CN102977370A - Preparation method of methylsilicone oil - Google Patents
Preparation method of methylsilicone oil Download PDFInfo
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- CN102977370A CN102977370A CN2011102598891A CN201110259889A CN102977370A CN 102977370 A CN102977370 A CN 102977370A CN 2011102598891 A CN2011102598891 A CN 2011102598891A CN 201110259889 A CN201110259889 A CN 201110259889A CN 102977370 A CN102977370 A CN 102977370A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a preparation method of methylsilicone oil, and specifically relates to methyl silicone oil with different viscosity (molecular weight) prepared by using supported solid superacid SO4<2->/ZrO2-ZSM-5 as a catalyst and by adopting inexpensive and commercially available methylsilicone oil (Dn), octamethylcyclotetrasiloxane (D4) and hexamethyldisiloxane (MM), so as to fit various needs. Compared with a conventional catalyst for producing methylsilicone oil, the supported solid superacid catalyst provided by the invention has higher catalytic activity, higher stability, lower cost and the like. More importantly, the supported solid superacid catalyst is in a solid state and can be separated via simple filtration and reused, thereby enabling the production to have the advantages of simple process, convenient operation, no pollutions, no corrosion toward equipment, and the like.
Description
Technical field
The present invention relates to a kind of preparation method of methyl-silicone oil, specifically is with the novel method of the multiple viscosity silicone oil of a kind of supported solid superacid acid preparation, belongs to new material technology field.
Background technology
Dimethyl silicone oil is tasteless nontoxic, have physiology inertia, good chemical stability, electric edge and weathering resistance, range of viscosities is wide, zero pour is low, and flash-point is high, and hydrophobic performance is good, and has a very high resistance to shear, can be in 50～180 ℃ of temperature life-time service, extensively be used as insulation, lubricated, shockproof, dust laying oil, dielectric liquid and thermal barrier, have and as the additive of froth breaking, demoulding, paint and daily cosmetics etc.Along with the development of society, not only the demand of the amount of methyl-silicone oil increased, the requirement of the methyl-silicone oil of different viscosity (molecular weight) is also constantly increased, and the kind that can buy on the market is limited.
Present existing methyl-silicone oil technology of preparing has hydrolyzing chlorosilane method [J.Am.Chem.Soc., 110 (1988), 3324; CN1240459A; CN1880361A] and the ring-opening polymerization method (Unexamined Patent 5-170913 communique) of cyclosilane, these two kinds of methods will be carried out catalysis with acid, and traditional catalyzer is the vitriol oil.Although its catalytic activity is good, but life-time service will bring great number of issues to industrial production: the residual vitriol oil need to pass through the methods processing such as neutralization, washing in the dimethyl silicone oil that obtains after the reaction, this not only makes the separation difficult, and will produce a large amount of trade effluents, sulfuric acid also corrodes production unit simultaneously.
Solid super-strong acid refers to the acid that the solid surface strength of acid is stronger than 100% sulfuric acid, have preparation simple, store convenient, catalytic activity is high, not etching apparatus, free from environmental pollution, regenerate easily and the advantage such as recycle, only needing to finish rear filtration in reaction and can realize that just catalyzer separates with reaction product, is a kind of commercial catalysts that has a extensive future.Solid super-strong acid has been applied in the multiple catalyzed reaction, is one of study hotspot of catalytic field.
Zhao has built grand reported first solid super-strong acid TiO
2/ SO
4 2-Catalyze and synthesize method [the meticulous and specialty chemicals of dimethyl silicone oil, 2006,14 (18), 21], but the activity of this catalyzer and stability remain further to be improved, patent of invention CN101851333A discloses a kind of method for preparing methyl phenyl silicone oil, and the method specifically is with solid super-strong acid TiO take rare earth super acid as catalyzer
2/ SO
4 2-Be composited with multiple rare earth compound, make rare earth and original atoms metal produce synergistic effect, further improve catalyst activity.If invent the solid catalyst that is suitable for multiple methyl-silicone oil preparation that a kind of catalytic activity is high, stability is higher, price is lower, will form a kind of new methyl-silicone oil preparation method, promote the raising of methyl-silicone oil production technology.
Summary of the invention
The present invention is directed to the demand of the deficiencies in the prior art and society, a kind of solid super acid catalyst SO of loading type is provided
4 2-/ ZrO
2-ZSM-5, this catalyzer has overcome the shortcoming of existing catalyzer, can be used for preparing the dimethyl silicone oil of multiple viscosity.
The present invention realizes by following technical scheme: a kind of preparation method of methyl-silicone oil is characterized in that preparing in the steps below:
Step (1) adds a certain proportion of octamethylcyclotetrasiloxane (D in reactor
4) and hexamethyldisiloxane (MM), perhaps octamethylcyclotetrasiloxane (D
4) and polymethyl siloxane (D
n);
Step (2) adding massfraction is 0.5～10% carried superstrong solid acid catalyzer, and the preferred mass mark is 1～2%;
Step (3) stirs lower reaction 1～10 hour under 50～～200 ℃, preferable reaction temperature is 80～120 ℃, 2～5 hours reaction times;
After step (4) reaction finishes, filtering recovering catalyst, the decompression extracting is also reclaimed low-boiling-point substance, gets the methyl-silicone oil product.
In step (1), it is characterized in that utilizing can the commercial low price that obtains methyl-silicone oil (D
n), octamethylcyclotetrasiloxane D
4Prepare the methyl-silicone oil of different viscosity (molecular weight) with hexamethyldisiloxane MM, to adapt to various special demands, adjust simply the ratio between them, just can obtain the methyl-silicone oil of different viscosity.
Carried superstrong solid acid catalyzer described in the step (2) specifically refers to SO
4 2-/ ZrO
2-ZSM-5 is to adopt sol-gel method to make, and its concrete preparation method is as follows:
(1) with hydration ZrOCl
28H
2O is soluble in water, drips concentration and be 2.5～2.8% ammoniacal liquor under rapid stirring, rate of addition be per 1～3 second one, to pH=9～10, obtain Zr (OH)
4Precipitation;
(2) throw out after filtration and the washing, until do not contain chlorion in the filtrate;
(3) filter cake of gained is smashed to pieces afterwards in 100-110 ℃ of lower oven dry 3-12 hour;
(4) with more than (3) gained solid porphyrize to 200 order, then join simultaneously in varing proportions with ZSM-5 molecular sieve and soak rear suction filtration in the dilute sulphuric acid;
(5) (4) are filtered the solid obtain 100～110 ℃ after lower dry 10～24 hours in air atmosphere in 550～700 ℃ of roastings 1.5～3.5 hours, namely obtain SO
4 2-/ ZrO
2-ZSM-5 solid super acid catalyst.
(OH) 4 of Zr among the present invention and ZSM-5 molecular sieve need strong stirring, used sulfuric acid concentration when soaking with sulfuric acid be 0.25～1.5mol/L, and the sulfuric acid soak time is 0.5～1 hour.
The invention allows for described SO
4 2-/ ZrO
2The application of-ZSM-5 solid super acid catalyst namely is applied in dimethyl silicone oil synthetic, and concrete reaction conditions is as follows:
Dimethyl siloxane and closure agent are mixed by a certain percentage, and the adding massfraction is 0.5～2.5% SO
4 2-/ ZrO
2-ZSM-5 solid super acid catalyst; Under 100～140 ℃, reacted under the magnetic agitation 0.5～2 hour.
In enforcement of the present invention, by regulating D
n, D
4Ratio with MM, by regulating the amount of molecular sieve in the catalyst preparation process etc., can select can the commercial inexpensive raw material that obtains, make the multiple methyl-silicone oil that can satisfy different demands, the catalyzer price of using in the preparation process is low, pollution-free, through simply filtering out separable and can reusing, overcome the shortcoming of existing catalyzer.
Embodiment
Example 1:
The preparation of catalyzer-1: with 25g ZrOCl
28H
2O is dissolved in the 150mL water, drips ammoniacal liquor under the strong magnetic agitation to pH=9～10, throw out after filtration and washing, until in the filtrate with the AgNO of 0.1mol/L
3Check does not contain Cl
-Ion, the filter cake that obtains is placed on 105 ℃ of lower dryings 2 hours through smashing to pieces, then with mortar with dried solid grinding powder after again 105 ℃ lower dry 20 minutes, with 200 mesh sieve dried pressed powder is screened, be 3% ZSM-5 molecular sieve and Zr (OH) with 1gZSM-5 content
4Mixture join in the sulphuric acid soln of 1.0mol/L, magnetic agitation 45 minutes is filtered, 105 ℃ after lower dry 12 hours in 700 ℃ of roastings of air atmosphere 2 hours, obtain catalyzer-1.
Catalyzer-1 is used for the building-up reactions of dimethyl silicone oil: take by weighing 10gD
4(octamethylcyclotetrasiloxane) and 0.32gMM (hexamethyldisiloxane) add 0.100g freshly prepd catalyzer-1, at 80 ℃ of lower magnetic force stirring reactions in round-bottomed flask in the 25mL round-bottomed flask.React after 2 hours, remove by filter catalyzer, the decompression extracting is also reclaimed low-boiling-point substance, obtains water white dimethyl silicone oil, and 25 ℃ of rotary viscosities are 285mpas.
Example 2:
Catalyzer-1 is used for the building-up reactions of dimethyl silicone oil: take by weighing 10gD
4(octamethylcyclotetrasiloxane) and 0.16gMM (hexamethyldisiloxane) add 0.100g freshly prepd catalyzer-1, at 120 ℃ of lower magnetic force stirring reactions in round-bottomed flask in the 25mL round-bottomed flask.React after 2 hours, the decompression extracting is also reclaimed low-boiling-point substance, obtains water white dimethyl silicone oil, and 25 ℃ of rotary viscosities are 350mpas.
Example 3:
Catalyzer-1 is used for the building-up reactions of dimethyl silicone oil: take by weighing 10gD4 (octamethylcyclotetrasiloxane) and 0.10gMM (hexamethyldisiloxane) in the 25mL round-bottomed flask, in round-bottomed flask, add 0.200g freshly prepd catalyzer-1, at 120 ℃ of lower magnetic force stirring reactions.React after 2 hours, remove by filter catalyzer, the decompression extracting is also reclaimed low-boiling-point substance, obtains water white dimethyl silicone oil, and 25 ℃ of rotary viscosities are 390mpas.
Example 4:
The preparation of catalyzer-2: with 25g ZrOCl
28H
2O is dissolved in the 150mL water, drips ammoniacal liquor under the strong magnetic agitation to PH=9～10, throw out after filtration and washing, until use 0.1mol/LAgNO in the filtrate
3Check does not contain Cl
-Ion, the filter cake that obtains is placed on 105 ℃ of lower dryings 2 hours through smashing to pieces, then lower dry 20 minutes at 105 ℃ again after with dried solid grinding powder with mortar, with 200 mesh sieve dried pressed powder is screened, be that 3% ZSM-5 molecular sieve and the mixture of Zr (OH) 4 join in the sulphuric acid soln of 1.0mol/L with 0.5gZSM-5 content, magnetic agitation 30 minutes is filtered, drying in 700 ℃ of roastings of air atmosphere 2 hours, obtained catalyzer-2 after 12 hours under 105 ℃.
Catalyzer-2 is used for the building-up reactions of dimethyl silicone oil: take by weighing 10gD
4(octamethylcyclotetrasiloxane) and 0.17gMM (hexamethyldisiloxane) add 0.100g freshly prepd catalyzer-2, at 120 ℃ of lower magnetic force stirring reactions in round-bottomed flask in the 25mL round-bottomed flask.React after 2 hours, the decompression extracting is also reclaimed low-boiling-point substance, obtains water white dimethyl silicone oil, and 25 ℃ of rotary viscosities are 410mpas.
Example 5:
The preparation of catalyzer-3: with 25g ZrOCl
28H
2O is dissolved in the 150mL water, drips ammoniacal liquor under the strong magnetic agitation to PH=9～10, throw out after filtration and washing, until use 0.1mol/LAgNO in the filtrate
3Check does not contain the Cl-ion, the filter cake that obtains is placed on 105 ℃ of lower dryings 2 hours through smashing to pieces, then lower dry 20 minutes at 105 ℃ again after with dried solid grinding powder with mortar, with 200 mesh sieve dried pressed powder being screened, is 3% ZSM-5 molecular sieve and Zr (OH) with 0.25gZSM-5 content
4Mixture join in the sulphuric acid soln of 1.25mol/L, magnetic agitation 30 minutes is filtered, 105 ℃ after lower dry 12 hours in 700 ℃ of roastings of air atmosphere 2 hours, obtain catalyzer-3.
Catalyzer-3 is used for the building-up reactions of dimethyl silicone oil: take by weighing 10gD
4(octamethylcyclotetrasiloxane) and 0.21gMM (hexamethyldisiloxane) add 0.100g freshly prepd catalyzer-3, at 120 ℃ of lower magnetic force stirring reactions in the round bottom ground flask in the 25mL round-bottomed flask.React after 2 hours, the decompression extracting is also reclaimed low-boiling-point substance, obtains water white dimethyl silicone oil, and 25 ℃ of rotary viscosities are 250mpas.
Example 6:
Catalyzer-2 is used for the building-up reactions of dimethyl silicone oil: take by weighing 25 ℃ of rotary viscosities of 10g and be 150 Dn (dimethyl silicone oil) and 15g D
4(octamethylcyclotetrasiloxane siloxanes) adds 0.25g freshly prepd catalyzer-2, at 120 ℃ of lower magnetic force stirring reactions in round-bottomed flask in the 25mL round-bottomed flask.React after 2 hours, the decompression extracting is also reclaimed low-boiling-point substance, obtains water white dimethyl silicone oil, and 25 ℃ of rotary viscosities are 4105mpas.
Example 7:
Catalyzer-2 be used for dimethyl silicone oil building-up reactions reuse experiment: take by weighing 10gD
4(octamethylcyclotetrasiloxane) and 0.17gMM (hexamethyldisiloxane) add 0.100g freshly prepd catalyzer-2, at 120 ℃ of lower magnetic force stirring reactions in round-bottomed flask in the 25mL round-bottomed flask.React after 2 hours, the decompression extracting is also reclaimed low-boiling-point substance, obtains water white dimethyl silicone oil, and 25 ℃ of rotary viscosities are 410mpas (catalyzer).The catalyzer that reclaims is repeated above-mentioned experiment, and measuring at last the dimethyl-silicon oil viscosity is 405mpas (quadric catalysis agent), by that analogy.When viscosity obviously descends, catalyzer in 700 ℃ of lower activating and regeneratings 2 hours, is continued to use experimental result such as following table:
| Catalyzer | Once | Secondary | Three times | Four times | Five times | Regeneration once |
| Viscosity mpas | 410 | 405 | 406 | 391 | 362 | 398 |
Claims (3)
1. the preparation method of a methyl-silicone oil is characterized in that preparing in the steps below:
(1) in reactor, adds a certain proportion of octamethylcyclotetrasiloxane (D
4) and hexamethyldisiloxane (MM), perhaps octamethylcyclotetrasiloxane (D
4) and polymethyl siloxane (D
n);
(2) the adding massfraction is 0.5～10% carried superstrong solid acid catalyzer;
(3) under 50～200 ℃, stir lower reaction 1～10 hour;
(4) after reaction finishes, filtering recovering catalyst, the decompression extracting is also reclaimed low-boiling-point substance, gets the silicone oil product.
2. preparation method according to claim 1 is characterized in that utilizing silicone oil (D at a low price
n), D
4Prepare the silicone oil of different viscosity (molecular weight) with MM, to adapt to various demands.
3. preparation method according to claim 1 is characterized in that with solid super-strong acid specifically referring to SO as catalyzer
4 2-/ ZrO
2-ZSM-5, its preparation method is as follows:
(1) with ZrOCl
2Soluble in water, under rapid stirring, drip ammoniacal liquor to PH=9～10, be precipitated;
(2) throw out after filtration and the washing, until do not contain chlorion in the filtrate;
(3) filter cake of gained is smashed to pieces afterwards in 100-110 ℃ of lower oven dry 3-12 hour;
(4) with (3) gained solid porphyrize, then join simultaneously in varing proportions with ZSM-5 molecular sieve and soak rear suction filtration in the dilute sulphuric acid;
(5) (4) are filtered the solid obtain 100～110 ℃ after lower dry 10～24 hours in air atmosphere in 550～700 ℃ of roastings 1.5～3.5 hours, namely obtain SO
4 2-/ ZrO
2-ZSM-5 solid super acid catalyst.
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|---|---|---|---|
| CN2011102598891A CN102977370A (en) | 2011-09-05 | 2011-09-05 | Preparation method of methylsilicone oil |
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|---|---|---|---|---|
| CN104059229A (en) * | 2014-06-18 | 2014-09-24 | 湖北兴发化工集团股份有限公司 | Preparation method for synthesizing methyl silicone oil under catalytic action of solid acid |
| CN105713200A (en) * | 2016-01-20 | 2016-06-29 | 江苏美思德化学股份有限公司 | Method for continuous preparation of polysiloxane by fixed-bed reactor |
| CN104072774B (en) * | 2014-06-13 | 2017-01-25 | 王金明 | Preparation technique of low-hydroxy-content dimethyl silicone oil |
| CN107441563A (en) * | 2017-06-27 | 2017-12-08 | 东莞御治医疗器械有限公司 | A kind of medicine equipment imports the preparation method of lubricant |
| CN108610484A (en) * | 2018-05-25 | 2018-10-02 | 广州盛泰诺新材料科技有限公司 | A kind of thermostable transparent methyl-silicone oil and its synthetic method |
| CN109022100A (en) * | 2018-07-19 | 2018-12-18 | 芜湖维软新材料有限公司 | The interior lubricated silicon oil containing octamethylcy-clotetrasiloxane |
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| CN114106332A (en) * | 2021-12-06 | 2022-03-01 | 甘肃银光聚银化工有限公司 | SO for catalytic synthesis of hydrogen-terminated silicone oil42-／ZrO2Process for preparing form catalyst |
-
2011
- 2011-09-05 CN CN2011102598891A patent/CN102977370A/en active Pending
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| CN104072774B (en) * | 2014-06-13 | 2017-01-25 | 王金明 | Preparation technique of low-hydroxy-content dimethyl silicone oil |
| CN104059229A (en) * | 2014-06-18 | 2014-09-24 | 湖北兴发化工集团股份有限公司 | Preparation method for synthesizing methyl silicone oil under catalytic action of solid acid |
| CN105713200A (en) * | 2016-01-20 | 2016-06-29 | 江苏美思德化学股份有限公司 | Method for continuous preparation of polysiloxane by fixed-bed reactor |
| CN105713200B (en) * | 2016-01-20 | 2018-11-02 | 江苏美思德化学股份有限公司 | A kind of method that fixed bed reactors continuously prepare polysiloxanes |
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| CN107441563B (en) * | 2017-06-27 | 2020-06-19 | 东莞御治医疗器械有限公司 | Preparation method of medical instrument introduction lubricant |
| CN108610484A (en) * | 2018-05-25 | 2018-10-02 | 广州盛泰诺新材料科技有限公司 | A kind of thermostable transparent methyl-silicone oil and its synthetic method |
| CN109022100A (en) * | 2018-07-19 | 2018-12-18 | 芜湖维软新材料有限公司 | The interior lubricated silicon oil containing octamethylcy-clotetrasiloxane |
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| CN109504971A (en) * | 2018-11-19 | 2019-03-22 | 湖北三环化学新材料股份有限公司 | A kind of preparation method for the cleaning agent that antifoaming speed is fast |
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| CN109370794B (en) * | 2018-11-19 | 2021-07-30 | 湖北三环化学新材料股份有限公司 | Preparation method of polyether modified organic silicon type defoaming agent |
| CN111085266A (en) * | 2019-12-30 | 2020-05-01 | 江苏美思德化学股份有限公司 | Method for synthesizing dimethyl silicone oil by catalysis of immobilized type bi-acid ionic liquid |
| CN111085266B (en) * | 2019-12-30 | 2023-01-03 | 江苏美思德化学股份有限公司 | Method for synthesizing dimethyl silicone oil by catalysis of immobilized type bi-acid ionic liquid |
| CN114106332A (en) * | 2021-12-06 | 2022-03-01 | 甘肃银光聚银化工有限公司 | SO for catalytic synthesis of hydrogen-terminated silicone oil42-／ZrO2Process for preparing form catalyst |
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Application publication date: 20130320 |