CN104910382B - The preparation method of MQ silicones - Google Patents
The preparation method of MQ silicones Download PDFInfo
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- CN104910382B CN104910382B CN201510368741.XA CN201510368741A CN104910382B CN 104910382 B CN104910382 B CN 104910382B CN 201510368741 A CN201510368741 A CN 201510368741A CN 104910382 B CN104910382 B CN 104910382B
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Abstract
The present invention relates to resin, and in particular to a kind of preparation method of MQ silicones.Described preparation method is comprised the following steps：Deionized water, alcohol, esters of silicon acis and closure agent are added in reaction vessel, stirring obtains emulsifying shape reaction system；The temperature of reaction system is maintained at 5~15min of hydrogen chloride gas is passed through under 20~55 DEG C, stirring, then be warming up to 60~80 DEG C, 2~4h of reaction；The feed postition of hydrogen chloride gas is that the ullage by hydrogen chloride gas in reaction system is added, and is absorbed by reaction system and dissolved；After the completion of reaction, reaction system static layering removes layer and obtains pre-polymerization resin layer, is warming up to 120~150 DEG C, and volatile components are removed under the vacuum condition of 300~2000Pa, obtains water white transparency MQ silicones.Course of reaction of the present invention is gentle, it is easy to control, and drastically increases reaction rate, is produced without gel or insoluble matter, the product clear for obtaining.The present invention is simple and easy to apply, and production efficiency is high, it is adaptable to industrialized production.
Description
Technical field
The present invention relates to resin, and in particular to a kind of preparation method of MQ silicones.
Background technology
MQ silicones is by monofunctional unit (R3SiO0.5Abbreviation M units) and four-functional group unit (SiO2Abbreviation Q is mono-
Unit) composition a kind of organic siliconresin, belong to polysiloxanes, MQ silicones is transparent liquid object or powdered, and is typically had
Machine compound has good compatibility, directly using good dispersion, with reactive active structure group.MQ silicones can use
Make the aspects such as organic pressure-sensitive gel, liquid silastic, personal skin care, due to its good light transmittance, in terms of optical package
Have to compare and be widely applied.
Prepare at this stage using silicic acid ester process more than high-quality MQ silicones, because tetraethyl orthosilicate or methyl silicate have
Reaction speed faster, charging sequence and charging rate are required for strict control, can just obtain the product of even structure.Reaction control
System is not proper, can have a strong impact on product transparency and yield.
The content of the invention
It is an object of the invention to provide a kind of preparation method of MQ silicones, solve esters of silicon acis method and prepare the reaction of MQ silicones
The uppity problem of process, safe operation is simple, it is easy to promote；The product stabilization for obtaining, with good compatibility.
The preparation method of MQ silicones of the present invention, comprises the following steps：
(1) deionized water, alcohol, esters of silicon acis and closure agent are added in reaction vessel, stirring obtains emulsifying shape reaction system；
(2) temperature of reaction system is maintained at and 5~15min of hydrogen chloride gas is passed through under 20~55 DEG C, stirring, then heated up
To 60~80 DEG C, 2~4h is reacted；The feed postition of hydrogen chloride gas is that the ullage by hydrogen chloride gas in reaction system adds
Enter, absorbed by reaction system and dissolved；
(3) after the completion of reacting, reaction system static layering removes layer and obtains pre-polymerization resin layer, is warming up to 120~150 DEG C,
Volatile components are removed under the vacuum condition of 300~2000Pa, water white transparency MQ silicones is obtained.
Wherein, preferred technical scheme is as follows：
The mol ratio of described deionized water, alcohol, esters of silicon acis and closure agent is (2~10):(0.1~4):1:(0.6~
1.4), further preferably, the mol ratio (6~8) of deionized water, alcohol, esters of silicon acis and closure agent:(0.25~2):1:(0.6~
1.2)。
Described hydrogen chloride, the mol ratio of deionized water are (0.0025~0.05):1, further preferably, hydrogen chloride, go
Ionized water mol ratio is (0.005~0.015):1.
Described alcohol is the one kind in methyl alcohol, ethanol or isopropanol, preferably methyl alcohol or ethanol.
Described esters of silicon acis is the one kind in methyl silicate, tetraethyl orthosilicate or positive silicic acid propyl ester, preferably positive silicic acid first
Ester or tetraethyl orthosilicate.
Described closure agent is one or more in following material：
(1) formula is XMe2SiOSiMe2The siloxanes of X；(2) formula is XMe2The compound of SiOR；
Wherein, X is the one kind in methyl, vinyl, hydrogen-based or phenyl, and R is in methyl, ethyl, propyl group or isopropyl
It is a kind of.XMe2SiOSi Me2The molal quantity of X is with XMe2SiO0.5Molal quantity metering.
Preferred formula is XMe2SiOSiMe2The siloxanes of X is used as closure agent.
In step (2), the temperature of step (1) reaction system is maintained at hydrogen chloride gas 5 are passed through under 35~50 DEG C, stirring
~15min, then it is warming up to 60~70 DEG C, 2.5~3.5h of reaction.
In step (3), vacuum condition preferably 500~1200Pa.
Beneficial effects of the present invention are as follows：
The present invention changes the feed way that tradition is added dropwise, and hydrogen chloride gas, chlorine are passed through using in reaction system ullage
Change hydrogen by uniform pickup, course of reaction is gentle, it is easy to control, and drastically increases reaction rate, without gel or insoluble matter
Produce, the product clear for obtaining.The present invention is simple and easy to apply, and production efficiency is high, it is adaptable to industrialized production.
Specific embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
Equipped with agitator, thermometer is added, deionized water 12mol, ethanol 0.5mol in the there-necked flask of condenser pipe,
Tetraethyl orthosilicate 2mol, HMDO 0.4mol and tetramethyl disiloxane 0.2mol, stirring, keep it in 35
DEG C, reactive component hydrogen chloride gas 0.03mol, 5min ventilation is passed through in whipping process and is finished, it is warming up to 60 DEG C, balanced reaction
2.5h.After completion of the reaction, static layering, lower floor is pre-polymerization resin layer, removes layer, 120 DEG C is warming up to, in the vacuum bar of 500Pa
Volatile components 4h is removed under part, water white transparency product, yield 80.5% is obtained.
Embodiment 2
Equipped with agitator, thermometer is added, deionized water 14mol, methyl alcohol 2mol, just in the there-necked flask of condenser pipe
Methyl silicate 2mol, HMDO 0.4mol and divinyl tetramethyl disiloxane 0.4mol, stirring, keep it
At 45 DEG C, reactive component hydrogen chloride gas 0.14mol, 10min ventilation is passed through in whipping process and is finished, be warming up to 65 DEG C, put down
Weighing apparatus reaction 3h.After completion of the reaction, static layering, lower floor is pre-polymerization resin layer, removes layer, 150 DEG C is warming up to, in the true of 800Pa
Volatile components 3h is removed under empty condition, water white transparency product, yield 86.2% is obtained.
Embodiment 3
Equipped with agitator, thermometer is added, deionized water 16mol, methyl alcohol 4mol, just in the there-necked flask of condenser pipe
Methyl silicate 2mol, HMDO 1.2mol, stirring, keep it in 50 DEG C, and reaction group is passed through in whipping process
Divide hydrogen chloride gas 0.24mol, 15min ventilation to finish, be warming up to 70 DEG C, balanced reaction 3.5h.After completion of the reaction, static point
Layer, lower floor is pre-polymerization resin layer, removes layer, is warming up to 140 DEG C, and volatile components 3h is removed under the vacuum condition of 1200Pa,
Obtain water white transparency product, yield 93.2%.
Claims (9)
1. a kind of preparation method of MQ silicones, it is characterised in that comprise the following steps：
（1）Deionized water, alcohol, esters of silicon acis and closure agent are added in reaction vessel, stirring obtains emulsifying shape reaction system；
（2）The temperature of reaction system is maintained at 5~15min of hydrogen chloride gas is passed through under 20~55 DEG C, stirring, then be warming up to 60
~80 DEG C, react 2~4h；The feed postition of hydrogen chloride gas is that the ullage by hydrogen chloride gas in reaction system is added,
Absorbed by reaction system and dissolved；
（3）After the completion of reaction, reaction system static layering removes layer and obtains pre-polymerization resin layer, is warming up to 120~150 DEG C,
Volatile components are removed under the vacuum condition of 300~2000Pa, water white transparency MQ silicones is obtained.
2. the preparation method of MQ silicones according to claim 1, it is characterised in that：Deionized water, alcohol, esters of silicon acis and envelope
Head agent mol ratio be（2~10）:（0.1~4）: 1 :（0.6~1.4）.
3. the preparation method of MQ silicones according to claim 1, it is characterised in that：Hydrogen chloride, deionized water mole
Than for（0.0025~0.05）: 1.
4. the preparation method of MQ silicones according to claim 1, it is characterised in that：Alcohol is methyl alcohol, ethanol or isopropanol
In one kind.
5. the preparation method of MQ silicones according to claim 1, it is characterised in that：Esters of silicon acis is methyl silicate, just
One kind in silester or positive silicic acid propyl ester.
6. the preparation method of MQ silicones according to claim 1, it is characterised in that：Closure agent is in following material
Plant or various：
（1）Formula is XMe2SiOSiMe2The siloxanes of X；（2）Formula is XMe2The compound of SiOR；
Wherein, X is the one kind in methyl, vinyl, hydrogen-based or phenyl, and R is the one kind in methyl, ethyl, propyl group or isopropyl.
7. the preparation method of MQ silicones according to claim 6, it is characterised in that：XMe2SiOSi Me2The molal quantity of X
It is with XMe2SiO0.5Molal quantity metering.
8. the preparation method of MQ silicones according to claim 1, it is characterised in that：Step（2）In, by reaction system
Temperature is maintained under 35~50 DEG C, stirring and is passed through 5~15min of hydrogen chloride gas, then is warming up to 60~70 DEG C, and reaction 2.5~
3.5h。
9. the preparation method of MQ silicones according to claim 1, it is characterised in that：Step（3）In, vacuum condition is
500~1200Pa.
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| CN110423351A (en) * | 2019-07-29 | 2019-11-08 | 中科广化（重庆）新材料研究院有限公司 | A kind of Vinyl MQ silicon resin and preparation method thereof |
| CN111116917B (en) * | 2019-12-18 | 2022-02-08 | 宁波辉宏新材料有限公司 | Method for synthesizing emulsion type MDQ silicon resin by emulsion polymerization method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391673A (en) * | 1993-12-30 | 1995-02-21 | Dow Corning Corporation | Silicon resins and methods for their preparation |
| CN101613475A (en) * | 2009-07-17 | 2009-12-30 | 南昌大学 | Preparing MQ silicon resin by organic acid catalysis |
| CN102181055A (en) * | 2011-01-14 | 2011-09-14 | 仲恺农业工程学院 | Preparation method of reactive MQ silicon resin |
| CN103951827A (en) * | 2014-05-08 | 2014-07-30 | 山东省科学院新材料研究所 | Phenylhydro-MQ silicone resin and preparation method thereof |
-
2015
- 2015-06-29 CN CN201510368741.XA patent/CN104910382B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391673A (en) * | 1993-12-30 | 1995-02-21 | Dow Corning Corporation | Silicon resins and methods for their preparation |
| CN101613475A (en) * | 2009-07-17 | 2009-12-30 | 南昌大学 | Preparing MQ silicon resin by organic acid catalysis |
| CN102181055A (en) * | 2011-01-14 | 2011-09-14 | 仲恺农业工程学院 | Preparation method of reactive MQ silicon resin |
| CN103951827A (en) * | 2014-05-08 | 2014-07-30 | 山东省科学院新材料研究所 | Phenylhydro-MQ silicone resin and preparation method thereof |
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Address after: 256401 Shandong City Dongfeng Group technical management center, Tangshan Town, Huantai, Zibo, Shandong Patentee after: Shandong Dongyue organosilicon material Limited by Share Ltd Address before: 256401 Shandong City Dongfeng Group technical management center, Tangshan Town, Huantai, Zibo, Shandong Patentee before: Shandong Dongyue Silicon Material co., Ltd. |
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