CN111004268A - Method for preparing organic silicon by hydrolyzing and condensing chlorosilane - Google Patents
Method for preparing organic silicon by hydrolyzing and condensing chlorosilane Download PDFInfo
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- CN111004268A CN111004268A CN201911336467.2A CN201911336467A CN111004268A CN 111004268 A CN111004268 A CN 111004268A CN 201911336467 A CN201911336467 A CN 201911336467A CN 111004268 A CN111004268 A CN 111004268A
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- Prior art keywords
- chlorosilane
- hydrolyzing
- condensing
- acid
- preparing
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- 239000005046 Chlorosilane Substances 0.000 title claims abstract description 36
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 20
- 239000010703 silicon Substances 0.000 title claims abstract description 20
- 230000003301 hydrolyzing effect Effects 0.000 title claims abstract description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 21
- 229960000583 acetic acid Drugs 0.000 claims abstract description 13
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 13
- 238000009833 condensation Methods 0.000 claims abstract 3
- 230000005494 condensation Effects 0.000 claims abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000413 hydrolysate Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- 239000012456 homogeneous solution Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006482 condensation reaction Methods 0.000 abstract description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 16
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 150000001367 organochlorosilanes Chemical class 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- -1 polysiloxane Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a method for preparing organic silicon by chlorosilane hydrolytic condensation, which adopts weak acid glacial acetic acid to replace strong acid such as hydrochloric acid, concentrated sulfuric acid and the like for hydrolytic condensation reaction, thereby not only reducing the corrosion of acid to equipment, avoiding the generation of a large amount of waste acid liquid, saving the production cost, but also reducing the temperature change in the hydrolytic condensation reaction, leading the purity of organic siloxane products to be higher and improving the quality of organic siloxane.
Description
Technical Field
The invention belongs to the technical field of chemical industry, relates to the technical field of organic silicon production, and particularly relates to a method for preparing organic silicon by catalyzing chlorosilane with weak acid.
Background
The organochlorosilane is converted into the intermediate oligomeric organosiloxane with a linear or cyclic structure through hydrolysis and polycondensation, and is the basis for synthesizing silicone oil, silicone rubber and silicone resin.
In the prior art for producing organic silicon resin, strong acids such as hydrochloric acid and concentrated sulfuric acid are mostly adopted for carrying out hydrolysis condensation reaction, for example, the invention patent of China (a continuous concentrated acid hydrolysis method of organochlorosilane) (publication No. CN 103183827A) adopts the concentrated acid for carrying out hydrolysis condensation reaction, and the acids have corrosivity to reaction equipment and do not meet the current green environmental protection requirement. In the post-treatment process of the product polysiloxane, a large amount of waste water and waste acid are also generated, and the environmental pollution is caused.
Disclosure of Invention
The invention aims to reduce the corrosion of acid to equipment and obtain a pure product, and develops a method for preparing organic silicon by catalyzing chlorosilane by weak acid. The invention is realized by the following scheme:
a method for preparing organic silicon by hydrolyzing and condensing chlorosilane is characterized in that the chlorosilane is hydrolyzed and condensed under the action of glacial acetic acid.
Further, the method for preparing the organic silicon by hydrolyzing and condensing the chlorosilane comprises the following steps:
(1) adding deionized water, an organic solvent, chlorosilane and glacial acetic acid in a mass ratio of (2-6): 1-4): 0.3-3): 0.01-0.05 into a reaction kettle, controlling the temperature at 25-40 ℃, and stirring to form a homogeneous solution;
(2) adding chlorosilane into a reaction kettle, uniformly stirring, and continuously reacting for 4 hours;
(3) standing, removing an acid water layer, repeatedly washing the hydrolysate to be neutral by water, and then transferring the hydrolysate into a polycondensation kettle;
(4) preparing organic silicon at 60-100 ℃ under reduced pressure, and recovering to room temperature.
On the basis of the technical scheme, the chlorosilane RSiCl is prepared by the method3、RR’SiCl2RR 'R "SiCl wherein R, R', R" is one of phenyl, methyl, ethyl, propyl, isopropyl aliphatic and aromatic groups.
The organic solvent is preferably one of toluene, xylene, ethanol and isopropanol.
Further, the mass ratio of the deionized water, the organic solvent, the chlorosilane and the glacial acetic acid in the step (1) is preferably 3:1:0.5:0.01 or 4:2:1: 0.03.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, weak acid glacial acetic acid is adopted to replace strong acids such as hydrochloric acid and concentrated sulfuric acid for hydrolysis condensation reaction, so that the corrosion of acid to equipment is reduced, the generation of a large amount of waste acid is avoided, the post-treatment cost of the product is reduced, the production cost is saved, the temperature change in the hydrolysis condensation reaction is reduced, the purity of the organic siloxane product is higher, and the quality of the organic siloxane is improved.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
Unless otherwise specified, various starting materials of the present invention are commercially available; or prepared according to conventional methods in the art. Unless defined or indicated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
Example 1
A method for preparing organic silicon by hydrolyzing and condensing chlorosilane comprises the following steps:
(1) adding deionized water, toluene, chlorosilane and glacial acetic acid in a mass ratio of 3:1:0.5:0.01 into a reaction kettle, controlling the temperature at 35 ℃, and stirring to form a homogeneous solution;
(2) adding chlorosilane into a reaction kettle, uniformly stirring, and continuously reacting for 4 hours;
(3) standing, removing an acid water layer, repeatedly washing the hydrolysate to be neutral by water, and then transferring the hydrolysate into a polycondensation kettle;
(4) preparing organic silicon at 80 ℃ under reduced pressure, and recovering to room temperature.
Example 2
A method for preparing organic silicon by hydrolyzing and condensing chlorosilane comprises the following steps:
(1) adding deionized water, isopropanol, chlorosilane and glacial acetic acid in a mass ratio of 3:1:0.5:0.01 into a reaction kettle, controlling the temperature at 35 ℃, and stirring to form a homogeneous solution;
(2) adding chlorosilane into a reaction kettle, uniformly stirring, and continuously reacting for 4 hours;
(3) standing, removing an acid water layer, repeatedly washing the hydrolysate to be neutral by water, and then transferring the hydrolysate into a polycondensation kettle;
(4) preparing organic silicon at 80 ℃ under reduced pressure, and recovering to room temperature.
Example 3
A method for preparing organic silicon by hydrolyzing and condensing chlorosilane comprises the following steps:
(1) adding deionized water, toluene, chlorosilane and glacial acetic acid in a mass ratio of 4:2:1:0.03 into a reaction kettle, controlling the temperature at 35 ℃, and stirring to form a homogeneous solution;
(2) adding chlorosilane into a reaction kettle, uniformly stirring, and continuously reacting for 4 hours;
(3) standing, removing an acid water layer, repeatedly washing the hydrolysate to be neutral by water, and then transferring the hydrolysate into a polycondensation kettle;
(4) preparing organic silicon at 80 ℃ under reduced pressure, and recovering to room temperature.
Example 4
A method for preparing organic silicon by hydrolyzing and condensing chlorosilane comprises the following steps:
(1) adding deionized water, isopropanol, chlorosilane and glacial acetic acid in a mass ratio of 4:2:1:0.03 into a reaction kettle, controlling the temperature at 35 ℃, and stirring to form a homogeneous solution;
(2) adding chlorosilane into a reaction kettle, uniformly stirring, and continuously reacting for 4 hours;
(3) standing, removing an acid water layer, repeatedly washing the hydrolysate to be neutral by water, and then transferring the hydrolysate into a polycondensation kettle;
(4) preparing organic silicon at 80 ℃ under reduced pressure, and recovering to room temperature.
The applicant states that on the basis of the above-mentioned examples, the specific content point values of the components in the above-mentioned examples are combined with the technical solutions in the summary of the invention, so as to generate a new numerical range, which is also one of the described ranges of the present invention, and the present application does not list these numerical ranges again for the sake of brevity.
Claims (6)
1. A method for preparing organic silicon by hydrolyzing and condensing chlorosilane is characterized by comprising the following steps: in the method, chlorosilane is subjected to hydrolytic condensation under the action of glacial acetic acid.
2. The method for preparing organosilicon by hydrolyzing and condensing chlorosilane as claimed in claim 1, wherein the hydrolyzing and condensing reaction comprises the following steps:
(1) adding deionized water, an organic solvent, chlorosilane and glacial acetic acid in a mass ratio of (2-6): 1-4): 0.3-3): 0.01-0.05 into a reaction kettle, controlling the temperature at 25-40 ℃, and stirring to form a homogeneous solution;
(2) adding chlorosilane into a reaction kettle, uniformly stirring, and continuously reacting for 4 hours;
(3) standing, removing an acid water layer, repeatedly washing the hydrolysate to be neutral by water, and then transferring the hydrolysate into a polycondensation kettle;
(4) preparing organic silicon at 60-100 ℃ under reduced pressure, and recovering to room temperature.
3. The method for preparing organosilicon by hydrolytic condensation of chlorosilane as claimed in claim 1, wherein the chlorosilane RSiCl is added to the reaction mixture3、RR’SiCl2RR 'R "SiCl wherein R, R', R" is one of phenyl, methyl, ethyl, propyl, isopropyl aliphatic and aromatic groups.
4. The method for preparing organosilicon by hydrolyzing and condensing chlorosilane as claimed in claim 1, wherein the organic solvent is one of toluene, xylene, ethanol and isopropanol.
5. The method for preparing organosilicon by hydrolyzing and condensing chlorosilane as claimed in claim 1, wherein the mass ratio of the deionized water to the organic solvent to the chlorosilane to the glacial acetic acid in step (1) is 3:1:0.5: 0.01.
6. The method for preparing organosilicon by hydrolyzing and condensing chlorosilane as claimed in claim 1, wherein the mass ratio of the deionized water to the organic solvent to the chlorosilane to the glacial acetic acid in step (1) is 4:2:1: 0.03.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911336467.2A CN111004268A (en) | 2019-12-23 | 2019-12-23 | Method for preparing organic silicon by hydrolyzing and condensing chlorosilane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911336467.2A CN111004268A (en) | 2019-12-23 | 2019-12-23 | Method for preparing organic silicon by hydrolyzing and condensing chlorosilane |
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| CN111004268A true CN111004268A (en) | 2020-04-14 |
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| CN201911336467.2A Pending CN111004268A (en) | 2019-12-23 | 2019-12-23 | Method for preparing organic silicon by hydrolyzing and condensing chlorosilane |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019167770A1 (en) * | 2018-02-28 | 2019-09-06 | セントラル硝子株式会社 | Silicon compound containing hexafluoroisopropanol group, and method for producing same |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019167770A1 (en) * | 2018-02-28 | 2019-09-06 | セントラル硝子株式会社 | Silicon compound containing hexafluoroisopropanol group, and method for producing same |
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| PB01 | Publication | ||
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| RJ01 | Rejection of invention patent application after publication | ||
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Application publication date: 20200414 |