CN102491993A - Preparation method of lithium trimethylsilanolate - Google Patents
Preparation method of lithium trimethylsilanolate Download PDFInfo
- Publication number
- CN102491993A CN102491993A CN2011103788249A CN201110378824A CN102491993A CN 102491993 A CN102491993 A CN 102491993A CN 2011103788249 A CN2011103788249 A CN 2011103788249A CN 201110378824 A CN201110378824 A CN 201110378824A CN 102491993 A CN102491993 A CN 102491993A
- Authority
- CN
- China
- Prior art keywords
- lithium
- preparation
- lithium hydroxide
- raw material
- trimethylsilanolate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OXOZHAWWRPCVGL-UHFFFAOYSA-N lithium;trimethyl(oxido)silane Chemical compound [Li+].C[Si](C)(C)[O-] OXOZHAWWRPCVGL-UHFFFAOYSA-N 0.000 title claims abstract 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract 21
- 229910052744 lithium Inorganic materials 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 19
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 17
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 17
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 2
- -1 polysiloxanes Polymers 0.000 abstract description 37
- 229920001296 polysiloxane Polymers 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 6
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 abstract description 5
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 4
- 239000003999 initiator Substances 0.000 abstract description 2
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 239000012046 mixed solvent Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 125000001979 organolithium group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000012653 anionic ring-opening polymerization Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
Abstract
The invention relates to a preparation method of lithium trimethylsilanolate. According to the method, lithium trimethylsilanolate is prepared through reacting a lithium hydroxide raw material with hexamethyldisiloxane under the protection of N2 with waterless ethanol, methanol or butanol and cyclohexane as a mixed solvent. The method has the characteristics of simple synthetic process, cheap and easily available raw material, and low cost. Obtained lithium trimethylsilanolate is mainly used for initiating the ring-opening polymerisation of cyclotrisiloxane as an initiator to prepare block polysiloxanes or single-terminal function group polysiloxanes.
Description
Technical field
The present invention relates to a kind of preparation method of trimethyl silicane lithium alkoxide, belong to the synthesis technical field of lithium based compound.
Background technology
Prepare in the used catalyzer of ZGK 5; Alkali metal cpds such as oxyhydroxide like potassium, sodium, lithium; When the lithium based compound makes the cyclotrisiloxane ring-opening polymerization prepare ZGK 5; Can only open the siliconoxygen bond in the cyclotrisiloxane, and the Si-O-Si key in can not the cracking linear polysiloxanes is suitable for preparing block polysiloxane or single-ended functional group polysiloxane.Such catalyzer mainly comprises n-Butyl Lithium, isobutyl-lithium and trimethyl silicane lithium alkoxide etc., wherein uses butyllithium, isobutyl-lithium to prepare block polysiloxane or single-ended functional group polysiloxane costs an arm and a leg.So research and development have that synthesis technique is simple, raw material cheaply is easy to get, trimethyl silicane lithium alkoxide with low cost has broad application prospects.The trimethyl silicane lithium alkoxide belongs to non-equilibrium catalyzer, as cyclosiloxane anionic ring-opening polymerization catalyzer, is particularly suitable for causing the cyclotrisiloxane ring-opening polymerization and prepares block polysiloxane or single-ended functional group polysiloxane.
In the prior art, relevant trimethyl silicane lithium alkoxide is synthetic mainly contains: 1, prepare trimethyl silicane lithium alkoxide report with phenyl lithium cracking SWS-F 221, referring to Reich; H.J.; Journal of the American Chemical Society, 1985,107 (13): 4101-4103; 2, prepare the trimethyl silicane lithium alkoxide with lithium methide cracking SWS-F 221, referring to Preuss, F., Zeitschrift fuer Naturforschung, B:Chemical Sciences, 2002,57 (7): 726-730.All be to use price comparison expensive organolithium and SWS-F 221 prepared in reaction trimethyl silicane lithium alkoxide in the prior art scheme.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of simple, safe and economic method for preparing the trimethyl silicane lithium alkoxide.
Technical scheme of the present invention is following:
A kind of preparation method of trimethyl silicane lithium alkoxide adds SWS-F 221, Lithium Hydroxide MonoHydrate raw material and mixed organic solvents, at N in reactor drum
2Protection down is heated to solvent refluxing, 24～48 hours reaction times, after reaction finishes, naturally cool to room temperature, and to filter, gained solid drying 2～4 hours under 80 ℃, 0.1MPa condition obtains trimethyl silicane lithium alkoxide product.Sealing is preserved.Said Lithium Hydroxide MonoHydrate raw material is the monohydrate of Lithium Hydroxide MonoHydrate, and molecular formula is LiOHH
2O.
Said mixed organic solvents is the combination of absolute ethyl alcohol, butanols or methyl alcohol and hexanaphthene.
Preferred according to the present invention, said SWS-F 221 and Lithium Hydroxide MonoHydrate raw material (LiOHH
2O) mol ratio is 0.5～2: 1; Most preferred, SWS-F 221 and Lithium Hydroxide MonoHydrate raw material (LiOHH
2O) mol ratio is 1: 1.
Preferred according to the present invention, the consumption of said mixed organic solvents is SWS-F 221 3～6 times of weight.
Preferred according to the present invention, what absolute ethyl alcohol, butanols or methyl alcohol and hexanaphthene can arbitrary proportions in the said mixed organic solvents mixes; Further preferred, the mass ratio of absolute ethyl alcohol, butanols or methyl alcohol and hexanaphthene is 1～2: 1 in the said mixed organic solvents.
Preferred according to the present invention, said mixed organic solvents is absolute ethyl alcohol and hexanaphthene (1～1.5): the combination of 1 mass ratio.
Preferred according to the present invention, to keep violent stirring and N in SWS-F 221 and the Lithium Hydroxide MonoHydrate reaction process
2Protection is heated to solvent refluxing.Mixing speed is 100～150 rev/mins.
Preferred according to the present invention, the water that generates in the reaction process is in time separated from reaction system.Said reactor drum is to be equipped with water trap, prolong, churned mechanically reactor drum.
The trimethyl silicane lithium alkoxide of the present invention's preparation is used to cause the cyclotrisiloxane ring-opening polymerization and prepares block polysiloxane or single-ended functional group polysiloxane mainly as initiator.
The present invention is unexpected to find that SWS-F 221 and Lithium Hydroxide MonoHydrate back flow reaction obtain the trimethyl silicane lithium alkoxide in mixed organic solvents.And the organic solvent that uses one of them merely can't obtain trimethyl silicane lithium alkoxide product.Method raw material of the present invention cheaply be easy to get and need not water treatment, simple to operate, aftertreatment is simple.Avoid the use of expensive organolithium raw material, the suitability for industrialized production that helps the trimethyl silicane lithium alkoxide is used.
Embodiment
Below in conjunction with embodiment the present invention is further specified, but be not limited thereto.Used Lithium Hydroxide MonoHydrate is a monohydrate among the embodiment, and molecular formula is LiOHH
2O, Tianjin good fortune chemical reagent in morning factory produces.
Embodiment 1
In assembling water trap, serpentine condenser, churned mechanically 250ml four-hole boiling flask, put into 4.2g Lithium Hydroxide MonoHydrate raw material (LiOHH
2O), the 16.6g SWS-F 221,40g hexanaphthene and 50g absolute ethyl alcohol are heated to solvent refluxing, N
2Protection was reacted 35 hours down, kept violent stirring in the reaction process, and mixing speed is 120 rev/mins.Naturally cool to room temperature after reaction finishes, filter, get solid and be the trimethyl silicane lithium alkoxide in 0.1MPa, 80 ℃ of dryings 2.5 hours, after the cooling 8.9g white trimethyl silicane lithium alkoxide solid phase prod, productive rate is 93%.N is filled in sealing
2Preserve.
Embodiment 2
In assembling water trap, serpentine condenser, churned mechanically 250ml four-hole boiling flask, put into 12.6g Lithium Hydroxide MonoHydrate LiOHH
2O, the 40g SWS-F 221,60g hexanaphthene and 60g absolute ethyl alcohol are heated to solvent refluxing, N
2Protection was reacted 27 hours down.Keep violent stirring in the reaction process, mixing speed is 120 rev/mins.Naturally cool to room temperature after reaction finishes, filter, the gained solid is the trimethyl silicane lithium alkoxide in 0.1MPa, 80 ℃ of dryings 3 hours, after the cooling 26g white trimethyl silicane lithium alkoxide solid phase prod, productive rate is 90%.N is filled in sealing
2Preserve.
Embodiment 3
In assembling water trap, serpentine condenser, churned mechanically 250ml four-hole boiling flask, put into 4.2g Lithium Hydroxide MonoHydrate LiOHH
2O, the 16g SWS-F 221,20g hexanaphthene and 30g absolute ethyl alcohol are heated to solvent refluxing, N
2Protection was reacted 30 hours down.Keep in the reaction process stirring, mixing speed is 100 rev/mins.Naturally cool to room temperature after reaction finishes, filter, the gained solid is the trimethyl silicane lithium alkoxide, in 0.1MPa, 80 ℃ of dryings 3.5 hours, after the cooling 7.7g white trimethyl silicane lithium alkoxide solid phase prod, productive rate is 80.2%.N is filled in sealing
2Preserve.
Embodiment 4
In assembling water trap, serpentine condenser, churned mechanically 250ml four-hole boiling flask, put into 5g Lithium Hydroxide MonoHydrate LiOHH
2O, the 18g SWS-F 221,20g hexanaphthene and 40g anhydrous methanol are heated to solvent refluxing, N
2Protection was reacted 26 hours down.Keep in the reaction process stirring, mixing speed is 150 rev/mins.Naturally cool to room temperature after reaction finishes, filter, the gained solid is the trimethyl silicane lithium alkoxide, in 0.1MPa, 80 ℃ of dryings 3.5 hours, after the cooling 8g white trimethyl silicane lithium alkoxide solid phase prod, productive rate is 70%.N is filled in sealing
2Preserve.
Comparative Examples:
1, in assembling water trap, serpentine condenser, churned mechanically 250ml four-hole boiling flask, puts into 4.2g Lithium Hydroxide MonoHydrate LiOHH
2O, the 16g SWS-F 221, the 60g hexanaphthene is heated to solvent refluxing, N
2Protection was reacted 30 hours down.Keep violent stirring in the reaction process, mixing speed is 100 rev/mins.Reaction naturally cools to room temperature after finishing, and filters, and the gained solid is a Lithium Hydroxide MonoHydrate, and trimethyl silicane lithium alkoxide product yield is 0.
2, in assembling water trap, serpentine condenser, churned mechanically 250ml four-hole boiling flask, put into 4.2g Lithium Hydroxide MonoHydrate LiOHH
2O, the 16g SWS-F 221, the 40g absolute ethyl alcohol is heated to solvent refluxing, N
2Protection was reacted 30 hours down.Keep violent stirring in the reaction process, mixing speed is 100 rev/mins.Reaction naturally cools to room temperature after finishing, and filters, and the gained solid is a Lithium Hydroxide MonoHydrate, and trimethyl silicane lithium alkoxide product yield is 0.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110378824.9A CN102491993B (en) | 2011-11-24 | 2011-11-24 | Preparation method of lithium trimethylsilanolate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110378824.9A CN102491993B (en) | 2011-11-24 | 2011-11-24 | Preparation method of lithium trimethylsilanolate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102491993A true CN102491993A (en) | 2012-06-13 |
| CN102491993B CN102491993B (en) | 2014-03-12 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110378824.9A Expired - Fee Related CN102491993B (en) | 2011-11-24 | 2011-11-24 | Preparation method of lithium trimethylsilanolate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102491993B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254898A (en) * | 2015-11-04 | 2016-01-20 | 山东东岳有机硅材料有限公司 | Preparation method of polypmethyl phenyl siloxane alcohol lithium |
| CN105330684A (en) * | 2014-08-08 | 2016-02-17 | 上海楚青新材料科技有限公司 | Preparation method for potassium trimethylsilanolate |
| CN113087907A (en) * | 2019-12-23 | 2021-07-09 | 万华化学集团股份有限公司 | Lithium silanol and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1080140A1 (en) * | 1998-04-09 | 2001-03-07 | Minnesota Mining And Manufacturing Company | Multi-layer compositions comprising a fluoropolymer |
| CN1477155A (en) * | 2003-07-04 | 2004-02-25 | 山东大学 | High-temperature vulcanized silicone rubber cross-linked by halogenated hydrocarbon-based compounds and its preparation method |
| CN101838393A (en) * | 2010-04-29 | 2010-09-22 | 山东大学 | Method for synthesizing high-molecular-weight ethyl polysiloxane |
-
2011
- 2011-11-24 CN CN201110378824.9A patent/CN102491993B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1080140A1 (en) * | 1998-04-09 | 2001-03-07 | Minnesota Mining And Manufacturing Company | Multi-layer compositions comprising a fluoropolymer |
| CN1477155A (en) * | 2003-07-04 | 2004-02-25 | 山东大学 | High-temperature vulcanized silicone rubber cross-linked by halogenated hydrocarbon-based compounds and its preparation method |
| CN101838393A (en) * | 2010-04-29 | 2010-09-22 | 山东大学 | Method for synthesizing high-molecular-weight ethyl polysiloxane |
Non-Patent Citations (1)
| Title |
|---|
| MARIJA L等，: "Scope and Limitations of Sodium and Potassium Trimethylsilanolate as Reagents for Conversion of Esters to Carboxylic Acids", 《CROATICA. CHEMICA. ACTA.》, vol. 80, no. 1, 31 December 2007 (2007-12-31), pages 109 - 115, XP002557064 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330684A (en) * | 2014-08-08 | 2016-02-17 | 上海楚青新材料科技有限公司 | Preparation method for potassium trimethylsilanolate |
| CN105254898A (en) * | 2015-11-04 | 2016-01-20 | 山东东岳有机硅材料有限公司 | Preparation method of polypmethyl phenyl siloxane alcohol lithium |
| CN105254898B (en) * | 2015-11-04 | 2018-11-02 | 山东东岳有机硅材料股份有限公司 | A kind of preparation method of polymethylphenylsiloxane lithium alkoxide |
| CN113087907A (en) * | 2019-12-23 | 2021-07-09 | 万华化学集团股份有限公司 | Lithium silanol and preparation method and application thereof |
| CN113087907B (en) * | 2019-12-23 | 2023-01-13 | 万华化学集团股份有限公司 | Lithium silanol and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN102491993B (en) | 2014-03-12 |
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