CN115532287B - Solid acid catalyst and low molecular weight hydrogen-containing polysiloxane and preparation method thereof - Google Patents
Solid acid catalyst and low molecular weight hydrogen-containing polysiloxane and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 239000011973 solid acid Substances 0.000 title claims abstract description 74
- 239000001257 hydrogen Substances 0.000 title claims abstract description 65
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 65
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 47
- -1 polysiloxane Polymers 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002243 precursor Substances 0.000 claims abstract description 34
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 16
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000975 co-precipitation Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000004821 distillation Methods 0.000 claims description 17
- 229920002545 silicone oil Polymers 0.000 claims description 17
- 150000002431 hydrogen Chemical class 0.000 claims description 16
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical group C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000002981 blocking agent Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000002210 silicon-based material Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 27
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000001914 filtration Methods 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 13
- 238000004817 gas chromatography Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- 101000793931 Bacillus pumilus Chloramphenicol acetyltransferase Proteins 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- 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
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- 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
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silicon Polymers (AREA)
Abstract
The application discloses a solid acid catalyst, low molecular weight hydrogen-containing polysiloxane and a preparation method thereof, and belongs to the technical field of organic silicon materials. The solid acid catalyst is prepared by the following method: carrying out coprecipitation reaction on aluminum sulfate solution, silica sol and ammonia water, and roasting a solid obtained by the coprecipitation reaction to obtain a precursor silicon-aluminum oxide; then mixing with sulfuric acid solution for reaction, and drying. The solid acid catalyst has high catalytic activity and is suitable for preparing low molecular weight hydrogen-containing polysiloxane. The solid acid catalyst is used as a catalyst for preparing low molecular weight hydrogen-containing polysiloxane, the yield of the obtained target product is high, and the corresponding preparation process is simple and environment-friendly.
Description
Technical Field
The application relates to the technical field of organic silicon materials, in particular to a solid acid catalyst, low-molecular-weight hydrogen-containing polysiloxane and a preparation method thereof.
Background
The active hydrogen on the main chain of the hydrogen-containing polysiloxane can react with a plurality of active groups, and a large number of side chain functional groups can be introduced through hydrosilylation reaction, so that various functional organic silicon products including surfactants, paint leveling agents and polyurethane foam stabilizers are prepared.
There are three main routes to the preparation of low molecular weight hydrogen containing polysiloxanes:
(1) Hydrolytic condensation of chlorosilane;
(2) Ring-opening polymerization of tetramethyl tetrahydrocyclotetrasiloxane;
(3) Telomerization of high hydrogen silicone oil.
The first method can generate acid HCl gas or liquid, and the preparation process is relatively complex, which is not beneficial to environmental protection; the tetramethyl tetrahydrocyclotetrasiloxane raw material used in the second method is expensive and has poor stability; the third method is more suitable for preparing low molecular weight hydrogen-containing polysiloxane.
In the third method, the conventional catalyst mainly comprises concentrated sulfuric acid, trifluoromethanesulfonic acid and cation exchange resin, and the conventional catalyst has some defects.
The concentrated sulfuric acid catalyst has strong corrosiveness, needs neutralization treatment, and has complex production process and generates a large amount of solid waste. The triflic acid or the strong acid cation exchange resin is expensive corresponding to the used raw materials, the reaction time is too long, and the production cost of the target product is higher.
In view of this, the present application has been made.
Disclosure of Invention
One of the purposes of the application is to provide a solid acid catalyst which is suitable for preparing low molecular weight hydrogen-containing polysiloxane, and the production cost of target products is low and the process is simple.
It is another object of the present application to provide a low molecular weight hydrogen-containing polysiloxane prepared by using the above solid acid catalyst as a catalyst for the reaction.
The third object of the present application is to provide a method for preparing the solid acid catalyst.
The application can be realized as follows:
in a first aspect, the present application provides a solid acid catalyst prepared by the process comprising: carrying out coprecipitation reaction on aluminum sulfate solution, silica sol and ammonia water, and roasting a solid obtained by the coprecipitation reaction to obtain a precursor silicon-aluminum oxide; then mixing with sulfuric acid solution for reaction, and drying.
In an alternative embodiment, the preparation of the solid acid catalyst includes at least one of the following features:
characteristic (1): the coprecipitation reaction is carried out for 8-10 hours under the condition that the pH value is 8-9;
feature (2): the concentration of the aluminum sulfate solution is 0.6-0.9g/mL, and/or the concentration of the ammonia water is 20-30wt%;
feature (3): roasting is carried out for 2-4 hours at 400-500 ℃;
feature (4): the model of the silica sol is LUDOX AS-30, LUDOX AS-40 or LUDOX HS-40;
feature (5): the concentration of the sulfuric acid solution is 1.0-1.5mol/L, and/or the volume of the sulfuric acid solution is 70-100mL;
feature (6): mixing the precursor silicon-aluminum oxide with the sulfuric acid solution at 70-80 ℃ for 3-6h;
feature (7): drying is carried out for 12-18h under the condition of 80-90 ℃;
feature (8): after drying, a grinding step is also included.
In an alternative embodiment, the molar ratio of elemental silicon to elemental aluminum in the solid acid catalyst is from 1:3 to 5;
and/or the particle size of the solid acid catalyst is 300-400 meshes.
In a second aspect, the present application provides a low molecular weight hydrogen-containing polysiloxane prepared by using the above solid acid catalyst as a catalyst for the reaction.
In an alternative embodiment, the low molecular weight hydrogen containing polysiloxane is 1,3, 5-heptamethyltrisiloxane having the structural formula:
in a third aspect, the present application also provides a method for preparing the above low molecular weight hydrogen-containing polysiloxane, comprising the steps of: reacting the reaction raw materials under the action of the solid acid catalyst, removing the solid acid catalyst, and distilling the residual reaction product;
wherein the reaction raw materials comprise high hydrogen silicone oil and a blocking agent.
In an alternative embodiment, the high hydrogen silicone oil has the formula:
wherein m=45-70;
and/or the end-capping agent is hexamethyldisiloxane.
In an alternative embodiment, the molar ratio of the high hydrogen silicone oil to the endcapping agent is from 1:30 to 80;
and/or the solid acid catalyst is used in an amount of 0.4 to 1.0wt% based on the total amount of the reaction raw materials.
In an alternative embodiment, the reaction of the reaction raw materials under the action of the solid acid catalyst is carried out at 40-80 ℃ for 2-6 hours.
In an alternative embodiment, the distillation comprises: removing low boiling point material below 130 ℃ in the reaction product by atmospheric distillation, and obtaining the fraction at 141-142 ℃ by atmospheric distillation.
The beneficial effects of the application include:
the solid acid catalyst provided by the application is prepared by a specific method, the preparation method is simple, the raw materials are easy to obtain, and the catalytic activity is high. The solid acid catalyst is applied to the production of low molecular weight hydrogen-containing polysiloxane, so that the low molecular weight hydrogen-containing polysiloxane with higher yield can be obtained, the whole preparation process is simple and easy to operate, the required reaction temperature is low, the energy conservation and consumption reduction are facilitated, the produced pollutants are less, and the preparation method is environment-friendly.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The solid acid catalyst and the low molecular weight hydrogen-containing polysiloxane and the preparation method thereof provided by the application are specifically described below.
The application provides a solid acid catalyst, which is prepared by the following method: carrying out coprecipitation reaction on aluminum sulfate solution, silica sol and ammonia water, and roasting a solid obtained by the coprecipitation reaction to obtain a precursor silicon-aluminum oxide; then mixing with sulfuric acid solution for reaction, and drying.
By way of reference, the aluminum sulfate solution may be prepared by 2 (SO 4 ) 3 Dissolving in deionized water, and stirring at 70-90deg.C for 2-4 hr.
Preferably, the concentration of the aluminum sulfate solution can be controlled to be 0.6-0.9g/mL, such as 0.6g/mL, 0.7g/mL, 0.8g/mL, 0.9g/mL, etc., and can be any other value within the range of 0.6-0.9 g/mL.
The silica sol used may be, for example, of the type LUDOX AS-30, LUDOX AS-40 or LUDOX HS-40.
The concentration of the aqueous ammonia may be 20 to 30wt%, such as 20wt%, 22wt%, 25wt%, 28wt%, 30wt%, etc., or may be any other value within the range of 20 to 30 wt%.
The coprecipitation reaction may be carried out, for example, by adding the silica sol and ammonia water to the aluminum sulfate solution prepared as described above, maintaining the pH of the system at 8 to 9, and stirring for 8 to 10 hours.
Further, filtering the substances after the coprecipitation reaction, washing 3 times with deionized water, drying in a vacuum drying oven at 80-90 ℃ for 12-18h, and roasting at 400-500 ℃ for 2-4h to obtain the catalyst precursor silicon-aluminum oxide.
The temperature of the vacuum drying may be 80℃at 81℃at 82℃at 83℃at 84℃at 85℃at 86℃at 87℃at 88℃at 89℃or at 90℃at 90℃or any other value within the range of 80 to 90 ℃.
The vacuum drying time can be 12h, 13h, 14h, 15h, 16h, 17h or 18h, etc., or any other value within the range of 12-18 h.
In the application, the drying mode is particularly a vacuum drying mode, and has the advantage of larger specific surface area of the catalyst compared with the modes such as forced air drying and the like. In addition, if the temperature of vacuum drying is higher than 90 ℃, it tends to cause a decrease in the specific surface area of the catalyst.
As a reference, the above-mentioned baking temperature may be 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, or the like, or may be any other value in the range of 400 to 500 ℃.
The roasting time can be 2h, 2.5h, 3h, 3.5h or 4h, and the like, and can be any other value within the range of 2-4 h.
If the roasting temperature is lower than 400 ℃, the catalyst precursor is easy to cause that a good crystal structure cannot be formed; if the roasting temperature is higher than 500 ℃, sintering or agglomeration of the catalyst precursor is easy to occur, and the specific surface area is reduced.
Stirring precursor silicon aluminum oxide and sulfuric acid solution at 70-80 ℃ for 3-6h, drying in a vacuum drying oven at 80-90 ℃ for 12-18h, and grinding into fine powder to obtain the solid acid catalyst.
The concentration of the sulfuric acid solution used for acidifying the precursor silicon aluminum oxide may be 1.0 to 1.5mol/L, such as 1.0mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L, etc., and may be any other value in the range of 1.0 to 1.5 mol/L. Accordingly, the volume of sulfuric acid solution used may be 70-100mL.
If the concentration of the sulfuric acid solution is less than 1.0mol/L, the amount of acid supported on the catalyst tends to be small; if the concentration of the sulfuric acid solution is higher than 1.5mol/L, a large amount of easily desorbed protonic acid is easily caused to exist on the surface of the catalyst, and the protonic acid can remain in the product, so that the storage stability of the product can be affected.
Preferably, the molar ratio of the silicon element to the aluminum element in the solid acid catalyst provided by the application can be 1:3-5, such as 1:3, 1:3.5, 1:4, 1:4.5 or 1:5, and the like, and can be any other value in the range of 1:3-5.
If the molar ratio of silicon element to aluminum element in the solid acid catalyst is less than 1:3 or more than 1:5, the catalytic activity tends to be lowered.
The particle size of the solid acid catalyst may be 300-400 mesh. In the particle size range, the reaction rate of the preparation process of the low molecular weight hydrogen-containing polysiloxane is favorably improved.
On the premise of bearing, the solid acid catalyst provided by the application has high catalytic activity and simple preparation process, is suitable for preparing low-molecular-weight hydrogen-containing polysiloxane, is beneficial to improving the yield of target products and reduces the production cost.
Correspondingly, the application also provides low molecular weight hydrogen-containing polysiloxane, and the solid acid catalyst is used as a catalyst for reaction in the preparation process.
In some exemplary embodiments, the low molecular weight hydrogen-containing polysiloxane is 1,3, 5-heptamethyltrisiloxane having the structural formula:
in addition, the application also provides a preparation method of the low molecular weight hydrogen-containing polysiloxane, which comprises the following steps: reacting the reaction raw materials under the action of the solid acid catalyst, removing the solid acid catalyst, and distilling the residual reaction product;
wherein the reaction raw materials comprise high hydrogen silicone oil and a blocking agent.
For reference, the structural formula of the high hydrogen silicone oil is:
where m=45-70, such as 45, 50, 55, 60, 65 or 70, etc., may be any other value within the range of 45-70.
For reference, the blocking agent is hexamethyldisiloxane.
In alternative embodiments, the molar ratio of the high hydrogen silicone oil to the endcapping agent may be in the range of 1:30 to 80, such as 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:70, 1:75, or 1:80, etc., as well as any other value in the range of 1:30 to 80.
If the molar ratio of the high hydrogen silicone oil to the end-capping agent is less than 1:30 or greater than 1:80, the yield of the target product is easily low.
The amount of the solid acid catalyst used is 0.4 to 1.0wt%, such as 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt% or 1.0wt%, etc., of the total amount of the reaction materials, and may be any other value within the range of 0.4 to 1.0wt%.
If the solid acid catalyst is used in an excessive amount (more than 1.0 wt%), more byproducts are produced in the reaction; if the amount of the solid acid catalyst used is low (less than 0.4 wt%), the conversion of the raw material will be low.
In the application, the reaction of the reaction raw materials under the action of the solid acid catalyst is carried out for 2-6 hours at the temperature of 40-80 ℃.
Specifically, the reaction temperature may be 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or the like, or any other value within the range of 40 to 80 ℃. The reaction time may be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h, etc., or any other value within the range of 2 to 6h.
If the reaction temperature of the reaction raw materials under the action of the solid acid catalyst is lower than 40 ℃ or the reaction time is shorter than 2 hours, less target products are generated in the reaction; if the reaction temperature is higher than 80℃or the reaction time is longer than 6 hours, the increase of by-products generated by the reaction is liable to occur.
After the reaction is completed, the solid acid catalyst may be separated and removed by filtration. The remaining reaction product is then distilled in the following manner.
For reference, distillation may include: removing low boiling point materials below 130 ℃ in the reaction product by atmospheric distillation, and obtaining a fraction (namely 1,3, 5-heptamethyltrisiloxane with purity more than 95%) at 141-142 ℃ by atmospheric distillation.
On the premise of bearing, the low molecular weight hydrogen-containing polysiloxane prepared by the method has the advantages of high target product yield, simple preparation process, low reaction temperature, energy conservation and consumption reduction, less produced pollutants and environmental protection.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1
This example provides a low molecular weight hydrogen-containing polysiloxane prepared by:
(1) Preparation of solid acid catalyst
Step (1): 40g of technical grade Al are reacted with 2 (SO 4 ) 3 Dissolving in deionized water at 80deg.CStirring for 3 hours to prepare 0.8g/mL aluminum sulfate solution, adding 15.6g LUDOX AS-30 silica sol, regulating the pH of the system to 8-9 by using 25wt% ammonia water, stirring for 10 hours, filtering and washing with deionized water for 3 times, drying in a vacuum drying oven at 80 ℃ for 12 hours, and roasting at 500 ℃ for 3 hours to obtain precursor silicon-aluminum oxide (wherein Si: al=1:3).
Step (2): 10g of precursor silicon aluminum oxide is weighed, 100mL of 1.0mol/L sulfuric acid solution is added, stirring is carried out for 3 hours at 80 ℃, drying is carried out for 15 hours in a vacuum drying oven at 80 ℃, and then the precursor silicon aluminum oxide is ground into fine powder, thus obtaining the solid acid catalyst with the particle size of 300-400 meshes.
(2) Preparation of low molecular weight hydrogen-containing polysiloxanes
According to the mol ratio of 1:40, respectively adding high hydrogen silicone oil (structural formula ism=55) and hexamethyldisiloxane, stirring and heating to 60 ℃, adding a solid acid catalyst accounting for 0.9wt% of the total mass of the raw materials (high hydrogen silicone oil and hexamethyldisiloxane) for telomerization for 3 hours, and separating the catalyst by filtration after the reaction is finished to obtain a crude product of low molecular weight hydrogen-containing polysiloxane. Removing low boiling point substances below 130 ℃ in the reaction product through atmospheric distillation, and obtaining a fraction of 141-142 ℃ through atmospheric distillation to obtain the 1,3, 5-heptamethyltrisiloxane.
The yield of 1,3, 5-heptamethyltrisiloxane was calculated as the formula yield = (fraction mass/total mass of raw material) ×100% based on the fraction mass and total mass of raw material, and was 33.7%, the same applies below. The content of 1,3, 5-heptamethyltrisiloxane in the fraction was 98.8wt% as determined by gas chromatography.
Example 2
This example provides a low molecular weight hydrogen-containing polysiloxane prepared by:
(1) Preparation of solid acid catalyst
Step (1): 40g of technical grade Al are reacted with 2 (SO 4 ) 3 Dissolving in deionized water, stirring at 80deg.C for 3 hr to obtain 0.9g/mL aluminum sulfate solutionThen, 11.7g of LUDOX AS-40 silica sol was added thereto, the pH of the system was adjusted to 8-9 with 20wt% ammonia water, stirred for 8 hours, filtered and washed 3 times with deionized water, dried in a vacuum oven at 90℃for 12 hours, and calcined at 400℃for 4 hours to obtain a precursor silicon aluminum oxide (wherein Si: al=1:3).
Step (2): 10g of precursor silicon aluminum oxide is weighed, 100mL of 1.0mol/L sulfuric acid solution is added, stirring is carried out for 4 hours at 80 ℃, drying is carried out for 18 hours in a vacuum drying oven at 80 ℃, and then the precursor silicon aluminum oxide is ground into fine powder, thus obtaining the solid acid catalyst with the particle size of 300-400 meshes.
(2) Preparation of low molecular weight hydrogen-containing polysiloxanes
Adding high hydrogen silicone oil (structural formula ism=60) and hexamethyldisiloxane, stirring and heating to 50 ℃, adding a solid acid catalyst accounting for 1.0wt% of the total mass of the raw materials, and carrying out telomerization for 4 hours, and separating the catalyst by filtration after the reaction is finished, thus obtaining a crude product of the low molecular weight hydrogen-containing polysiloxane. Removing low boiling point substances below 130 ℃ in the reaction product through atmospheric distillation, and obtaining a fraction of 141-142 ℃ through atmospheric distillation to obtain the 1,3, 5-heptamethyltrisiloxane.
According to the distillate quality and the total raw material quality, the yield of the 1,3, 5-heptamethyltrisiloxane is calculated to be 31.9 percent, the content of 1,3, 5-heptamethyltrisiloxane in the fraction was 97.8wt% as determined by gas chromatography.
Example 3
This example provides a low molecular weight hydrogen-containing polysiloxane prepared by:
(1) Preparation of solid acid catalyst
Step (1): 40g of technical grade Al are reacted with 2 (SO 4 ) 3 Dissolving in deionized water, stirring at 90deg.C for 2 hr to obtain 0.7g/mL aluminum sulfate solution, adding 10.0g LUDOX HS-40 silica sol, adjusting pH to 8-9 with 25wt% ammonia water, stirring for 10 hr, filtering, washing with deionized water for 3 times, and vacuum-treating at 90deg.CDrying in an empty drying oven for 12 hours, and roasting at 400 ℃ for 3 hours to obtain the precursor silicon-aluminum oxide (wherein Si is Al=1:3.5).
Step (2): 10g of precursor silicon aluminum oxide is weighed, 70mL of 1.5mol/L sulfuric acid solution is added, stirring is carried out for 5 hours at 70 ℃, drying is carried out for 12 hours in a vacuum drying oven at 90 ℃, and then the precursor silicon aluminum oxide is ground into fine powder, thus obtaining the solid acid catalyst with the particle size of 300-400 meshes.
(2) Preparation of low molecular weight hydrogen-containing polysiloxanes
Adding high hydrogen silicone oil (structural formula ism=45) and hexamethyldisiloxane, stirring and heating to 40 ℃, adding a solid acid catalyst accounting for 0.8wt% of the total mass of the raw materials, and carrying out telomerization reaction for 6 hours, and separating the catalyst by filtration after the reaction is finished, thus obtaining a crude product of the low molecular weight hydrogen-containing polysiloxane. Removing low boiling point substances below 130 ℃ in the reaction product through atmospheric distillation, and obtaining a fraction of 141-142 ℃ through atmospheric distillation to obtain the 1,3, 5-heptamethyltrisiloxane.
According to the distillate quality and the total raw material quality, the yield of the 1,3, 5-heptamethyltrisiloxane is calculated to be 34.2 percent, the content of 1,3, 5-heptamethyltrisiloxane in the fraction was 99.1wt% as determined by gas chromatography.
Example 4
This example provides a low molecular weight hydrogen-containing polysiloxane prepared by:
(1) Preparation of solid acid catalyst
Step (1): 40g of technical grade Al are reacted with 2 (SO 4 ) 3 Dissolving in deionized water, stirring at 80deg.C for 4 hr to obtain 0.9g/mL aluminum sulfate solution, adding 7.5g LUDOX AS-40 silica sol, adjusting pH to 8-9 with 25wt% ammonia water, stirring for 10 hr, filtering, washing with deionized water for 3 times, drying at 80deg.C in vacuum oven for 15 hr, and calcining at 500deg.C for 2 hr to obtain precursor silicon aluminum oxide (wherein Si: al=1:4.7).
Step (2): 10g of precursor silicon aluminum oxide is weighed, 80mL of 1.2mol/L sulfuric acid solution is added, stirring is carried out for 6 hours at 70 ℃, drying is carried out for 18 hours in a vacuum drying oven at 80 ℃, and then the precursor silicon aluminum oxide is ground into fine powder, thus obtaining the solid acid catalyst with the particle size of 300-400 meshes.
(2) Preparation of low molecular weight hydrogen-containing polysiloxanes
Adding high hydrogen silicone oil (structural formula ism=70) and hexamethyldisiloxane, stirring and heating to 70 ℃, adding a solid acid catalyst accounting for 0.7wt% of the total mass of the raw materials for telomerization for 2 hours, and separating the catalyst by filtration after the reaction is finished to obtain a crude product of the low molecular weight hydrogen-containing polysiloxane. Removing low boiling point substances below 130 ℃ in the reaction product through atmospheric distillation, and obtaining a fraction of 141-142 ℃ through atmospheric distillation to obtain the 1,3, 5-heptamethyltrisiloxane.
According to the distillate quality and the total raw material quality, the yield of the 1,3, 5-heptamethyltrisiloxane is calculated to be 30.5 percent, the content of 1,3, 5-heptamethyltrisiloxane in the fraction was 98.3wt% as determined by gas chromatography.
Example 5
This example provides a low molecular weight hydrogen-containing polysiloxane prepared by:
(1) Preparation of a solid acid catalyst: the same as in example 1.
(2) Preparation of low molecular weight hydrogen-containing polysiloxanes
Adding high hydrogen silicone oil (structural formula ism=45) and hexamethyldisiloxane, stirring and heating to 80 ℃, adding a solid acid catalyst accounting for 0.4wt% of the total mass of the raw materials for telomerization for 2 hours, and separating the catalyst by filtration after the reaction is finished to obtain a crude product of the low molecular weight hydrogen-containing polysiloxane. Removing low boiling point material below 130 deg.C from reaction product by atmospheric distillation, thenDistilling at normal pressure to obtain 141-142 deg.C fraction to obtain 1,3, 5-heptamethyltrisiloxane.
According to the distillate quality and the total raw material quality, the yield of the 1,3, 5-heptamethyltrisiloxane is calculated to be 34.7 percent, the content of 1,3, 5-heptamethyltrisiloxane in the fraction was 99.3wt% as determined by gas chromatography.
Example 6
This example provides a low molecular weight hydrogen-containing polysiloxane prepared by:
(1) Preparation of solid acid catalyst
Step (1): 40g of technical grade Al are reacted with 2 (SO 4 ) 3 Dissolving in deionized water, stirring at 80deg.C for 3 hr to obtain 0.9g/mL aluminum sulfate solution, adding 8.8g LUDOX HS-40 silica sol, adjusting pH to 8-9 with 30wt% ammonia water, stirring for 10 hr, filtering, washing with deionized water for 3 times, drying at 80deg.C in vacuum oven for 15 hr, and calcining at 400deg.C for 4 hr to obtain precursor silicon-aluminum oxide (wherein Si: al=1:4).
Step (2): 10g of precursor silicon aluminum oxide is weighed, 80mL of 1.2mol/L sulfuric acid solution is added, stirring is carried out for 3 hours at 80 ℃, drying is carried out for 15 hours in a vacuum drying oven at 90 ℃, and then the precursor silicon aluminum oxide is ground into fine powder, thus obtaining the solid acid catalyst with the particle size of 300-400 meshes.
(2) Preparation of low molecular weight hydrogen-containing polysiloxanes: the same as in example 1.
According to the distillate quality and the total raw material quality, the yield of the 1,3, 5-heptamethyltrisiloxane is calculated to be 32.9 percent, the content of 1,3, 5-heptamethyltrisiloxane in the fraction was 98.4wt% as determined by gas chromatography.
Comparative example 1
The difference between this comparative example and example 1 is that: the drying conditions of the precursor are different.
(1) Preparation of a solid acid catalyst:
step (1): 40g of technical grade Al are reacted with 2 (SO 4 ) 3 Dissolved in deionized water, stirred at 80℃for 3 hours to prepare 0.8g/mL aluminum sulfate solution, and 15 was added thereto.6g of LUDOX AS-30 silica sol, adjusting the pH of the system to 8-9 with 25wt% ammonia water, stirring for 10 hours, filtering and washing with deionized water 3 times, drying in a forced air drying oven at 120 ℃ for 12 hours, and roasting at 500 ℃ for 3 hours to obtain a precursor silicon aluminum oxide (wherein Si: al=1:3).
The rest of the procedure is the same as in example 1.
According to the distillate quality and the total raw material quality, the yield of the 1,3, 5-heptamethyltrisiloxane is calculated to be 13.1 percent, the content of 1,3, 5-heptamethyltrisiloxane in the fraction was 98.2wt% as determined by gas chromatography.
Comparative example 2
The difference between this comparative example and example 1 is that: the firing conditions of the precursors are different.
(1) Preparation of a solid acid catalyst:
step (1): 40g of technical grade Al are reacted with 2 (SO 4 ) 3 Dissolving in deionized water, stirring at 80deg.C for 3 hr to obtain 0.8g/mL aluminum sulfate solution, adding 15.6g LUDOX AS-30 silica sol, adjusting pH to 8-9 with 25wt% ammonia water, stirring for 10 hr, filtering, washing with deionized water for 3 times, drying at 80deg.C in vacuum oven for 12 hr, and calcining at 200deg.C for 3 hr to obtain precursor silicon aluminum oxide (wherein Si: al=1:3).
The rest of the procedure is the same as in example 1.
According to the distillate quality and the total raw material quality, the yield of the 1,3, 5-heptamethyltrisiloxane is calculated to be 14.6 percent, the content of 1,3, 5-heptamethyltrisiloxane in the fraction was 97.1wt% as determined by gas chromatography.
Comparative example 3
The difference between this comparative example and example 1 is that: the molar ratio of silicon to aluminum in the solid acid catalyst is different.
(1) Preparation of a solid acid catalyst:
step (1): 40g of technical grade Al are reacted with 2 (SO 4 ) 3 Dissolving in deionized water, stirring at 80deg.C for 3 hr to obtain 0.8g/mL aluminum sulfate solution, adding 6.7g LUDOX AS-30 silica sol, adjusting pH to 8-9 with 25wt% ammonia water, stirring for 10 hrAt this time, the precursor silicon aluminum oxide (where Si: al=1:7) was prepared by filtering and washing with deionized water 3 times, drying in a vacuum oven at 80 ℃ for 12 hours, and baking at 500 ℃ for 3 hours.
The rest of the procedure is the same as in example 1.
According to the distillate quality and the total raw material quality, the yield of the 1,3, 5-heptamethyltrisiloxane is calculated to be 19.4 percent, the content of 1,3, 5-heptamethyltrisiloxane in the fraction was 97.9wt% as determined by gas chromatography.
Comparative example 4
The difference between this comparative example and example 1 is that: the sulfuric acid solutions used to acidify the precursor are at different concentrations.
(1) Preparation of a solid acid catalyst:
step (1) is the same as in example 1.
Step (2): 10g of precursor silicon aluminum oxide is weighed, 100mL of 0.5mol/L sulfuric acid solution is added, stirring is carried out for 3 hours at 80 ℃, drying is carried out for 15 hours in a vacuum drying oven at 80 ℃, and then the precursor silicon aluminum oxide is ground into fine powder, thus obtaining the solid acid catalyst with the particle size of 300-400 meshes.
The rest of the procedure is the same as in example 1.
According to the distillate quality and the total raw material quality, the yield of the 1,3, 5-heptamethyltrisiloxane is calculated to be 17.7 percent, the content of 1,3, 5-heptamethyltrisiloxane in the fraction was 97.6wt% as determined by gas chromatography.
As can be seen from a comparison of example 1 and comparative examples 1-4: when the drying condition of the precursor, the roasting condition of the precursor, the silicon-aluminum mole ratio in the solid acid catalyst or the concentration of the sulfuric acid solution used for acidifying the precursor is changed and exceeds the range provided by the application in the preparation process of the solid acid catalyst, the yield and purity of the 1,3, 5-heptamethyltrisiloxane are reduced.
In conclusion, the preparation method of the solid acid catalyst provided by the application is simple, raw materials are easy to obtain, and the catalytic activity is high. The solid acid catalyst is applied to the production of low molecular weight hydrogen-containing polysiloxane, so that the low molecular weight hydrogen-containing polysiloxane with higher yield can be obtained, the whole preparation process is simple and easy to operate, the required reaction temperature is low, the energy conservation and consumption reduction are facilitated, the produced pollutants are less, and the preparation method is environment-friendly.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A solid acid catalyst, characterized in that the solid acid catalyst is prepared by the following method: carrying out coprecipitation reaction on aluminum sulfate solution, silica sol and ammonia water, and roasting a solid obtained by the coprecipitation reaction to obtain a precursor silicon-aluminum oxide; then mixing with sulfuric acid solution for reaction, and drying;
the coprecipitation reaction is carried out for 8-10 hours under the condition that the pH value is 8-9; the concentration of the aluminum sulfate solution is 0.6-0.9g/mL, and the concentration of the ammonia water is 20-30wt%; roasting is carried out for 2-4 hours at 400-500 ℃; the model of the silica sol is LUDOX AS-30, LUDOX AS-40 or LUDOX HS-40; the concentration of the sulfuric acid solution is 1.0-1.5mol/L, and the volume of the sulfuric acid solution is 70-100mL; mixing the precursor silicon-aluminum oxide with the sulfuric acid solution at 70-80 ℃ for 3-6h; drying is carried out for 12-18h under the condition of 80-90 ℃; the mole ratio of the silicon element to the aluminum element in the solid acid catalyst is 1:3-5.
2. The solid acid catalyst according to claim 1, further comprising a grinding step after drying.
3. The solid acid catalyst according to claim 1, wherein the solid acid catalyst has a particle size of 300 to 400 mesh.
4. A low molecular weight hydrogen-containing polysiloxane, characterized in that the solid acid catalyst as claimed in any one of claims 1 to 3 is used as a catalyst for the reaction in the preparation of the low molecular weight hydrogen-containing polysiloxane.
5. The low molecular weight hydrogen-containing polysiloxane according to claim 4, wherein the low molecular weight hydrogen-containing polysiloxane is 1,3, 5-heptamethyltrisiloxane having the structural formula:
6. the method for producing a low molecular weight hydrogen-containing polysiloxane according to claim 4 or 5, comprising the steps of: reacting the reaction raw materials under the action of the solid acid catalyst as claimed in any one of claims 1 to 3, then removing the solid acid catalyst, and distilling the residual reaction product;
wherein the reaction raw materials comprise high-hydrogen silicone oil and a blocking agent.
7. The preparation method according to claim 6, wherein the high hydrogen silicone oil has a structural formula:
wherein m=45-70;
and/or the end-capping agent is hexamethyldisiloxane.
8. The preparation method according to claim 7, wherein the molar ratio of the high hydrogen silicone oil to the blocking agent is 1:30-80;
and/or the solid acid catalyst is used in an amount of 0.4 to 1.0wt% based on the total amount of the reaction raw materials.
9. The process of claim 6, wherein the reaction of the starting materials under the action of the solid acid catalyst is carried out at 40-80℃for 2-6 hours.
10. The method of claim 6, wherein distilling comprises: removing low boiling point material below 130 ℃ in the reaction product by atmospheric distillation, and obtaining the fraction at 141-142 ℃ by atmospheric distillation.
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