CN106084230A - A kind of preparation method of low thermal weight loss low-refraction Narrow Molecular Weight Distribution silicones - Google Patents
A kind of preparation method of low thermal weight loss low-refraction Narrow Molecular Weight Distribution silicones Download PDFInfo
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- CN106084230A CN106084230A CN201610562580.2A CN201610562580A CN106084230A CN 106084230 A CN106084230 A CN 106084230A CN 201610562580 A CN201610562580 A CN 201610562580A CN 106084230 A CN106084230 A CN 106084230A
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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
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic 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
Abstract
A kind of low thermal weight loss low-refraction Narrow Molecular Weight Distribution silicones preparation method, the method is to add appropriate acid in four-hole bottle, vinyl double-seal head, hexamethyl disiloxane, the water of alcohol and trace is in stirring, react 12 hours under heating condition, make double-seal head fully disconnect Si O Si key-like and become silanol, it is simultaneously added dropwise water and esters of silicon acis the most in acid condition, enable esters of silicon acis while hydrolysis generates silicone hydroxyl key, Si O Si key can be formed with silicone hydroxyl key generation condensation reaction, be subsequently adding alkali be reaction system be alkaline environment, make Si O Si key generation rearrangement reaction or make the silane epoxide condensation of remnants, obtain the low thermal weight loss low-refraction methyl vinyl MQ silicon resin that structure is more perfect.The method has that raw material is cheap and easily-available and unsuitable gel, simple to operate, reaction condition is gentle, post processing is simple, solvent load is little, double-seal head utilization rate high, structure is easily controllable and advantages of environment protection.
Description
Technical field
The present invention relates to the novel preparation method of low thermal weight loss low-refraction Narrow Molecular Weight Distribution methyl vinyl MQ silicon resin,
Belong to the synthesis technical field of silicones.
Background technology
Silicones is as the series products earlier that comes out in organosilicon material, owing to it has dielectric constant excellence, performance
Stable, the characteristic such as excellent resistance to oxidation, chemicals-resistant, electrical insulating property, resistance to irradiation and weatherability.Therefore silicones can be used for electricity
Insullac, coating, moulding compound, laminate layer material, ingot stripper etc., have at aspects such as Aero-Space, electronic device, building, machineries
Purposes widely.
In existing technology, the synthetic method about methyl vinyl MQ silicon resin is mainly: 1, cohydrolysis condensation method,
Will be added drop-wise in the mixed liquor of esters of silicon acis and double-seal head etc. with sour mixed liquor by water, carry out condensation reaction and prepare vinyl MQ silicon
Resin；2, solve condensation method against the current, will be added drop-wise in the mixed solution of double-seal head, water, acid etc. by esters of silicon acis, carry out condensation reaction system
Standby Vinyl MQ silicon resin.There is easy gelation in prior art, solvent load is big, double-seal head utilization rate is low, environmental pollution is tight
The problem such as heavily.
Summary of the invention
For the deficiencies in the prior art, the present invention provides that a kind of unsuitable gel, solvent load are little, double-seal head utilization rate high,
Easy control of structure and environmentally friendly synthetic method.
Technical scheme is as follows:
The preparation method of a kind of low thermal weight loss low-refraction Narrow Molecular Weight Distribution methyl vinyl MQ silicon resin: at four-hole bottle
The water of acid, vinyl double-seal head, hexamethyl disiloxane (MM), alcohol and 2-5g that middle addition is appropriate is stirring, is being heated to 25 DEG C
React 1-2 hour, after having reacted, be at room temperature simultaneously added dropwise remaining total water and esters of silicon acis, the temperature in control system
(in water droplet to acid, exothermic temperature can raise, system temperature to be controlled) is between 30-40 DEG C, anti-at 70 DEG C after dropping
Answer 1-2 hour, then steam the alcohol in system, be subsequently adding the toluene with the quality such as theoretical synthetic resin and alkali regulation system
PH=9-10, at 90 DEG C react 1 hour, then heat up steam system in remaining alcohol and water, lower the temperature the most again, with acid neutralize,
It is washed to the pH=6-7 of system.120 DEG C of backspins are evaporated off toluene and i.e. obtain methyl vinyl MQ silicon resin.
Wherein, the mass ratio of acid, vinyl double-seal head, MM, alcohol, water and esters of silicon acis is (1.18-1.99): (5.58-
38.50): (30.46-113.24): (11.80-19.95): (43.20-64.80): 208.33.
According to currently preferred, use the method that water and esters of silicon acis are simultaneously added dropwise；
According to currently preferred, addition alcohol is used to play the compatibility of increase system and suppress reaction too fast；
According to currently preferred, described esters of silicon acis is methyl silicate, tetraethyl orthosilicate, positive isopropyl silicate；
According to currently preferred, described acid is hydrochloric acid, sulphuric acid, phosphoric acid, Emathlite, trifluoromethane sulfonic acid and acidity sun
Ion exchange resin；
According to currently preferred, the consumption of water is 2.4-3.6 times of esters of silicon acis molal weight；
According to currently preferred, described alcohol is ethanol, methanol, isopropanol；
According to currently preferred, described alkali is Na2CO3、NaHCO3、K2CO3、KHCO3、NaOH、KOH；
According to currently preferred, described reaction temperature is 30～120 DEG C；
According to currently preferred, speed of agitator is 200-450 rev/min；
According to currently preferred, vinyl mass percent is that (this refers to that vinyl quality accounts for synthesis to 1.5%-6%
The mass percent of resin)；
According to currently preferred, the value of R/Si is that (this refers to the mole of organic group in synthetic resin to 1.1-1.8
Ratio with the mole of silicon atom)；
According to currently preferred, the methyl vinyl MQ silicon resin of synthesis accurately can be controlled by the amount of abjection alcohol
The surplus of alkoxyl；
According to currently preferred, described reactor is equipped with thermometer, constant pressure funnel, spherical condensation tube, tetrafluoro
Four mouthfuls of round-bottomed flasks of stirring rod.
MQ silicones prepared by the present invention is mainly used in the reinforcing agent of packaging plastic, organosilicon adhesive and organosilicon molding
Material.
The method of the present invention has that raw material is cheap and easily-available and unsuitable gel, simple to operate, reaction condition is gentle, post processing is simple
List, solvent load are little, double-seal head utilization rate high, structure is easily controllable and advantages of environment protection.
Accompanying drawing explanation
Fig. 1 is the TGA of the organic siliconresin of the embodiment of the present invention 1 preparation.
Fig. 2 is the GPC of the organic siliconresin of the embodiment of the present invention 1 preparation.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described, but is not limited to this.
Embodiment 1
The concentrated hydrochloric acid of 1.77g, 15.13g vinyl double-seal head, the ethanol of 67.70gMM, 15.10g is added in four-hole bottle
It is 300 turns/min with 3.00g water at rotating speed, reacts 1 hour at 25 DEG C, after having reacted, be at room temperature simultaneously added dropwise 50.40g's
Water and the tetraethyl orthosilicate of 208.33g, the temperature in control system between 30 DEG C, after dropping at 70 DEG C react 2 hours,
Then 80 DEG C of ethanol steamed in system, is subsequently adding 142.10g toluene and the pH=9 of appropriate NaOH regulation system, at 90 DEG C
React 1 hour, then heat to 120 DEG C steam system in remaining second alcohol and water, lower the temperature the most again, acid adding neutralize, be washed to
The pH=6-7 of system；120 DEG C of backspins steam the toluene in system and i.e. obtain methyl vinyl MQ silicon resin, and its productivity is
93%.
Embodiment 2
The concentrated hydrochloric acid of 1.17g, 15.13g vinyl double-seal head, the methanol of 67.70gMM, 15.10g is added in four-hole bottle
It is 300 turns/min with 3.00g water at rotating speed, reacts 1 hour at 25 DEG C, after having reacted, be at room temperature simultaneously added dropwise 47.00g's
Water and the methyl silicate of 152.22g, the temperature in control system at 35 DEG C, after dropping at 70 DEG C react 2 hours, then
70 DEG C steam the methanol in system, are subsequently adding 126.61g toluene and the pH=9 of appropriate KOH regulation system, react 1 at 90 DEG C
Hour, then heat to 120 DEG C steam system in remaining first alcohol and water, lower the temperature the most again, acid adding neutralize, be washed to system
PH=6-7；120 DEG C of backspins steam the toluene in system and i.e. obtain methyl vinyl MQ silicon resin, and its productivity is 94%.
Embodiment 3
The concentrated hydrochloric acid of 1.50g, 15.13g vinyl double-seal head, the isopropyl of 67.70gMM, 15.10g is added in four-hole bottle
Alcohol and 3.00g water are 300 turns/min at rotating speed, react 1 hour at 25 DEG C, are at room temperature simultaneously added dropwise 60.00g after having reacted
Water and the positive isopropyl silicate of 152.22g, the temperature in control system at 40 DEG C, after dropping at 70 DEG C react 2 hours,
Then 90 DEG C of isopropanols steamed in system, are subsequently adding 126.61g toluene and appropriate Na2CO3The pH=9 of regulation system, 90 DEG C
Lower reaction 1 hour, then heat to 120 DEG C steam system in remaining isopropyl alcohol and water, lower the temperature the most again, acid adding neutralize, water
It is washed till the pH=6-7 of system；120 DEG C of backspins steam the toluene in system and i.e. obtain methyl vinyl MQ silicon resin, its productivity
It is 90%.
Embodiment 4
The concentrated sulphuric acid of 1.60g, 17.00g vinyl double-seal head, the ethanol of 46.08gMM, 19.10g is added in four-hole bottle
It is 300 turns/min with 3.00g water at rotating speed, reacts 1 hour at 25 DEG C, after having reacted, be at room temperature simultaneously added dropwise 50.40g's
Water and the tetraethyl orthosilicate of 208.33g, the temperature in control system at 40 DEG C, after dropping at 70 DEG C react 2 hours, then
The ethanol alcohol that 80 DEG C steam in system, is subsequently adding 123.10g toluene and appropriate NaHCO3The pH=9 of regulation system, at 90 DEG C
React 1 hour, then heat to 120 DEG C steam system in remaining ethanol alcohol and water, lower the temperature the most again, acid adding neutralize, washing
PH=6-7 to system.120 DEG C of backspins steam the toluene in system and i.e. obtain methyl vinyl MQ silicon resin, and its productivity is
93%.
From Fig. 1 and Fig. 2 it can be seen that MQ silicones start weightlessness temperature about at 250 DEG C, when 300 DEG C resin residue
94.93%, when 400 DEG C, resin surplus is 78.79%, and when 500 DEG C, resin surplus is 74..27%, and when 600 DEG C, resin remains
Surplus is 61.95%；Mn=1544, Mw=1809, Mw/Mn=1.17, molecular weight distribution is the narrowest.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (7)
1. the preparation method of one kind low thermal weight loss low-refraction Narrow Molecular Weight Distribution silicones, it is characterised in that in four-hole bottle
Add acid, vinyl double-seal head, hexamethyl disiloxane, alcohol and 2-5g water stirring, be heated to 25 DEG C of reactions 1-2 hour, instead
At room temperature being simultaneously added dropwise remaining total water and esters of silicon acis after should completing, the temperature in control system, between 30-40 DEG C, is dripped
React 1-2 hour at 70 DEG C after adding, then steam the alcohol in system, be subsequently adding and the first of the quality such as theoretical synthetic resin
Benzene and the pH=9-10 of alkali regulation system, 90 DEG C are reacted 1 hour, and then heat up remaining alcohol and water in steaming system, the most again
Cooling, with acid neutralization, be washed to the pH=6-7 of system；120 DEG C of backspins are evaporated off toluene and i.e. obtain silicones；
The mass ratio of described acid, vinyl double-seal head, hexamethyl disiloxane, alcohol, water and esters of silicon acis is (1.18-1.99):
(5.58-38.50): (30.46-113.24): (11.80-19.95): (43.20-64.80): 208.33.
Preparation method the most according to claim 1, it is characterised in that described esters of silicon acis is methyl silicate, positive silicic acid second
One in ester, positive isopropyl silicate.
Preparation method the most according to claim 1, it is characterised in that described acid be hydrochloric acid, sulphuric acid, phosphoric acid, Emathlite,
One in trifluoromethane sulfonic acid and acid cation exchange resin.
Preparation method the most according to claim 1, it is characterised in that described alcohol is in ethanol, methanol, isopropanol
Kind.
Preparation method the most according to claim 1, it is characterised in that described alkali is Na2CO3、NaHCO3、K2CO3、KHCO3、
One in NaOH, KOH.
Preparation method the most according to claim 1, it is characterised in that speed of agitator is 200-450 rev/min.
Preparation method the most according to claim 1, it is characterised in that the consumption of water is the 2.4-of esters of silicon acis molal weight
3.6 again.
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| CN201610562580.2A CN106084230A (en) | 2016-07-15 | 2016-07-15 | A kind of preparation method of low thermal weight loss low-refraction Narrow Molecular Weight Distribution silicones |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106700077A (en) * | 2016-11-11 | 2017-05-24 | 烟台德邦先进硅材料有限公司 | Preparation method of high-temperature-resistant anti-cracking MDQ silicon resin |
| CN109438709A (en) * | 2018-10-31 | 2019-03-08 | 莱芜市雅达电子材料有限公司 | A kind of methyl MQ process for preparing resins |
| CN109608640A (en) * | 2018-12-27 | 2019-04-12 | 浙江新安化工集团股份有限公司 | A kind of high molecular weight MQ silicone resin and its synthetic method, application |
| CN110498925A (en) * | 2019-09-16 | 2019-11-26 | 南昌大学 | A kind of preparation method of reinforcement silicon rubber MQ resin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4707531A (en) * | 1985-02-22 | 1987-11-17 | Toray Silicone Co., Ltd. | Method for producing organosilicon polymers and the polymers prepared thereby |
-
2016
- 2016-07-15 CN CN201610562580.2A patent/CN106084230A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4707531A (en) * | 1985-02-22 | 1987-11-17 | Toray Silicone Co., Ltd. | Method for producing organosilicon polymers and the polymers prepared thereby |
Non-Patent Citations (1)
| Title |
|---|
| 曾启华等: ""MQ硅树脂的制备及热性能研究"", 《有机硅材料》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106700077A (en) * | 2016-11-11 | 2017-05-24 | 烟台德邦先进硅材料有限公司 | Preparation method of high-temperature-resistant anti-cracking MDQ silicon resin |
| CN109438709A (en) * | 2018-10-31 | 2019-03-08 | 莱芜市雅达电子材料有限公司 | A kind of methyl MQ process for preparing resins |
| CN109438709B (en) * | 2018-10-31 | 2022-01-07 | 济南雅达新材料科技有限公司 | Preparation method of methyl MQ resin |
| CN109608640A (en) * | 2018-12-27 | 2019-04-12 | 浙江新安化工集团股份有限公司 | A kind of high molecular weight MQ silicone resin and its synthetic method, application |
| CN109608640B (en) * | 2018-12-27 | 2020-09-29 | 浙江新安化工集团股份有限公司 | High molecular weight MQ silicon resin and synthesis method and application thereof |
| CN110498925A (en) * | 2019-09-16 | 2019-11-26 | 南昌大学 | A kind of preparation method of reinforcement silicon rubber MQ resin |
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