CN114292291A - Solvent-free synthesis method of gamma-aminopropyl triethoxysilane - Google Patents
Solvent-free synthesis method of gamma-aminopropyl triethoxysilane Download PDFInfo
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000001308 synthesis method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 104
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- ABKFMURDLHTMLE-UHFFFAOYSA-N palladium;3-prop-2-enylidenecyclopentene Chemical compound [Pd].C=C[CH-]C1=CC=CC1 ABKFMURDLHTMLE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000004821 distillation Methods 0.000 claims description 223
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 212
- 239000007788 liquid Substances 0.000 claims description 88
- 239000000047 product Substances 0.000 claims description 82
- 239000012452 mother liquor Substances 0.000 claims description 68
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 51
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 48
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 42
- 238000005886 esterification reaction Methods 0.000 claims description 40
- 238000005086 pumping Methods 0.000 claims description 39
- 238000003860 storage Methods 0.000 claims description 39
- 238000004064 recycling Methods 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 32
- 239000012043 crude product Substances 0.000 claims description 30
- 230000032050 esterification Effects 0.000 claims description 30
- 238000010992 reflux Methods 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 22
- 229960001545 hydrotalcite Drugs 0.000 claims description 22
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 22
- 238000003825 pressing Methods 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000002309 gasification Methods 0.000 claims description 20
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 20
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 20
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 20
- 239000005052 trichlorosilane Substances 0.000 claims description 20
- 239000002699 waste material Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- -1 mercaptosiloxane Chemical class 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 15
- 238000005576 amination reaction Methods 0.000 claims description 13
- 239000006227 byproduct Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 235000019270 ammonium chloride Nutrition 0.000 claims description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 6
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 claims description 5
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 235000019441 ethanol Nutrition 0.000 description 63
- 239000000203 mixture Substances 0.000 description 31
- 238000001035 drying Methods 0.000 description 16
- 238000001914 filtration Methods 0.000 description 16
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 9
- YZBVIYJNUQVTTQ-UHFFFAOYSA-N 1-prop-2-enylpyrrolidine Chemical compound C=CCN1CCCC1 YZBVIYJNUQVTTQ-UHFFFAOYSA-N 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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Abstract
The invention relates to the technical field of fine chemical engineering, in particular to a solvent-free synthesis method of gamma-aminopropyl triethoxysilane; the invention provides a preparation method of a cocatalyst, and the addition of cyclopentadienyl allyl palladium and 1-allyl pyrrolidine-2-formamide in the cocatalyst is beneficial to improving the activity of the catalyst in a reaction system, and has the effect of absorbing moisture, so that the loss of raw materials can be reduced, and the product yield can be improved.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a solvent-free synthesis method of gamma-aminopropyltriethoxysilane.
Background
CN200910256074.0 discloses a method for synthesizing gamma-aminopropyl triethoxysilane, which comprises the following steps: (1) adding a toluene solution dissolved with a catalyst and gamma-chloropropyltriethoxysilane into a reaction kettle under a vacuum condition, and adding ammonia under a stirring state. Heating the materials in the reaction kettle to 60-70 ℃, wherein the reaction pressure is 0.5-3 MPa, and reacting for 4-7 h; (2) after the amination reaction is finished, filtering and separating to remove byproducts, and pumping filtrate into a distillation kettle; (3) after the temperature at the top of the distillation still is more than or equal to 102 ℃, the temperature of the materials in the distillation still is less than or equal to 80 ℃, the vacuum degree of reduced pressure distillation is more than or equal to 0.099MPa, and the gamma-aminopropyltriethoxysilane is obtained after reduced pressure distillation.
In the process of catalytically synthesizing gamma-chloropropyltrichlorosilane by using a traditional organosilicon catalyst, the following defects exist: (1) the reaction rate is low, the temperature is high, the pressure is high, and the energy consumption is large; (2) the loss of reaction raw materials is large, the product yield is low, and in addition, a large amount of solvents are used in the prior art, so the method does not meet the requirement of green chemistry.
Disclosure of Invention
In order to solve the problems, the invention discloses a solvent-free synthesis method of gamma-aminopropyl triethoxysilane, belonging to the technical field of fine chemical engineering.
A solvent-free synthesis method of gamma-aminopropyl triethoxysilane is characterized by comprising the following steps:
s1: according to the weight parts, 250 parts of trichlorosilane 180 and 150 parts of chloropropene 100 are pressed into a mixing tank by nitrogen from a storage tank, mixed and added into a synthesis reaction kettle by a high-level dropping tank, the reaction kettle is heated to 70-90 ℃ by jacket steam, and then 20-50x10 is added-5The catalyst and the cocatalyst are added in parts by weight, after the reaction is started, the reaction temperature is controlled to be 75-90 ℃, the reaction time is 1-4 hours, the reaction is filtered, the gamma-chloropropyl trichlorosilane crude product generated by the reaction is sent to a distillation still for normal pressure distillation, then the reduced pressure distillation is carried out to obtain the gamma-chloropropyl trichlorosilane product, and the finished product enters a product collection tank;
s2: pumping 150-200 parts of gamma-chloropropyltrichlorosilane into a metering tank, pumping 100-200 parts of ethanol into an ethanol overhead tank and an ethanol gasification tank from an ethanol storage tank, starting steam to heat the ethanol gasification tank, an ethanol buffer tank and an esterification tower kettle to 80-100 ℃ and 0.02-0.1MPa, feeding the gamma-chloropropyltrichlorosilane and ethanol into the top of an esterification tower through a pre-reactor, completing esterification reaction in the esterification tower to obtain gamma-chloropropyltriethoxysilane esterified liquid and hydrogen chloride gas, feeding the esterified liquid into an esterified liquid storage tank, collecting the produced hydrogen chloride to prepare trichlorosilane, pumping the esterified liquid into a distillation kettle, and performing reduced pressure distillation to obtain gamma-chloropropyltriethoxysilane;
s3: pumping 850 parts by weight of 700-plus-material gamma-chloropropyltriethoxysilane into a metering tank by a pump, metering, then feeding into an ammoniation kettle, adding 120 parts by weight of liquid ammonia of 100-plus-material for amination, controlling the temperature of 180-plus-material in the kettle and the pressure of 7-10MPa, obtaining a crude product of gamma-aminopropyltriethoxysilane and a byproduct ammonium chloride after the amination is finished, reacting for 3-6 hours, after the reaction is completed, pressing the kettle material into a stirring kettle for stirring, removing unreacted ammonia gas in the ammoniation kettle from a compressor to a condenser, condensing and recovering the unreacted ammonia gas to a liquid ammonia recovery tank for recycling, pressing the material to a centrifugal machine for centrifugal separation after the stirring is finished, removing centrifugal liquid from the crude product tank for temporary storage, then transferring to a distillation kettle, controlling the temperature in the kettle for reduced pressure distillation, respectively distilling out a front fraction and a finished product, and returning the front fraction to the ammoniation kettle for recycling, and (4) receiving the finished product into a finished product tank, sending the kettle liquid to a high-boiling distillation kettle for reduced pressure distillation after distillation is finished, receiving the finished product into a finished product tank, putting the kettle liquid into a kettle liquid tank after distillation is finished, and sending the waste to waste treatment.
More preferably, the catalyst in the step S1 comprises Speier catalyst and/or Karstedt catalyst;
more preferably, the Speier catalyst is an isopropanol solution of chloroplatinic acid and contains cyclohexanone with the same volume as the isopropanol;
more preferably, the Karstedt's catalyst is a complex of chloroplatinic acid and 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane;
more preferably, the preparation scheme of the cocatalyst in the step S1 is as follows:
drying 120 parts by mass of 100-class hydrotalcite at 350 ℃ for 5-10h, adding 600 parts by mass of 500-class anhydrous ethanol, 5-10 parts by mass of mercaptosiloxane and 2.1-4.3 parts by mass of acetic acid, stirring for 60-120min at 60-70 ℃, then adding 2-5 parts by mass of cyclopentadienyl allyl palladium, 5-10 parts by mass of 1-allyl pyrrolidine-2-formamide and 5-8 parts by mass of triethylamine, reacting for a certain time under set reaction conditions, filtering the mixed material after the reaction is finished, drying for 10-20h at 80-90 ℃, and obtaining the cocatalyst after the reaction is finished;
more preferably, the mercaptosiloxane is one or more of 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and mercaptopropylmethyldimethoxysilane;
more preferably, the reaction conditions are: the temperature is set to be 50-70 ℃, the reaction time is 1-4h, and the stirring speed is 120-;
more preferably, the normal pressure distillation in the step S1 is to inject the mother liquor into a distillation kettle, the tower top temperature of the rectification tower is 40-50 ℃, the tower bottom temperature is 160-; the reflux feed ratio is 2.5-4.5;
more preferably, the reduced pressure distillation in the step S1 is to heat the mother liquor to 90-130 ℃ in a distillation kettle, the vacuum degree is 0.08-0.1 Mpa, and the distillate is collected by reduced pressure distillation and is gamma-chloropropyltrichlorosilane;
more preferably, the reduced pressure distillation in the step S2 is to heat the mother liquor to 90-130 ℃ in a distillation kettle, the vacuum degree is 0.08-0.1 Mpa, and the distillate is collected by reduced pressure distillation and is gamma-chloropropyltriethoxysilane;
more preferably, the normal pressure distillation in the step S3 is to inject the mother liquor into a distillation kettle, the tower top temperature of the rectification tower is 40-50 ℃, the tower kettle temperature is 160-180 ℃, and the reflux feed ratio is 2.5-4.5;
more preferably, the normal pressure distillation in the step S3 is to inject the mother liquor into a distillation kettle, the tower top temperature of the rectification tower is 40-50 ℃, the tower bottom temperature is 160-; the reflux feed ratio is 2.5-4.5.
The reaction mechanism is as follows:
the reaction formula is as follows:
ClCH2CH2CH2Si(OCH2CH3)3+2NH3＝NH2CH2CH2CH2Si(OCH2CH3)3+NH4Cl↓
the invention has the beneficial effects that:
(1) the addition of cyclopentadienyl allyl palladium and 1-allyl pyrrolidine-2-formamide in the cocatalyst is beneficial to improving the activity of the catalyst in a reaction system, and can also form a complex with platinum with catalytic activity, thereby improving the stability of the catalyst and effectively inhibiting the aggregation and inactivation of the platinum with catalytic activity in the reaction process.
(2) The cocatalyst also has the effect of absorbing water, so that water is prevented from being brought in, side reaction with gamma-chloropropyltriethoxysilane is avoided, and separation is facilitated.
(3) The invention has simple process, low production cost, high reaction rate and low energy consumption.
(4) The invention has the advantages of less side reaction, less loss of reaction raw materials and high product yield.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a map of the 1H-NRM of gamma chloropropyltriethoxysilane prepared in example 3.
The specific implementation mode is as follows:
the invention is further illustrated by the following specific examples:
example 1
A solvent-free synthesis method of gamma aminopropyl triethoxysilane is characterized by comprising the following steps:
s1: pressing 180g of trichlorosilane and 100g of chloropropene into a mixing tank through nitrogen from a storage tank, mixing, adding the mixture into a synthesis reaction kettle through a high-level dropwise adding tank, heating the reaction kettle to 70 ℃ through jacket steam, and adding 20x105The catalyst and 3g of cocatalyst are added, after the reaction is started, the reaction temperature is controlled at 75 ℃, the reaction time is 4 hours,filtering, feeding the gamma chloropropyl trichlorosilane crude product generated by the reaction into a distillation kettle, distilling at normal pressure, then distilling at reduced pressure to obtain a product gamma chloropropyl trichlorosilane, and feeding the finished product into a product collection tank;
s2: pumping 150g of gamma-chloropropyl trichlorosilane into a metering tank, pumping 100g of ethanol from an ethanol storage tank into an ethanol overhead tank and an ethanol gasification tank, starting steam to heat the ethanol gasification tank, an ethanol buffer tank and an esterification tower kettle to 80 ℃, and keeping the temperature at 0.02MPa, enabling the gamma-chloropropyl trichlorosilane and the ethanol to enter the top of an esterification tower through a pre-reactor and finish esterification reaction in the esterification tower to obtain gamma-chloropropyl triethoxy silane esterified liquid and hydrogen chloride gas, enabling the esterified liquid to flow into an esterified liquid storage tank, collecting the produced hydrogen chloride to prepare trichlorosilane, pumping the esterified liquid into a distillation kettle, and carrying out reduced pressure distillation to obtain gamma-chloropropyl triethoxy silane;
s3: pumping 700g of gamma-chloropropyltriethoxysilane into a metering tank by a pump for metering, then feeding the metered gamma-chloropropyltriethoxysilane into an ammoniation kettle, then adding 100g of liquid ammonia for amination reaction, controlling the temperature of 180 ℃ and the pressure of 7MPa in the kettle, obtaining a gamma-aminopropyltriethoxysilane crude product and a byproduct ammonium chloride after the ammoniation reaction is finished, reacting for 3 hours, after the reaction is completed, pressing the kettle material into a stirring kettle for stirring, feeding unreacted ammonia gas in the ammoniation kettle into a condenser after a compressor, condensing and recycling the ammonia gas into a liquid ammonia recycling tank for recycling, pressing the material to a centrifugal machine for centrifugal separation after the stirring is finished, feeding centrifugal liquid into the crude product tank, transferring the centrifugal liquid into a distillation kettle, controlling the temperature in the kettle for temporary storage and reduced pressure distillation, respectively evaporating front fraction and finished product, returning the front fraction to the ammoniation kettle for recycling, receiving the finished product into a finished product tank, feeding the kettle liquid into the high-boiling distillation kettle for reduced pressure distillation after the distillation is finished, and (4) receiving the finished product into a finished product tank, putting the kettle liquid into a kettle liquid tank after distillation is finished, and sending the waste to waste treatment.
The catalyst in the step S1 is a Speier catalyst;
the Speier catalyst is an isopropanol solution of chloroplatinic acid and contains cyclohexanone with the same volume as the isopropanol;
the preparation scheme of the cocatalyst in the step S1 is as follows:
drying 100g of hydrotalcite at 200 ℃ for 5h, adding the hydrotalcite into 500g of absolute ethyl alcohol, 5g of mercaptosiloxane and 2.1g of acetic acid after the hydrotalcite is dried, stirring the mixture for 60min at 60 ℃, adding 2g of cyclopentadienyl allyl palladium, 5g of 1 allyl pyrrolidine 2 formamide and 5g of triethylamine, reacting the mixture for a certain time under a set reaction condition, filtering the mixture after the reaction is finished, and drying the mixture for 20h at 80 ℃ to obtain the cocatalyst;
the mercaptosiloxane is 3 mercaptopropyltriethoxysilane;
the reaction conditions are as follows: setting the temperature at 50 ℃, the reaction time at 4h, and the stirring speed at 120 r/min;
in the step S1, the normal pressure distillation is to feed the mother liquor into a distillation kettle, wherein the top temperature of a rectifying tower is 40 ℃, the bottom temperature of the rectifying tower is 160 ℃, and the top pressure of the rectifying tower is 800 kPa; the reflux feed ratio was 2.5;
in the step S1, the reduced pressure distillation is to put the mother liquor into a distillation kettle, heat the mother liquor to 90 ℃, reduce the pressure and vacuum degree to 0.08Mpa, and collect distillate which is gamma chloropropyl trichlorosilane through reduced pressure distillation;
in the step S2, the reduced pressure distillation is to put the mother liquor into a distillation kettle, heat the mother liquor to 90 ℃, reduce the pressure and vacuum degree to 0.08Mpa, and collect distillate which is gamma chloropropyl triethoxysilane through reduced pressure distillation;
in the step S3, the normal pressure distillation is to feed the mother liquor into a distillation kettle, wherein the top temperature of a rectifying tower is 40 ℃, the bottom temperature of the rectifying tower is 160 ℃, and the top pressure of the rectifying tower is 800 kPa; the reflux feed ratio was 2.5;
in the step S3, the normal pressure distillation is to feed the mother liquor into a distillation kettle, wherein the top temperature of a rectifying tower is 40 ℃, the bottom temperature of the rectifying tower is 160 ℃, and the top pressure of the rectifying tower is 800 kPa; the reflux to feed ratio was 2.5.
Example 2
A solvent-free synthesis method of gamma aminopropyl triethoxysilane is characterized by comprising the following steps:
s1: 200g of trichlorosilane and 100g of chloropropene are pressed into a proportioning tank from a storage tank through nitrogen, the mixture is added into a synthesis reaction kettle through a high-level dropping tank after being mixed, the reaction kettle is heated to 75 ℃ through jacket steam, and then 25x10 is added5Part of catalyst, 3g of cocatalyst, after the start of the reaction, controlThe reaction temperature is between 80 ℃, the reaction time is 4 hours, the gamma chloropropyl trichlorosilane crude product generated by the reaction is sent to a distillation still for atmospheric distillation, then the gamma chloropropyl trichlorosilane product is obtained by reduced pressure distillation, and the finished product enters a product collection tank;
s2: pumping 200g of gamma-chloropropyl trichlorosilane into a metering tank, pumping 120g of ethanol from an ethanol storage tank into an ethanol overhead tank and an ethanol gasification tank, starting steam to heat the ethanol gasification tank, an ethanol buffer tank and an esterification tower kettle to 85 ℃, and keeping the pressure at 0.04MPa, enabling the gamma-chloropropyl trichlorosilane and the ethanol to enter the top of an esterification tower through a pre-reactor and finish esterification reaction in the esterification tower to obtain gamma-chloropropyl triethoxy silane esterified liquid and hydrogen chloride gas, enabling the esterified liquid to flow into an esterified liquid storage tank, collecting the produced hydrogen chloride to prepare trichlorosilane, pumping the esterified liquid into a distillation kettle, and carrying out reduced pressure distillation to obtain gamma-chloropropyl triethoxy silane;
s3: pumping 700g of gamma-chloropropyltriethoxysilane into a metering tank by a pump for metering, then feeding the metered gamma-chloropropyltriethoxysilane into an ammoniation kettle, then adding 100g of liquid ammonia for amination reaction, controlling the temperature at 190 ℃ and the pressure at 7MPa in the kettle, obtaining a gamma-aminopropyltriethoxysilane crude product and a byproduct ammonium chloride after the ammoniation reaction is finished, reacting for 3 hours, after the reaction is completed, pressing the kettle material into a stirring kettle for stirring, feeding unreacted ammonia gas in the ammoniation kettle into a condenser after a compressor, condensing and recycling the ammonia gas into a liquid ammonia recycling tank for recycling, pressing the material to a centrifugal machine for centrifugal separation after the stirring is finished, feeding centrifugal liquid into the crude product tank, transferring the centrifugal liquid into a distillation kettle, controlling the temperature in the kettle for temporary storage and reduced pressure distillation, respectively evaporating front fraction and finished product, returning the front fraction to the ammoniation kettle for recycling, receiving the finished product into a finished product tank, feeding the kettle liquid into the high-boiling distillation kettle for reduced pressure distillation after the distillation is finished, and (4) receiving the finished product into a finished product tank, putting the kettle liquid into a kettle liquid tank after distillation is finished, and sending the waste to waste treatment.
The catalyst in step S1 is Karstedt' S catalyst;
the Karstedt catalyst is a complex of chloroplatinic acid with 1,3 divinyl 1,1,3,3 tetramethyldisiloxane;
the preparation scheme of the cocatalyst in the step S1 is as follows:
drying 100g of hydrotalcite at 250 ℃ for 5h, adding the hydrotalcite into 500g of absolute ethyl alcohol, 6g of mercaptosiloxane and 2.5g of acetic acid after the hydrotalcite is dried, stirring the mixture for 80min at 60 ℃, adding 2g of cyclopentadienyl allyl palladium, 6g of 1 allyl pyrrolidine 2 formamide and 5g of triethylamine, reacting the mixture for a certain time under a set reaction condition, filtering the mixture after the reaction is finished, and drying the mixture for 10h at 90 ℃ to obtain the cocatalyst after the reaction is finished;
the mercaptosiloxane is 3 mercaptopropyltrimethoxysilane;
the reaction conditions are as follows: setting the temperature at 60 ℃, the reaction time at 2h and the stirring speed at 120 r/min;
in the step S1, the normal pressure distillation is to inject the mother liquor into a distillation kettle, the top temperature of a rectifying tower is 40 ℃, the bottom temperature of the rectifying tower is 160 ℃, and the top pressure is 850 kPa; the reflux feed ratio was 3.5;
in the step S1, the reduced pressure distillation is to put the mother liquor into a distillation kettle, heat the mother liquor to 100 ℃, reduce the pressure and vacuum degree to 0.08Mpa, and collect distillate which is gamma chloropropyl trichlorosilane through reduced pressure distillation;
in the step S2, the reduced pressure distillation is to put the mother liquor into a distillation kettle, heat the mother liquor to 100 ℃, reduce the pressure and vacuum degree to 0.08Mpa, and collect distillate which is gamma chloropropyl triethoxysilane through reduced pressure distillation;
in the step S3, the normal pressure distillation is to feed the mother liquor into a distillation kettle, wherein the top temperature of a rectifying tower is 40 ℃, the bottom temperature of the rectifying tower is 160 ℃, and the top pressure of the rectifying tower is 900 kPa; the reflux feed ratio was 3.5;
in the step S3, the normal pressure distillation is to feed the mother liquor into a distillation kettle, wherein the top temperature of a rectifying tower is 40 ℃, the bottom temperature of the rectifying tower is 160 ℃, and the top pressure of the rectifying tower is 900 kPa; the reflux to feed ratio was 3.5.
Example 3
A solvent-free synthesis method of gamma aminopropyl triethoxysilane is characterized by comprising the following steps:
s1: 200g of trichlorosilane and 120g of chloropropene are pressed into a proportioning tank from a storage tank through nitrogen, the mixture is added into a synthesis reaction kettle through a high-level dropping tank after being mixed, the reaction kettle is heated to 80 ℃ through jacket steam, and then 30x10 is added5The method comprises the following steps of (1) reacting 4g of catalyst and cocatalyst, controlling the reaction temperature to be 85 ℃ after the reaction is started, reacting for 3 hours, filtering, feeding a gamma chloropropyl trichlorosilane crude product generated by the reaction into a distillation kettle, distilling at normal pressure, distilling at reduced pressure to obtain a gamma chloropropyl trichlorosilane product, and feeding the finished product into a product collection tank;
s2: pumping 240g of gamma-chloropropyl trichlorosilane into a metering tank, pumping 150g of ethanol from an ethanol storage tank into an ethanol overhead tank and an ethanol gasification tank, starting steam to heat the ethanol gasification tank, an ethanol buffer tank and an esterification tower kettle to 90 ℃, and raising the temperature to 0.06MPa, wherein the gamma-chloropropyl trichlorosilane and the ethanol enter the top of an esterification tower through a pre-reactor and finish esterification reaction in the esterification tower to obtain gamma-chloropropyl triethoxy silane esterified liquid and hydrogen chloride gas, the esterified liquid flows into an esterified liquid storage tank, the produced hydrogen chloride is collected and used for preparing trichlorosilane, and the esterified liquid is pumped into a distillation kettle to perform reduced pressure distillation to obtain gamma-chloropropyl triethoxy silane;
s3: 750g of gamma-chloropropyltriethoxysilane is pumped into a metering tank by a pump for metering, then the gamma-chloropropyltriethoxysilane enters an ammoniation kettle, then 100g of liquid ammonia is added for amination reaction, the temperature in the kettle is controlled to be 190 ℃ and the pressure to be 8MPa, after the ammoniation reaction is finished, a gamma-aminopropyltriethoxysilane crude product and a byproduct ammonium chloride are obtained, the reaction time is 4 hours, after the reaction is completed, kettle materials are pressed into a stirring kettle for stirring, unreacted ammonia gas in the ammoniation kettle passes through a compressor and then goes into a condenser, the ammonia gas is condensed and recovered to a liquid ammonia recovery tank for recycling, the materials are pressed to a centrifugal machine for centrifugal separation after the stirring is finished, centrifugal solid is the byproduct ammonium chloride, centrifugal liquid goes into the crude product tank, then the centrifugal liquid is transferred to a distillation kettle, the temperature in the temporary storage kettle is controlled for reduced pressure distillation, a front fraction and a finished product are respectively evaporated, the front fraction returns to the ammoniation kettle for recycling, the finished product is received into a finished product tank, after the distillation is finished, the kettle liquid is sent to the high-boiling distillation kettle for reduced pressure distillation, and (4) receiving the finished product into a finished product tank, putting the kettle liquid into a kettle liquid tank after distillation is finished, and sending the waste to waste treatment.
The catalyst in step S1 is Karstedt' S catalyst;
the Karstedt catalyst is a complex of chloroplatinic acid with 1,3 divinyl 1,1,3,3 tetramethyldisiloxane;
the preparation scheme of the cocatalyst in the step S1 is as follows:
drying 110g of hydrotalcite at 250 ℃ for 8h, adding the hydrotalcite into 550g of absolute ethyl alcohol, 6g of mercaptosiloxane and 2.9g of acetic acid, stirring the mixture for 80min at 65 ℃, adding 3g of cyclopentadienyl allyl palladium, 7g of 1 allyl pyrrolidine 2 formamide and 6g of triethylamine, reacting the mixture for a certain time under a set reaction condition, filtering the mixture after the reaction is finished, and drying the mixture for 10h at 90 ℃ to obtain the cocatalyst;
the mercaptosiloxane is mercaptopropyl methyldimethoxysilane;
the reaction conditions are as follows: setting the temperature at 60 ℃, the reaction time at 3h, and the stirring speed at 130 r/min;
in the step S1, the normal pressure distillation is to inject the mother liquor into a distillation kettle, the tower top temperature of a rectifying tower is 45 ℃, the tower kettle temperature is 170 ℃, and the tower top pressure is 850 kPa; the reflux feed ratio was 3.5;
in the step S1, the reduced pressure distillation is to put the mother liquor into a distillation kettle, heat the mother liquor to 100 ℃, reduce the pressure and vacuum degree to 0.09Mpa, and collect distillate which is gamma chloropropyl trichlorosilane through reduced pressure distillation;
in the step S2, the reduced pressure distillation is to put the mother liquor into a distillation kettle, heat the mother liquor to 100 ℃, reduce the pressure and vacuum degree to 0.09Mpa, and collect distillate through reduced pressure distillation, namely gamma chloropropyl triethoxysilane;
in the step S3, the normal pressure distillation is to feed the mother liquor into a distillation kettle, wherein the tower top temperature of a rectifying tower is 45 ℃, the tower kettle temperature is 170 ℃, and the tower top pressure is 800 kPa; the reflux feed ratio was 3.5;
in the step S3, the normal pressure distillation is to feed the mother liquor into a distillation kettle, wherein the tower top temperature of a rectifying tower is 45 ℃, the tower kettle temperature is 170 ℃, and the tower top pressure is 800 kPa; the reflux to feed ratio was 3.5.
Example 4
A solvent-free synthesis method of gamma aminopropyl triethoxysilane is characterized by comprising the following steps:
s1: 220g of trichlorosilane and 130g of chloropropene are pressed into a mixing tank from a storage tank through nitrogen, the mixture is added into a synthesis reaction kettle through a high-level dropping tank after being mixed, and the reaction kettle passes through a jacketHeating with steam to 85 deg.C, adding 40x105The method comprises the following steps of (1) mixing a catalyst and 5g of a cocatalyst, controlling the reaction temperature to be 85 ℃ after the reaction is started, reacting for 3 hours, filtering, feeding a gamma chloropropyl trichlorosilane crude product generated by the reaction into a distillation kettle, distilling at normal pressure, distilling at reduced pressure to obtain a gamma chloropropyl trichlorosilane product, and feeding the finished product into a product collection tank;
s2: pumping 260g of gamma-chloropropyl trichlorosilane into a metering tank, pumping 160g of ethanol from an ethanol storage tank into an ethanol overhead tank and an ethanol gasification tank, starting steam to heat the ethanol gasification tank, an ethanol buffer tank and an esterification tower kettle to 90 ℃, and keeping the pressure at 0.08MPa, enabling the gamma-chloropropyl trichlorosilane and the ethanol to enter the top of an esterification tower through a pre-reactor and finish esterification reaction in the esterification tower to obtain gamma-chloropropyl triethoxy silane esterified liquid and hydrogen chloride gas, enabling the esterified liquid to flow into an esterified liquid storage tank, collecting the produced hydrogen chloride to prepare trichlorosilane, pumping the esterified liquid into a distillation kettle, and carrying out reduced pressure distillation to obtain gamma-chloropropyl triethoxy silane;
s3: pumping 800g of gamma-chloropropyltriethoxysilane into a metering tank by a pump for metering, then feeding the metered gamma-chloropropyltriethoxysilane into an ammoniation kettle, then adding 100g of liquid ammonia for amination reaction, controlling the temperature in the kettle to be 200 ℃ and the pressure to be 8MPa, obtaining a gamma-aminopropyltriethoxysilane crude product and a byproduct ammonium chloride after the ammoniation reaction is finished, reacting for 5 hours, after the reaction is completed, pressing a kettle material into a stirring kettle for stirring, feeding unreacted ammonia gas in the ammoniation kettle into a condenser after a compressor, condensing and recycling the unreacted ammonia gas into a liquid ammonia recovery tank for recycling, pressing the material to a centrifugal machine for centrifugal separation after the stirring is finished, feeding centrifugal solid into the byproduct ammonium chloride, feeding the centrifugal liquid into the crude product tank, transferring the centrifugal liquid into a distillation kettle, controlling the temperature in the kettle for reduced pressure distillation, respectively evaporating front fraction and finished product, returning the front fraction to the ammoniation kettle for recycling, receiving the finished product into a finished product tank, feeding the kettle liquid into the high-boiling distillation kettle for reduced pressure distillation after the distillation is finished, and (4) receiving the finished product into a finished product tank, putting the kettle liquid into a kettle liquid tank after distillation is finished, and sending the waste to waste treatment.
The catalyst in the step S1 is a Speier catalyst;
the Speier catalyst is an isopropanol solution of chloroplatinic acid and contains cyclohexanone with the same volume as the isopropanol;
the preparation scheme of the cocatalyst in the step S1 is as follows:
drying 110g of hydrotalcite at 300 ℃ for 8h, adding the hydrotalcite into 550g of absolute ethyl alcohol, 7g of mercaptosiloxane and 3.5g of acetic acid after the hydrotalcite is dried, stirring the mixture for 90min at 65 ℃, adding 4g of cyclopentadienyl allyl palladium, 8g of 1 allyl pyrrolidine 2 formamide and 6g of triethylamine, reacting the mixture for a certain time under a set reaction condition, filtering the mixture after the reaction is finished, and drying the mixture for 15h at 85 ℃ to obtain the cocatalyst after the reaction is finished;
the mercaptosiloxane is 3 mercaptopropyltriethoxysilane;
the reaction conditions are as follows: setting the temperature at 65 ℃, the reaction time at 2h and the stirring speed at 150 r/min;
in the step S1, the normal pressure distillation is to inject the mother liquor into a distillation kettle, the tower top temperature of a rectifying tower is 45 ℃, the tower kettle temperature is 170 ℃, and the tower top pressure is 850 kPa; the reflux feed ratio was 4.5;
in the step S1, the reduced pressure distillation is to put the mother liquor into a distillation kettle, heat the mother liquor to 110 ℃, reduce the pressure and vacuum degree to 0.09Mpa, and collect the distillate by reduced pressure distillation, namely gamma chloropropyl trichlorosilane;
in the step S2, the reduced pressure distillation is to put the mother liquor into a distillation kettle, heat the mother liquor to 110 ℃, reduce the pressure and vacuum degree to 0.09Mpa, and collect distillate through reduced pressure distillation, namely gamma chloropropyl triethoxysilane;
in the step S3, the normal pressure distillation is to inject the mother liquor into a distillation kettle, the tower top temperature of a rectifying tower is 45 ℃, the tower kettle temperature is 170 ℃, and the tower top pressure is 850 kPa; the reflux feed ratio was 4.5;
in the step S3, the normal pressure distillation is to inject the mother liquor into a distillation kettle, the tower top temperature of a rectifying tower is 45 ℃, the tower kettle temperature is 170 ℃, and the tower top pressure is 850 kPa; the reflux to feed ratio was 4.5.
Example 5
A solvent-free synthesis method of gamma aminopropyl triethoxysilane is characterized by comprising the following steps:
s1: pressing 240g of trichlorosilane and 140g of chloropropene into a proportioning tank from a storage tank through nitrogen, mixing, and adding through a high-level dropwise adding tankMixing the materials in a synthesis reaction kettle, heating the reaction kettle to 90 ℃ by jacket steam, and adding 45x105The method comprises the following steps of (1) reacting 6g of a catalyst and a cocatalyst, controlling the reaction temperature to be 85 ℃ after the reaction is started, reacting for 4 hours, filtering, feeding a gamma chloropropyl trichlorosilane crude product generated by the reaction into a distillation kettle, distilling at normal pressure, distilling under reduced pressure to obtain a gamma chloropropyl trichlorosilane product, and feeding the finished product into a product collection tank;
s2: pumping 280g of gamma-chloropropyl trichlorosilane into a metering tank, pumping 180g of ethanol from an ethanol storage tank into an ethanol overhead tank and an ethanol gasification tank, starting steam to heat the ethanol gasification tank, an ethanol buffer tank and an esterification tower kettle to 95 ℃, and keeping the pressure at 0.09MPa, enabling the gamma-chloropropyl trichlorosilane and the ethanol to enter the top of an esterification tower through a pre-reactor and finish esterification reaction in the esterification tower to obtain gamma-chloropropyl triethoxy silane esterified liquid and hydrogen chloride gas, enabling the esterified liquid to flow into an esterified liquid storage tank, collecting the produced hydrogen chloride to prepare trichlorosilane, pumping the esterified liquid into a distillation kettle, and carrying out reduced pressure distillation to obtain gamma-chloropropyl triethoxy silane;
s3: pumping 800g of gamma-chloropropyltriethoxysilane into a metering tank by a pump for metering, then feeding the metered gamma-chloropropyltriethoxysilane into an ammoniation kettle, then adding 110g of liquid ammonia for amination reaction, controlling the temperature at 210 ℃ and the pressure at 9MPa in the kettle, obtaining a gamma-aminopropyltriethoxysilane crude product and a byproduct ammonium chloride after the ammoniation reaction is finished, reacting for 5 hours, after the reaction is completed, pressing the kettle material into a stirring kettle for stirring, feeding unreacted ammonia gas in the ammoniation kettle into a condenser after a compressor, condensing and recycling the ammonia gas into a liquid ammonia recycling tank for recycling, pressing the material to a centrifugal machine for centrifugal separation after the stirring is finished, feeding centrifugal liquid into the crude product tank, transferring the centrifugal liquid into a distillation kettle, controlling the temperature in the kettle for temporary storage and reduced pressure distillation, respectively evaporating front fraction and finished product, returning the front fraction to the ammoniation kettle for recycling, receiving the finished product into a finished product tank, feeding the kettle liquid into the high-boiling distillation kettle for reduced pressure distillation after the distillation is finished, and (4) receiving the finished product into a finished product tank, putting the kettle liquid into a kettle liquid tank after distillation is finished, and sending the waste to waste treatment.
The catalyst in the step S1 is a Speier catalyst;
the Speier catalyst is an isopropanol solution of chloroplatinic acid and contains cyclohexanone with the same volume as the isopropanol;
the preparation scheme of the cocatalyst in the step S1 is as follows:
drying 110g of hydrotalcite at 300 ℃ for 10h, adding the hydrotalcite into 550g of absolute ethyl alcohol, 8g of mercaptosiloxane and 3.9g of acetic acid after the hydrotalcite is dried, stirring the mixture for 100min at 70 ℃, adding 5g of cyclopentadienyl allyl palladium, 9g of 1 allyl pyrrolidine 2 formamide and 7g of triethylamine, reacting the mixture for a certain time under a set reaction condition, filtering the mixture after the reaction is finished, and drying the mixture for 20h at 85 ℃ to obtain the cocatalyst after the reaction is finished;
the mercaptosiloxane is 3 mercaptopropyltriethoxysilane;
the reaction conditions are as follows: setting the temperature at 70 ℃, the reaction time at 2h and the stirring speed at 160 r/min;
in the step S1, the normal pressure distillation is to inject the mother liquor into a distillation kettle, the top temperature of a rectifying tower is 50 ℃, the bottom temperature of the rectifying tower is 180 ℃, and the top pressure is 850 kPa; the reflux feed ratio was 4.5;
in the step S1, the reduced pressure distillation is to put the mother liquor into a distillation kettle, heat the mother liquor to 120 ℃, reduce the pressure and vacuum degree to 0.09Mpa, and collect distillate which is gamma chloropropyl trichlorosilane through reduced pressure distillation;
in the step S2, the reduced pressure distillation is to put the mother liquor into a distillation kettle, heat the mother liquor to 120 ℃, reduce the pressure and vacuum degree to 0.09Mpa, and collect distillate through reduced pressure distillation, namely gamma chloropropyl triethoxysilane;
in the step S3, the normal pressure distillation is to inject the mother liquor into a distillation kettle, the tower top temperature of a rectifying tower is 45 ℃, the tower kettle temperature is 180 ℃, and the tower top pressure is 850 kPa; the reflux feed ratio was 4.5;
in the step S3, the normal pressure distillation is to inject the mother liquor into a distillation kettle, the tower top temperature of a rectifying tower is 45 ℃, the tower kettle temperature is 180 ℃, and the tower top pressure is 850 kPa; the reflux to feed ratio was 4.5.
Example 6
A solvent-free synthesis method of gamma aminopropyl triethoxysilane is characterized by comprising the following steps:
s1: passing 250g of trichlorosilane and 150g of chloropropene from a storage tank through nitrogenPressing into a mixing tank, adding the mixture into a synthesis reaction kettle through a high-level dropwise adding tank after mixing, heating the reaction kettle to 90 ℃ through jacket steam, and adding 50x105The method comprises the following steps of (1) mixing a catalyst and 6g of a cocatalyst, controlling the reaction temperature to be 90 ℃ after the reaction is started, reacting for 4 hours, filtering, feeding a gamma chloropropyl trichlorosilane crude product generated by the reaction into a distillation kettle, distilling at normal pressure, distilling under reduced pressure to obtain a gamma chloropropyl trichlorosilane product, and feeding the finished product into a product collection tank;
s2: pumping 300g of gamma-chloropropyl trichlorosilane into a metering tank, pumping 200g of ethanol from an ethanol storage tank into an ethanol overhead tank and an ethanol gasification tank, starting steam to heat the ethanol gasification tank, an ethanol buffer tank and an esterification tower kettle to 100 ℃, and keeping the pressure at 0.1MPa, enabling the gamma-chloropropyl trichlorosilane and the ethanol to enter the top of an esterification tower through a pre-reactor and finish esterification reaction in the esterification tower to obtain gamma-chloropropyl triethoxy silane esterified liquid and hydrogen chloride gas, enabling the esterified liquid to flow into an esterified liquid storage tank, collecting the produced hydrogen chloride to prepare trichlorosilane, pumping the esterified liquid into a distillation kettle, and carrying out reduced pressure distillation to obtain gamma-chloropropyl triethoxy silane;
s3: pumping 850g of gamma chloropropyltriethoxysilane into a metering tank by a pump for metering, then feeding the metered gamma chloropropyltriethoxysilane into an ammoniation kettle, then adding 120g of liquid ammonia for amination reaction, controlling the temperature and the pressure in the kettle to be 220 ℃ and 10MPa, obtaining a gamma aminopropyltriethoxysilane crude product and a byproduct ammonium chloride after the ammoniation reaction is finished, reacting for 6 hours, after the reaction is completed, pressing the kettle material into a stirring kettle for stirring, feeding unreacted ammonia gas in the ammoniation kettle into a condenser after a compressor, condensing and recycling the unreacted ammonia gas into a liquid ammonia recycling tank for recycling, pressing the material to a centrifugal machine for centrifugal separation after the stirring is finished, feeding centrifugal liquid into the crude product tank, transferring the centrifugal liquid into a distillation kettle, controlling the temperature in the kettle for temporary storage and reduced pressure distillation, respectively evaporating front fraction and finished product, returning the front fraction to the ammoniation kettle for recycling, receiving the finished product into a finished product tank, feeding the kettle liquid to the high-boiling distillation kettle for reduced pressure distillation after the distillation is finished, and (4) receiving the finished product into a finished product tank, putting the kettle liquid into a kettle liquid tank after distillation is finished, and sending the waste to waste treatment.
The catalyst in step S1 is Karstedt' S catalyst;
the Karstedt catalyst is a complex of chloroplatinic acid with 1,3 divinyl 1,1,3,3 tetramethyldisiloxane;
the preparation scheme of the cocatalyst in the step S1 is as follows:
drying 120g of hydrotalcite at 350 ℃ for 10h, adding the hydrotalcite into 600g of absolute ethyl alcohol, 10g of mercaptosiloxane and 4.3g of acetic acid after the hydrotalcite is dried, stirring for 120min at 70 ℃, then adding 5g of cyclopentadienyl allyl palladium, 10g of 1 allyl pyrrolidine 2 formamide and 8g of triethylamine, reacting for a certain time under the set reaction condition, filtering the mixed material after the reaction is finished, and drying for 20h at 90 ℃ to obtain the cocatalyst;
the mercaptosiloxane is 3 mercaptopropyltrimethoxysilane;
the reaction conditions are as follows: setting the temperature at 70 ℃, the reaction time at 4h and the stirring speed at 160 r/min;
in the step S1, the normal pressure distillation is to feed the mother liquor into a distillation kettle, wherein the top temperature of a rectifying tower is 50 ℃, the bottom temperature of the rectifying tower is 180 ℃, and the top pressure of the rectifying tower is 900 kPa; the reflux feed ratio was 4.5;
in the step S1, the reduced pressure distillation is to put the mother liquor into a distillation kettle, heat the mother liquor to 130 ℃, reduce the pressure and vacuum degree to 0.1Mpa, and collect distillate which is gamma chloropropyl trichlorosilane through reduced pressure distillation;
in the step S2, the reduced pressure distillation is to put the mother liquor into a distillation kettle, heat the mother liquor to 130 ℃, reduce the pressure and vacuum degree to 0.1Mpa, and collect distillate by reduced pressure distillation, namely gamma chloropropyl triethoxysilane;
in the step S3, the normal pressure distillation is to feed the mother liquor into a distillation kettle, wherein the top temperature of a rectifying tower is 50 ℃, the bottom temperature of the rectifying tower is 180 ℃, and the top pressure of the rectifying tower is 900 kPa; the reflux feed ratio was 4.5;
in the step S3, the normal pressure distillation is to feed the mother liquor into a distillation kettle, wherein the top temperature of a rectifying tower is 50 ℃, the bottom temperature of the rectifying tower is 180 ℃, and the top pressure of the rectifying tower is 900 kPa; the reflux to feed ratio was 4.5.
Comparative example 1
A solvent-free synthesis method of gamma aminopropyl triethoxysilane is characterized by comprising the following steps:
S1：pressing 180g of trichlorosilane and 100g of chloropropene into a mixing tank through nitrogen from a storage tank, mixing, adding the mixture into a synthesis reaction kettle through a high-level dropwise adding tank, heating the reaction kettle to 70 ℃ through jacket steam, and adding 20x105The catalyst is added, after the reaction is started, the reaction temperature is controlled to be 75 ℃, the reaction time is 4 hours, the filtration is carried out, the gamma chloropropyl trichlorosilane crude product generated by the reaction is sent to a distillation still for atmospheric distillation, then the reduced pressure distillation is carried out to obtain the product gamma chloropropyl trichlorosilane, and the finished product enters a product collection tank;
s2: pumping 150g of gamma-chloropropyl trichlorosilane into a metering tank, pumping 100g of ethanol from an ethanol storage tank into an ethanol overhead tank and an ethanol gasification tank, starting steam to heat the ethanol gasification tank, an ethanol buffer tank and an esterification tower kettle to 80 ℃, and keeping the temperature at 0.02MPa, enabling the gamma-chloropropyl trichlorosilane and the ethanol to enter the top of an esterification tower through a pre-reactor and finish esterification reaction in the esterification tower to obtain gamma-chloropropyl triethoxy silane esterified liquid and hydrogen chloride gas, enabling the esterified liquid to flow into an esterified liquid storage tank, collecting the produced hydrogen chloride to prepare trichlorosilane, pumping the esterified liquid into a distillation kettle, and carrying out reduced pressure distillation to obtain gamma-chloropropyl triethoxy silane;
s3: pumping 700g of gamma-chloropropyltriethoxysilane into a metering tank by a pump for metering, then feeding the metered gamma-chloropropyltriethoxysilane into an ammoniation kettle, then adding 100g of liquid ammonia for amination reaction, controlling the temperature of 180 ℃ and the pressure of 7MPa in the kettle, obtaining a gamma-aminopropyltriethoxysilane crude product and a byproduct ammonium chloride after the ammoniation reaction is finished, reacting for 3 hours, after the reaction is completed, pressing the kettle material into a stirring kettle for stirring, feeding unreacted ammonia gas in the ammoniation kettle into a condenser after a compressor, condensing and recycling the ammonia gas into a liquid ammonia recycling tank for recycling, pressing the material to a centrifugal machine for centrifugal separation after the stirring is finished, feeding centrifugal liquid into the crude product tank, transferring the centrifugal liquid into a distillation kettle, controlling the temperature in the kettle for temporary storage and reduced pressure distillation, respectively evaporating front fraction and finished product, returning the front fraction to the ammoniation kettle for recycling, receiving the finished product into a finished product tank, feeding the kettle liquid into the high-boiling distillation kettle for reduced pressure distillation after the distillation is finished, and (4) receiving the finished product into a finished product tank, putting the kettle liquid into a kettle liquid tank after distillation is finished, and sending the waste to waste treatment.
The catalyst in the step S1 is a Speier catalyst;
the Speier catalyst is an isopropanol solution of chloroplatinic acid and contains cyclohexanone with the same volume as the isopropanol;
in the step S1, the normal pressure distillation is to feed the mother liquor into a distillation kettle, wherein the top temperature of a rectifying tower is 40 ℃, the bottom temperature of the rectifying tower is 160 ℃, and the top pressure of the rectifying tower is 800 kPa; the reflux feed ratio was 2.5;
in the step S1, the reduced pressure distillation is to put the mother liquor into a distillation kettle, heat the mother liquor to 90 ℃, reduce the pressure and vacuum degree to 0.08Mpa, and collect distillate which is gamma chloropropyl trichlorosilane through reduced pressure distillation;
in the step S2, the reduced pressure distillation is to put the mother liquor into a distillation kettle, heat the mother liquor to 90 ℃, reduce the pressure and vacuum degree to 0.08Mpa, and collect distillate which is gamma chloropropyl triethoxysilane through reduced pressure distillation;
in the step S3, the normal pressure distillation is to feed the mother liquor into a distillation kettle, wherein the top temperature of a rectifying tower is 40 ℃, the bottom temperature of the rectifying tower is 160 ℃, and the top pressure of the rectifying tower is 800 kPa; the reflux feed ratio was 2.5;
in the step S3, the normal pressure distillation is to feed the mother liquor into a distillation kettle, wherein the top temperature of a rectifying tower is 40 ℃, the bottom temperature of the rectifying tower is 160 ℃, and the top pressure of the rectifying tower is 800 kPa; the reflux to feed ratio was 2.5.
Comparative example 2
A solvent-free synthesis method of gamma aminopropyl triethoxysilane is characterized by comprising the following steps:
s1: pressing 180g of trichlorosilane and 100g of chloropropene into a proportioning tank through nitrogen from a storage tank, mixing, adding a mixture into a synthesis reaction kettle through a high-position dropwise adding tank, heating the reaction kettle to 70 ℃ through jacket steam, adding 3g of cocatalyst, controlling the reaction temperature to be 75 ℃ after the reaction is started, reacting for 4 hours, filtering, conveying a gamma chloropropyl trichlorosilane crude product generated by the reaction to a distillation kettle, distilling at normal pressure, distilling at reduced pressure to obtain a gamma chloropropyl trichlorosilane product, and feeding the finished product into a product collecting tank;
s2: pumping 150g of gamma-chloropropyl trichlorosilane into a metering tank, pumping 100g of ethanol from an ethanol storage tank into an ethanol overhead tank and an ethanol gasification tank, starting steam to heat the ethanol gasification tank, an ethanol buffer tank and an esterification tower kettle to 80 ℃, and keeping the temperature at 0.02MPa, enabling the gamma-chloropropyl trichlorosilane and the ethanol to enter the top of an esterification tower through a pre-reactor and finish esterification reaction in the esterification tower to obtain gamma-chloropropyl triethoxy silane esterified liquid and hydrogen chloride gas, enabling the esterified liquid to flow into an esterified liquid storage tank, collecting the produced hydrogen chloride to prepare trichlorosilane, pumping the esterified liquid into a distillation kettle, and carrying out reduced pressure distillation to obtain gamma-chloropropyl triethoxy silane;
s3: pumping 700g of gamma-chloropropyltriethoxysilane into a metering tank by a pump for metering, then feeding the metered gamma-chloropropyltriethoxysilane into an ammoniation kettle, then adding 100g of liquid ammonia for amination reaction, controlling the temperature of 180 ℃ and the pressure of 7MPa in the kettle, obtaining a gamma-aminopropyltriethoxysilane crude product and a byproduct ammonium chloride after the ammoniation reaction is finished, reacting for 3 hours, after the reaction is completed, pressing the kettle material into a stirring kettle for stirring, feeding unreacted ammonia gas in the ammoniation kettle into a condenser after a compressor, condensing and recycling the ammonia gas into a liquid ammonia recycling tank for recycling, pressing the material to a centrifugal machine for centrifugal separation after the stirring is finished, feeding centrifugal liquid into the crude product tank, transferring the centrifugal liquid into a distillation kettle, controlling the temperature in the kettle for temporary storage and reduced pressure distillation, respectively evaporating front fraction and finished product, returning the front fraction to the ammoniation kettle for recycling, receiving the finished product into a finished product tank, feeding the kettle liquid into the high-boiling distillation kettle for reduced pressure distillation after the distillation is finished, and (4) receiving the finished product into a finished product tank, putting the kettle liquid into a kettle liquid tank after distillation is finished, and sending the waste to waste treatment.
The preparation scheme of the cocatalyst in the step S1 is as follows:
drying 100g of hydrotalcite at 200 ℃ for 5h, adding the hydrotalcite into 500g of absolute ethyl alcohol, 5g of mercaptosiloxane and 2.1g of acetic acid after the hydrotalcite is dried, stirring the mixture for 60min at 60 ℃, adding 2g of cyclopentadienyl allyl palladium, 5g of 1 allyl pyrrolidine 2 formamide and 5g of triethylamine, reacting the mixture for a certain time under a set reaction condition, filtering the mixture after the reaction is finished, and drying the mixture for 20h at 80 ℃ to obtain the cocatalyst;
the mercaptosiloxane is 3 mercaptopropyltriethoxysilane;
the reaction conditions are as follows: setting the temperature at 50 ℃, the reaction time at 4h, and the stirring speed at 120 r/min;
in the step S1, the normal pressure distillation is to feed the mother liquor into a distillation kettle, wherein the top temperature of a rectifying tower is 40 ℃, the bottom temperature of the rectifying tower is 160 ℃, and the top pressure of the rectifying tower is 800 kPa; the reflux feed ratio was 2.5;
in the step S1, the reduced pressure distillation is to put the mother liquor into a distillation kettle, heat the mother liquor to 90 ℃, reduce the pressure and vacuum degree to 0.08Mpa, and collect distillate which is gamma chloropropyl trichlorosilane through reduced pressure distillation;
in the step S2, the reduced pressure distillation is to put the mother liquor into a distillation kettle, heat the mother liquor to 90 ℃, reduce the pressure and vacuum degree to 0.08Mpa, and collect distillate which is gamma chloropropyl triethoxysilane through reduced pressure distillation;
in the step S3, the normal pressure distillation is to feed the mother liquor into a distillation kettle, wherein the top temperature of a rectifying tower is 40 ℃, the bottom temperature of the rectifying tower is 160 ℃, and the top pressure of the rectifying tower is 800 kPa; the reflux feed ratio was 2.5;
in the step S3, the normal pressure distillation is to feed the mother liquor into a distillation kettle, wherein the top temperature of a rectifying tower is 40 ℃, the bottom temperature of the rectifying tower is 160 ℃, and the top pressure of the rectifying tower is 800 kPa; the reflux to feed ratio was 2.5.
Test results of examples and comparative examples:
Claims (12)
1. a solvent-free synthesis method of gamma-aminopropyl triethoxysilane comprises the following operation steps:
s1: according to the weight parts, 250 parts of trichlorosilane 180 and 150 parts of chloropropene 100 are pressed into a mixing tank by nitrogen from a storage tank, mixed and added into a synthesis reaction kettle by a high-level dropping tank, the reaction kettle is heated to 70-90 ℃ by jacket steam, and then 20-50x10 is added-5The catalyst and the cocatalyst are added in parts by weight, after the reaction is started, the reaction temperature is controlled to be 75-90 ℃, the reaction time is 1-4 hours, the reaction is filtered, the gamma-chloropropyl trichlorosilane crude product generated by the reaction is sent to a distillation still for normal pressure distillation, then the reduced pressure distillation is carried out to obtain the gamma-chloropropyl trichlorosilane product, and the finished product enters a product collection tank;
s2: pumping 150-200 parts of gamma-chloropropyltrichlorosilane into a metering tank, pumping 100-200 parts of ethanol into an ethanol overhead tank and an ethanol gasification tank from an ethanol storage tank, starting steam to heat the ethanol gasification tank, an ethanol buffer tank and an esterification tower kettle to 80-100 ℃ and 0.02-0.1MPa, feeding the gamma-chloropropyltrichlorosilane and ethanol into the top of an esterification tower through a pre-reactor, completing esterification reaction in the esterification tower to obtain gamma-chloropropyltriethoxysilane esterified liquid and hydrogen chloride gas, feeding the esterified liquid into an esterified liquid storage tank, collecting the produced hydrogen chloride to prepare trichlorosilane, pumping the esterified liquid into a distillation kettle, and performing reduced pressure distillation to obtain gamma-chloropropyltriethoxysilane;
s3: pumping 850 parts by weight of 700-plus-material gamma-chloropropyltriethoxysilane into a metering tank by a pump, metering, then feeding into an ammoniation kettle, adding 120 parts by weight of liquid ammonia of 100-plus-material for amination, controlling the temperature of 180-plus-material in the kettle and the pressure of 7-10MPa, obtaining a crude product of gamma-aminopropyltriethoxysilane and a byproduct ammonium chloride after the amination is finished, reacting for 3-6 hours, after the reaction is completed, pressing the kettle material into a stirring kettle for stirring, removing unreacted ammonia gas in the ammoniation kettle from a compressor to a condenser, condensing and recovering the unreacted ammonia gas to a liquid ammonia recovery tank for recycling, pressing the material to a centrifugal machine for centrifugal separation after the stirring is finished, removing centrifugal liquid from the crude product tank for temporary storage, then transferring to a distillation kettle, controlling the temperature in the kettle for reduced pressure distillation, respectively distilling out a front fraction and a finished product, and returning the front fraction to the ammoniation kettle for recycling, and (4) receiving the finished product into a finished product tank, sending the kettle liquid to a high-boiling distillation kettle for reduced pressure distillation after distillation is finished, receiving the finished product into a finished product tank, putting the kettle liquid into a kettle liquid tank after distillation is finished, and sending the waste to waste treatment.
2. The solvent-free synthesis method of vinyltrimethoxysilane according to claim 1, wherein: the catalyst in the step S1 comprises a Speier catalyst and/or a Karstedt catalyst.
3. The solvent-free synthesis method of gamma-aminopropyltriethoxysilane as claimed in claim 2, wherein: the Speier catalyst is an isopropanol solution of chloroplatinic acid and contains cyclohexanone in equal volume to the isopropanol.
4. The solvent-free synthesis method of gamma-aminopropyltriethoxysilane as claimed in claim 2, wherein: the Karstedt catalyst is a complex of chloroplatinic acid with 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane.
5. The solvent-free synthesis method of gamma-aminopropyltriethoxysilane as claimed in claim 1, wherein: the preparation scheme of the cocatalyst in the step S1 is as follows:
according to the mass portion, 120 portions of 100-200-350 ℃ hydrotalcite is dried for 5-10h, then added into 600 portions of 500-350 anhydrous ethanol, 5-10 portions of mercaptosiloxane and 2.1-4.3 portions of acetic acid, stirred for 60-120min at 60-70 ℃, then added with 2-5 portions of cyclopentadienyl allyl palladium, 5-10 portions of 1-allyl pyrrolidine-2-formamide and 5-8 portions of triethylamine, reacted for a certain time under the set reaction condition, the mixed material is filtered after the reaction is finished, dried for 10-20h at 80-90 ℃ and the cocatalyst can be obtained after the reaction is finished.
6. The solvent-free synthesis method of gamma-aminopropyltriethoxysilane as claimed in claim 5, wherein: the mercaptosiloxane is one or more of 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and mercaptopropylmethyldimethoxysilane.
7. The solvent-free synthesis method of gamma-aminopropyltriethoxysilane as claimed in claim 5, wherein: the reaction conditions are as follows: the temperature is set to be 50-70 ℃, the reaction time is 1-4h, and the stirring speed is 120-160 r/min.
8. The solvent-free synthesis method of gamma-aminopropyltriethoxysilane as claimed in claim 1, wherein: the normal pressure distillation in the step S1 is to inject the mother liquor into a distillation kettle, the tower top temperature of the rectification tower is 40-50 ℃, and the tower kettle temperature is 160-180 ℃; the reflux feed ratio is 2.5-4.5.
9. The solvent-free synthesis method of gamma-aminopropyltriethoxysilane as claimed in claim 1, wherein: and in the step S1, the reduced pressure distillation is to inject the mother liquor into a distillation kettle, heat the mother liquor to 90-130 ℃, reduce the pressure and vacuum degree to 0.08-0.1 Mpa, and collect the distillate which is gamma-chloropropyltrichlorosilane by reduced pressure distillation.
10. The solvent-free synthesis method of gamma-aminopropyltriethoxysilane as claimed in claim 1, wherein: and in the step S2, the reduced pressure distillation is to inject the mother liquor into a distillation kettle, heat the mother liquor to 90-130 ℃, reduce the pressure and vacuum degree to 0.08-0.1 Mpa, and collect the distillate which is gamma-chloropropyltriethoxysilane.
11. The solvent-free synthesis method of gamma-aminopropyltriethoxysilane as claimed in claim 1, wherein: the normal pressure distillation in the step S3 is to inject the mother liquor into a distillation kettle, the tower top temperature of the rectification tower is 40-50 ℃, the tower kettle temperature is 160-180 ℃, and the tower top pressure is 800-900 kPa; the reflux feed ratio is 2.5-4.5.
12. The solvent-free synthesis method of gamma-aminopropyltriethoxysilane as claimed in claim 1, wherein: and in the step S3, the reduced pressure distillation is to inject the mother liquor into a distillation kettle to be heated to 110 ℃ and 130 ℃, the reduced pressure vacuum degree is 0.08MPa-0.1MPa, and the distillate is collected by reduced pressure distillation and is the gamma-aminopropyltriethoxysilane.
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