component precursor solution, wherein and the mass ratio of above-mentioned platinum nitrate aqueous solution and Aluminum sol is 1:6,
The molar ratio of above-mentioned platinum nitrate and hydrazine hydrate is 1:1.8, obtains active component precursor solution；
It takes 10g aluminium oxide spherical shape carrier impregnation in the above-mentioned active component precursor solution of 30mL, impregnates 3 times, impregnate every time
Time is 1h, and naturally dry, through 350 DEG C of roasting 3.5h, obtains supported alumina catalyst after 90 DEG C of dry 2.5h；
Reduce ethyl alcohol in polysulfide silanes coupling agent
474g (1mol) bis- (triethoxies are added in the three-necked flask equipped with blender, thermometer and distiller condenser
Propyl) disulphide, 396g (4.5mol) amylalcohol and 1.5g supported alumina catalyst formation reaction system, by the reaction
System reacts 3.5h at 80 DEG C, and the ethyl alcohol in reaction process is steamed at any time, stop reaction, then in -0.08MPa vacuum,
It is evaporated under reduced pressure at a temperature of 110 DEG C to no fraction and is flowed out, be cooled to -10 DEG C, stand overnight, filtered, be reduced second
The polysulfide silanes coupling agent of alcohol content, through detecting, the content of ethyl alcohol group is less in polysulfide silanes coupling agent
99.5%.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.
For those of ordinary skill in the art, other various forms of changes can also be made on the basis of the above description
Change or changes.There is no necessity and possibility to exhaust all the enbodiments.And obvious change extended from this
Change or changes still within the protection scope of the invention.
Claims (10)
1. a kind of method for reducing ethyl alcohol in polysulfide silanes coupling agent, which comprises the steps of:
(1) by polysulfide silanes coupling agent, C5-C8Pure and mild supported alumina catalyst is mixed to form reaction system and carries out
Reaction；
Wherein, the supported alumina catalyst the preparation method is as follows: prepare the aqueous solution of soluble metallic salt, will be described
Aqueous solution is added in Aluminum sol, obtains metal salt glue, and reducing agent aqueous solution is added in the backward metal salt glue, is obtained
To active component precursor solution, using the active component precursor solution oxide impregnation aluminium ball type carrier, then dry, roasting
It burns, obtains the supported alumina catalyst.
(2) by the step (1) reaction system after reaction at a temperature of -0.10~-0.01MPa, 90 DEG C~130 DEG C
Vacuum distillation to no fraction flows out, and is cooled to -15 DEG C~0 DEG C, filtering.
2. the method according to claim 1 for reducing ethyl alcohol in polysulfide silanes coupling agent, which is characterized in that the step
Suddenly in (1),
The temperature of the reaction system is 70~85 DEG C, and the reaction time is 3~4h；
The polysulfide silanes coupling agent and the C5-C8The molar ratio of alcohol is 1:(3~5)；
The ethyl alcohol generated during the reaction is distilled out of at any time.
3. the method according to claim 1 or 2 for reducing ethyl alcohol in polysulfide silanes coupling agent, which is characterized in that institute
It states in step (1), the C5-C8Alcohol is 2-Ethylhexyl Alcohol, amylalcohol or hexanol.
4. the method according to claim 1 for reducing ethyl alcohol in polysulfide silanes coupling agent, which is characterized in that described negative
In the preparation method of load type aluminium oxide catalyst,
The reducing agent is hydrazine hydrate or formaldehyde；The mass concentration of reducing agent is 1g/L~30g/L in the reducing agent aqueous solution；
The molar ratio of the soluble metallic salt and the reducing agent is 1:(1.5~2.5).
5. the method according to claim 1 for reducing ethyl alcohol in polysulfide silanes coupling agent, which is characterized in that described negative
In the preparation method of load type aluminium oxide catalyst, the active component needed for the aluminium oxide ball type carrier of unit mass part
The parts by volume of precursor solution is 1~5；
The relationship of the mass parts and the parts by volume is g/mL.
6. the method according to claim 5 for reducing ethyl alcohol in polysulfide silanes coupling agent, which is characterized in that described negative
In the preparation method of load type aluminium oxide catalyst, the active component is calculated as platinum or palladium with metal.
7. the method according to claim 1 for reducing ethyl alcohol in polysulfide silanes coupling agent, which is characterized in that described negative
In the preparation method of load type aluminium oxide catalyst, the mass percentage of soluble metallic salt is 3~20% in the aqueous solution.
8. the method according to claim 1 for reducing ethyl alcohol in polysulfide silanes coupling agent, which is characterized in that described negative
In the preparation method of load type aluminium oxide catalyst, the mass ratio of the aqueous solution and the Aluminum sol is 1:(5~10).
9. the method according to claim 1 for reducing ethyl alcohol in polysulfide silanes coupling agent, which is characterized in that described negative
In the preparation method of load type aluminium oxide catalyst, drying temperature is 70~95 DEG C, and the time is 1~3h；Maturing temperature be 300~
500 DEG C, the time is 2~4h.
10. the described in any item methods of claim 1-9 are in the purposes for reducing the ethyl alcohol in polysulfide silanes coupling agent.
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