CN109320722A - A kind of synthesis preparation method of MQ type organic siliconresin - Google Patents
A kind of synthesis preparation method of MQ type organic siliconresin Download PDFInfo
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- CN109320722A CN109320722A CN201811070073.2A CN201811070073A CN109320722A CN 109320722 A CN109320722 A CN 109320722A CN 201811070073 A CN201811070073 A CN 201811070073A CN 109320722 A CN109320722 A CN 109320722A
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- silicon substrate
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- sulfate mixture
- sulfuric acid
- certain temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Silicon Polymers (AREA)
Abstract
The present invention relates to a kind of synthesis preparation method of MQ type organic siliconresin, this method feature includes mixing silicon substrate sulfate mixture with alkoxy silane, and solvent is added, water is added under fast stirring after mixing.Condensation reaction is hydrolyzed at a certain temperature, is neutralized and is post-processed after the completion of hydrolytic condensation.Present invention process can reduce the generation of gel, improve yield, and M/Q ratio may be implemented preferably to control closer to feed ratio to target product structure.
Description
Technical field
The present invention relates to a kind of preparation method of organic siliconresin more particularly to a kind of preparation methods of MQ type silicone resin.
Background technique
MQ resin is made of simple function chain link and tetrafunctional chain link, the polysiloxane with double-layer structure.It has
There are excellent high and low temperature resistance, corrosion resistance, adhesive property, radiation resistance etc., and is widely used as polysiloxanes
Surface treating agent, supporting material, tackifier or other additives.
MQ resin has a variety of preparation methods, is broadly divided into silester method and soluble glass method, respectively with silester or
The polymeric form and sodium metasilicate of silester are raw material progress.Wherein silester method is with its ease for operation, and yield is high, structure control
System is easy, and product molecular weight distribution is relatively narrow and is widely used.Such as it is described in United States Patent (USP) US4707531, hexamethyl two
Siloxanes is added silester after mixing with water, reaction mixture carries out static layering, lower organic layer by washing, concentration with
And target organosilicon MQ resin is obtained after filtering.It is for another example described in Chinese patent CN106750304, poly- ethyl orthosilicate and pregnancy
Hydrolysis of the base disiloxane under sulfuric acid catalysis adds alkali neutralization after the completion of certain temperature and time response, generates salt,
Salt lease making filters pressing removal.In addition some scholars attempt mixed in ethyl alcohol and water under hydrochloric acid catalysis with TEOS and hexamethyldisiloxane
Back hydrolysis in solution is closed, hexamethyldisiloxane is used to extract MQ resin from reaction solution as extractant later, by
It neutralizes and vacuum distillation obtains organosilicon MQ naval stores.It is found from experiment when the additional amount of hexamethyldisiloxane is insufficient
When, the blocking units M wretched insufficiency of generation, ending ratio is lower, and yield is also low, and TEOS self-condensation reaction degree increases at this time
Add, often generates gel or precipitation.
At present from the technique that silester or ethyl polysilicate prepare organosilicon MQ resin, two silicon of hexamethyl is mainly used
Oxygen alkane (MM) is end-capping reagent, but since the hydrolysing activity of MM is not high, and the hydrolysis rate compared to TEOS is slow, this is also resulted in
Polycondensation reaction exceeds design degree in preparation process, increases the generation of gel, reduces yield and subsequent mention is significantly greatly increased
Pure complexity.
Summary of the invention
The present invention relates to a kind of synthesis preparation method of MQ type organic siliconresin, MQ resin referred herein is that have simultaneously
There is the M (RMe of single functionality2) and the Q (SiO of tetra functional SiO-2) structure organic siliconresin.Wherein R be hydrogen or have 1
To the alkyl of 20 carbon, for example, methyl, ethyl, phenyl, vinyl etc..
Preparation method of the invention includes first mutually mixing a certain amount of silicon substrate sulfate mixture with alkoxy silane
It closes.Silicon substrate sulfate mixture herein be containing bis- (trimethyl silicon substrate) sulfuric esters, trimethyl silicon substrate sulfuric acid monoester and
The mixture of hexamethyldisiloxane, wherein the sum of sulfuric acid dibasic acid esters and sulfuric acid monoester account for the ratio of silicon substrate sulfate mixture and are,
Weight percent 0.5% to 50%.Silicon substrate sulfuric ester can there are many synthesis modes, such as are existed by trim,ethylchlorosilane and the concentrated sulfuric acid
Reacting in benzene 12 hours can get bis- (trimethyl silicon substrate) sulfuric esters, yield 76%.It can also be obtained by trialkyl silanol, such as
Triethyl silanol reacts bis- (triethyl group silicon substrate) sulfuric acid that 2 hours available yields are 50% with the concentrated sulfuric acid in the presence of ammonium sulfate
Ester.And triethyl-ethoxy-silicane alkane and the concentrated sulfuric acid can get triethyl group silicon substrate sulfuric acid monoester.Additionally by six alkyl disiloxane
It also can get corresponding dibasic acid esters and mono-ester product with effect of sulfuric acid.It is described in US20100010188 and utilizes sulfur trioxide and six
Tetramethyldisiloxane prepares bis- (trimethyl silicon substrate) sulfuric esters, and its uses the dibasic acid esters as the catalysis of organosilicon balanced reaction
Agent.
Silicon substrate sulfuric ester is an extraordinary silication reagent, such as bis- (trimethyl silicon substrate) sulfuric esters can be used to and two
The hydroxyl of silicon oxide surface carries out silanization, and by-product is few, and absolutely not sulfonation generates, this and formd using sulfuric acid distinct
Comparison.
Silicon substrate sulfate mixture of the present invention is containing bis- (trimethyl silicon substrate) sulfuric esters, trimethyl silicon substrate sulfuric acid
The mixture of monoesters and hexamethyldisiloxane, the molar ratio of sulfuric acid dibasic acid esters and monoesters is 0.1:1 to 10:1 in mixture, should
Ratio can be adjusted by reaction condition and reactant ratio.The weight ratio that hexamethyldisiloxane accounts for sulfate mixture is 0%
To 80%, hexamethyldisiloxane, which can be to be added in reaction, to be also possible to be mixed into before use.In addition to this, the silicon substrate
Also containing one or more kinds of organic solvents in sulfate mixture, organic solvent can be the alcohol containing 1 to 20 carbon,
Ether, acid and aromatic hydrocarbon or saturated alkane, such as methanol, ethyl alcohol, isopropanol, ether, acetic acid, benzene or n-hexane, normal heptane etc.,
The weight percent that organic solvent accounts for silicon substrate sulfate mixture is 0 to 50%.
Alkoxy silane described in this patent is tetra functional organosilan or its prehydrolysis oligomer, including but is not limited to
In, tetramethoxy-silicane, tetraethoxysilane, ethyl polysilicates, methyl polysilicon acid esters etc..Silicon substrate sulfate mixture and alkane
The weight ratio of oxysilane is 0.1 to 1.The mixed process of silicon substrate sulfate mixture and alkoxy silane is preferably stirred strongly
It mixes down, alkoxy silane is slowly added in silicon substrate sulfate mixture, be heated to 30 to 70 degrees Celsius, mix 10 minutes to 30
Minute.
Preparation method of the invention includes, and after silicon substrate sulfate mixture and alkoxy silane mix, is added organic
Solvent, the organic solvent refer to arene, such as toluene, dimethylbenzene, ethylbenzene；Or esters, such as ethyl acetate, methyl acetate；
Or halogenated hydrocarbon, such as dichloroethanes, carbon tetrachloride etc..
Preparation method of the invention includes water being added under fast stirring after mixing, and carry out at a certain temperature
Hydrolysis-condensation reaction.The ratio of water should be enough to make the alkoxyl silicone in raw materials used to hydrolyze, so the molar ratio of water and alkoxy
Example is 0.5:1 to 10:1.The hydrolysis-condensation reaction carries out at a certain temperature, and certain temperature refers to 0 to 150 degree Celsius.
Preparation method of the invention includes in carrying out after the completion of hydrolytic condensation and and post-processing.Nothing can be used in neutralization
Machine or organic basic substance, such as alkali metal oxide or hydroxide, organic amine or ammonium salt, the alkali metal salt of alcohol, alkyl gold
Belong to compound etc..
Organosilicon MQ resin is prepared according to present invention process method, does not need in addition to add strong acid as catalyst, and by
In the good silanization performance of silicon substrate phosphate, the excessive autohemagglutination of silester or ethyl polysilicate is reduced, the production of gel is reduced
It is raw to improve yield, and M/Q ratio may be implemented preferably to control closer to feed ratio to target product structure.
Application example:
Comparison example,
722 grams of hexamethyldisiloxane are added in 5 liters of reaction kettles, 1.9 kilograms of ethyl polysilicate, 12 grams of the concentrated sulfuric acid are mixed
It closes, water (375 grams) is added dropwise into system after being uniformly mixed, system temperature is kept to be no more than 40 degrees Celsius.
Temperature is risen to 70 degrees Celsius after being added dropwise to complete and keeps the temperature 3 hours by water, adjusts pH value to 9, it is small to be heated to reflux 1
When.PH is adjusted to 7 again after the reaction was completed, water removal again removes low-boiling-point substance after filtering at reduced pressure conditions, and obtaining solid has
Machine silicon MQ resin, 1349.5 grams (yield 90.07%), M/Q=0.62, molecular weight Mn is equal to 4280, DPI=2.08.
Example one,
849.3 grams of silicon substrate sulfate mixture is added in 5 liters of reaction kettles, which becomes double containing weight ratio 2%
(trimethyl silicon substrate) sulfuric ester, the hexamethyldisiloxane of weight ratio 76% and the ethyl alcohol of weight ratio 22%.Polysilicon acid second is added
Ester (1727.4 grams) is mixed, and water (350 grams) are added dropwise into system after being uniformly mixed, and keeps system temperature to be no more than 40 Celsius
Degree.
Temperature is risen to 70 degrees Celsius after being added dropwise to complete and keeps the temperature 3 hours by water, adjusts pH value to 9, it is small to be heated to reflux 1
When.PH is adjusted to 7 again after the reaction was completed, water removal again removes low-boiling-point substance after filtering at reduced pressure conditions, and obtaining solid has
Machine silicon MQ resin, 1322.9 grams (yield 97.13%), M/Q=0.66, molecular weight Mn is equal to 4613, DPI=1.91.
Claims (9)
1. the present invention relates to a kind of synthesis preparation method of MQ type organic siliconresin, this method feature includes
Silicon substrate sulfate mixture is mixed with alkoxy silane, solvent is added, is added under fast stirring after mixing
Condensation reaction is hydrolyzed at a certain temperature, is neutralized and is post-processed after the completion of hydrolytic condensation for water.
2. according to claim 1, in the preparation method, the silicon substrate sulfate mixture is to contain bis- (trimethyl silicon substrate) sulphur
Acid esters, the mixture of trimethyl silicon substrate sulfuric acid monoester and hexamethyldisiloxane.
3. sulfuric acid dibasic acid esters accounts for silicon substrate sulfuric ester with sulfuric acid monoester and mixes in the silicon substrate sulfate mixture according to claim 2
The ratio of object is weight percent 0.5% to 50%.
4. also being had containing one or more kinds of organic solvents in the silicon substrate sulfate mixture according to claim 2
Solvent can be the alcohol containing 1 to 20 carbon, ether, acid and aromatic hydrocarbon or saturated alkane.
5. the weight percent that the organic solvent accounts for silicon substrate sulfate mixture is 0 to 50% according to claim 4.
6. according to claim 1, in the preparation method, the alkoxy silane is tetra functional organosilan or its prehydrolysis
Oligomer, including but not limited to, tetramethoxy-silicane, tetraethoxysilane, ethyl polysilicates, methyl polysilicon acid esters.
7. according to claim 1, in the preparation method, the weight ratio of silicon substrate sulfate mixture and alkoxy silane is 0.1
To 1.
8. organic solvent refers to arene, such as toluene, dimethylbenzene, ethylbenzene according to claim 1, in the preparation method；Or
Esters, such as ethyl acetate, methyl acetate；Or halogenated hydrocarbon, such as dichloroethanes, carbon tetrachloride etc..
9. hydrolysis-condensation reaction carries out at a certain temperature, and certain temperature refers to 0 according to claim 1, in the preparation method
To 150 degrees Celsius.
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| CN201811070073.2A CN109320722B (en) | 2018-09-13 | 2018-09-13 | Synthetic preparation method of MQ type organic silicon resin |
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|---|---|---|---|
| CN201811070073.2A CN109320722B (en) | 2018-09-13 | 2018-09-13 | Synthetic preparation method of MQ type organic silicon resin |
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| CN109320722A true CN109320722A (en) | 2019-02-12 |
| CN109320722B CN109320722B (en) | 2021-03-19 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113462349A (en) * | 2021-07-14 | 2021-10-01 | 深圳市华源宏新材料有限公司 | Silica gel and 3M double-faced adhesive bonding treating agent and preparation method thereof |
| CN114426667A (en) * | 2022-03-16 | 2022-05-03 | 江西海多化工有限公司 | Continuous preparation system and process method of narrow molecular weight MQ resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1046631A1 (en) * | 1999-04-19 | 2000-10-25 | Rolic AG | Liquid crystalline compounds |
| CN101094858A (en) * | 2004-10-29 | 2007-12-26 | 瑙威出口有限公司 | Process for preparing functionalised silanes and siloxanes |
| CN101421333A (en) * | 2006-03-01 | 2009-04-29 | 诺沃出口私人有限公司 | Improving one's methods of polymerizing silicone fluid |
-
2018
- 2018-09-13 CN CN201811070073.2A patent/CN109320722B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1046631A1 (en) * | 1999-04-19 | 2000-10-25 | Rolic AG | Liquid crystalline compounds |
| CN101094858A (en) * | 2004-10-29 | 2007-12-26 | 瑙威出口有限公司 | Process for preparing functionalised silanes and siloxanes |
| CN101421333A (en) * | 2006-03-01 | 2009-04-29 | 诺沃出口私人有限公司 | Improving one's methods of polymerizing silicone fluid |
Non-Patent Citations (2)
| Title |
|---|
| 侯銮荣: "《有机硅单体及聚合物》", 31 December 1986, 化学工业出版社 * |
| 黄文润: "《硅烷偶联剂及硅树脂》", 31 August 2010, 四川科学技术出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113462349A (en) * | 2021-07-14 | 2021-10-01 | 深圳市华源宏新材料有限公司 | Silica gel and 3M double-faced adhesive bonding treating agent and preparation method thereof |
| CN114426667A (en) * | 2022-03-16 | 2022-05-03 | 江西海多化工有限公司 | Continuous preparation system and process method of narrow molecular weight MQ resin |
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| CN109320722B (en) | 2021-03-19 |
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