CN100348646C - Method for catalytic synthesis of alpha, omega-dihydroxy polydimethylsiloxane - Google Patents
Method for catalytic synthesis of alpha, omega-dihydroxy polydimethylsiloxane Download PDFInfo
- Publication number
- CN100348646C CN100348646C CNB2005100681441A CN200510068144A CN100348646C CN 100348646 C CN100348646 C CN 100348646C CN B2005100681441 A CNB2005100681441 A CN B2005100681441A CN 200510068144 A CN200510068144 A CN 200510068144A CN 100348646 C CN100348646 C CN 100348646C
- Authority
- CN
- China
- Prior art keywords
- omega
- alpha
- potassium hydroxide
- temperature
- described method
- 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.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000004205 dimethyl polysiloxane Substances 0.000 title claims abstract description 12
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 title claims abstract description 12
- -1 polydimethylsiloxane Polymers 0.000 title abstract description 18
- 238000007036 catalytic synthesis reaction Methods 0.000 title 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 42
- 238000010924 continuous production Methods 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 10
- 230000003472 neutralizing effect Effects 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 7
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229920001296 polysiloxane Polymers 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
The continuous process for synthesizing alpha, omega-dihydroxy polydimethylsiloxane by using potassium hydroxide as catalyst and water vapour method under normal pressure is simple and stable in operation, easy to control, mild in condition, prominent in technical index, not harsh in requirements for reactor, good in continuity and high in safety.
Description
Technical field
The present invention relates to a kind of production method of silicone rubber products.
Background technology
α, alpha, omega-dihydroxy polydimethyl siloxane (being called for short the hydroxyl polysiloxane) are one of staple products in the silicon rubber.All have a wide range of applications as fields such as building, coating, industrial art in many aspects.Along with the fast development of Building Trade in China in recent years, hydroxyl polysiloxane (building sealant main raw material) demand increases sharply, and simultaneously, industries such as coating, molding are also all keeping great demand to the hydroxyl polysiloxane.Intermittently flow process is adopted in the production of present domestic hydroxyl polysiloxane basically, and its technology is divided polymerization, degraded, termination, devolatilization four-stage, and four processes are all finished in same reactor.The shortcoming of this type of technology is that technology is numerous and diverse, quality product is wayward, the viscosity first-time qualification rate only about 50%, single still production cycle is long, throughput is low, and this process catalyst adopts Tetramethylammonium hydroxide, shortcomings such as exist product colour dark, smell is big, and molecular weight distribution is wide.
US 5,475, and 077 to have introduced with KOH be that catalyzer will encircle the dimethyl siloxane ring-opening polymerization, feed the method for water vapour with the air in the reactor and other gas displacements after 30 minutes.Under 170 ℃, 315 mmhg pressures, the airtight maintenance of reactor 30 minutes adds neutralizing agent ethylene chlorhydrin or other subsequently, and sylvite and the precipitation in the reactant that generates that will neutralize then removed, and hydroxyl polysiloxane molecule amount is regulated by the control water vapour pressure.This method is a discontinuous method.
US 4,780,519 and US 5,173,558 to have introduced with silanol potassium be that catalyzer, the silica-based acetic ester of dimethyl vinyl are the method for neutralizing agent.Hydroxy radical content in the polymkeric substance is controlled by water vapour pressure in the controlling reactor in polymerization process.This method is not to be used to produce the hydroxyl polysiloxane, but is used to produce the polysiloxane of other bigger group end capping of molecular weight, reduces the content of hydroxyl simultaneously with the method for control water vapour pressure, to enhance product performance.
US 4,551, and 515 have introduced the method for continuous production organopolysiloxane.Mixed methylcyclosiloxane and chain termination agent must dewater before adding catalyzer in this method; The silanol potassium that contains 5%KOH is catalyzer, and silica-based phosphoric acid ester is a neutralizing agent.This method is used to produce full-bodied polysiloxane, rather than the hydroxyl polysiloxane.
US 4,250, and 290 have introduced a kind of technology of continuous production hydroxyl polysiloxane.Polyreaction is carried out in static mixer, and catalyzer is the siloxanes potassium alcoholate, and temperature of reaction is 160-190 ℃, and neutralizing agent is silica-based phosphoric acid ester, and polymerization pressure is 1.17Mpa; If water is chain termination agent, then add at twice, the front end at polymeric part adds water for the first time, amount is 100ppm-500ppm, at polymerization rear end Jia Shui, primary water is mainly used in the growth of the viscosity of controlling polymers for the second time, to guarantee the mixed effect of static mixer; Secondary water is used for regulating the total amount of water.Product viscosity is 0.5-500Pa.s.System pressure is 170Psig, promptly is equivalent to 1.17Mpa, is pressurized conditions operation down, thereby higher to equipment requirements, and production cost is also higher.Japan, spy open flat 5-43,694 methods of being introduced and above-mentioned resemble process.
In sum, the synthetic method of hydroxyl polysiloxane can be selected different catalyzer, neutralizing agent and raw material, generally believe better as catalyzer with potassium hydroxide, raw material adopts ring body more, the neutralizing agent range of choice is corresponding bigger, but mentioned method has following problem in the document: production method has uses interrupter method, can not form the continuous process flow process, only be confined to be unfavorable for industrialization in laboratory or the small mode scope; Continuous process needs to carry out under pressurized conditions, and is relatively harsher to equipment requirements, is unfavorable for reducing production costs.
Summary of the invention
The purpose of this invention is to provide a kind ofly under normal pressure, carry the steam method secretly with nitrogen, potassium hydroxide is made the continuous process of the synthetic α of catalyzer, alpha, omega-dihydroxy polydimethyl siloxane.
The invention provides a kind ofly under normal pressure, adopt potassium hydroxide to make catalyzer, the continuous process with the synthetic α of steam method, alpha, omega-dihydroxy polydimethyl siloxane comprises the steps:
(A) methyl cyclosiloxane and potassium hydroxide carry out polyreaction in polymeric kettle, and polymerization temperature is 130-170 ℃;
(B) be in the neutralizing agent and polymerisate with silica-based phosphoric acid ester, neutral temperature is 100-160 ℃;
(C) remove low molecule and unreacted ring body in the neutralized reaction product, taking off low temperature is 170-190 ℃, takes off low vacuum 0.08-0.10Mpa, obtains α, alpha, omega-dihydroxy polydimethyl siloxane.
Concrete operations are as follows:
The methyl cyclosiloxane is pressed in the batching still and after catalyzer stirs, is pressed into feed chamber with nitrogen through test tank, enters polymeric kettle continuously after the spinner-type flowmeter metering, carries steam secretly with nitrogen and enters polymeric kettle continuously, carries out polyreaction.During hydroxyl polysiloxane after the polymerization is squeezed into continuously with the single pole spiral pump and still, during the silica-based phosphoric acid ester of neutralizing agent enters continuously and still, the siloxane polymer after the neutralization enters and takes off low still, removes low molecule and unreacted ring body under vacuum condition.Take off polymkeric substance after low through packing, be α, alpha, omega-dihydroxy polydimethyl siloxane finished product.
The preferred 140-160 of polymerization temperature among the present invention ℃; The preferred 120-140 of neutral temperature ℃
The methyl cyclosiloxane among the present invention and the weight ratio of potassium hydroxide are 100: (10-15).
The tank reactor that polymerization reactor of the present invention stirs for band.The used reactor of neutralization reaction is a static mixer.
In the polymeric kettle residence time of reactant make polyreaction after unreacted methyl cyclosiloxane be less than 12-14%.
The methyl cyclosiloxane that the present invention uses is colourless transparent liquid, neutrality, and no bromine flavor, nontoxic, flammable, two sense chain link content (molar percentage) 〉=99.99%, no free-water, density is 0.970-0.980.
The α, the alpha, omega-dihydroxy polydimethyl siloxane range of viscosities that obtain by the inventive method are 5-80Pa.s.
The continuation method of the down synthetic α of a kind of normal pressure provided by the invention, alpha, omega-dihydroxy polydimethyl siloxane, the continuous process that has overcome prior art needs to carry out under pressurized conditions, and is relatively harsher to equipment requirements, is unfavorable for the shortcoming that reduces production costs.The present invention simultaneously adopts the method for nitrogen water entrainment to make stable operation of the present invention, is easy to control.This processing method is simple, mild condition, and technical indicator is outstanding, and not harsh to the reactor requirement, continuity is better, and security is higher.
Embodiment
The invention will be further described below by embodiment.
Embodiment one
The methyl cyclosiloxane is pressed in the batching still through test tank, after the adding potassium hydroxide catalyst stirs, be pressed into feed chamber, after the spinner-type flowmeter metering, enter polymeric kettle continuously with given pace with nitrogen, water is done carrier gas with nitrogen after the vaporizer vaporization, enter polymeric kettle continuously with given pace.Under 150 ℃, carry out polyreaction, leave polymeric kettle then, during hydroxyl polysiloxane after the polymerization is squeezed into continuously with the single pole spiral pump and still, during the silica-based phosphoric acid ester of neutralizing agent enters continuously with certain speed and still, neutral temperature is 130 ℃, siloxane polymer after the neutralization enters and takes off low still, 180 ℃ ,-remove low molecule and unreacted ring body under the 0.096Mpa.Other processing condition such as following table (1,2,3 are respectively three kinds of differential responses conditions).
| 1 | 2 | 3 | |
| Methyl cyclosiloxane feeding rate (l/h) | 35 | 35 | 35 |
| Potassium hydroxide feeding rate (kg/s) | 3.40 | 3.40 | 3.40 |
| Silica-based phosphoric acid ester feeding rate (kg/s) | 18 | 18 | 18 |
| Working pressure | Normal pressure | Normal pressure | Normal pressure |
| The residence time (h) nitrogen flow rate (m 3/ h) introducing speed (l/h) viscosity (Pas) transformation efficiency (%) fugitive constituent (%) of water | 2 0.5 0.60 13.80 85.00 1.69 | 2 0.5 0.72 7.80 85.58 1.64 | 2 0.5 0.96 4.84 86.87 1.56 |
Embodiment two
Operational process of craft such as example one.Polymerization temperature is 155 ℃, and neutral temperature is 150 ℃, and taking off low temperature is 185 ℃, takes off low pressure and is-0.096Mpa other processing condition such as following table (1,2 are respectively two kinds of differential responses conditions).
| 1 | 2 | |
| Introducing speed (l/h) nitrogen flow rate (m of the silica-based phosphate feed rate of methyl cyclosiloxane feed rate (l/h) potassium hydroxide feed rate (kg/s) (kg/s) the operating pressure time of staying (h) water3/ h) viscosity (Pas) transformation efficiency (%) fugitive constituent (%) | 35 3.40 18 normal pressures 2 0.96 0.5 5.26 86.10 1.56 | 35 3.40 18 normal pressures 2 0.96 1.0 5.13 89.30 1.85 |
Embodiment three
Operational process of craft such as example one.Polymerization temperature is 160 ℃, and neutral temperature is 155 ℃, and taking off low temperature is 190 ℃, takes off low pressure and is-0.095Mpa other processing condition such as following table (1,2 are respectively two kinds of differential responses conditions).
| 1 | 2 |
| Introducing speed (l/h) catalyst amount (ppm) viscosity (Pas) conversion ratio (%) fugitive constituent (%) of the silica-based phosphate feed rate of methyl cyclosiloxane feed rate (l/h) (kg/s) the operating pressure time of staying (h) water | 35 18 normal pressures 2 0.96 19 4.82 77.25 1.64 | 35 18 normal pressures 2 0.96 27 5.24 86.43 1.42 |
Claims (5)
- One kind under normal pressure, adopt potassium hydroxide to make catalyzer, the continuous process with the synthetic α of steam method, alpha, omega-dihydroxy polydimethyl siloxane comprises the steps:(A) methyl cyclosiloxane and potassium hydroxide carry out polyreaction in polymeric kettle, and polymerization temperature is 130-170 ℃;(B) be in the neutralizing agent and polymerisate with silica-based phosphoric acid ester, neutral temperature is 100-160 ℃;(C) remove low molecule and unreacted ring body in the neutralized reaction product, taking off low temperature is 170-190 ℃, takes off low vacuum 0.08-0.10Mpa, obtains α, alpha, omega-dihydroxy polydimethyl siloxane.
- 2. the described method of claim 1 is characterized in that polymeric reaction temperature wherein is 140-160 ℃.
- 3. the described method of claim 1 is characterized in that neutral temperature wherein is 120-140 ℃.
- 4. the described method of claim 1, it is characterized in that wherein the methyl cyclosiloxane and the weight ratio of potassium hydroxide be 100: (10-15).
- 5. the described method of claim 1, it is characterized in that reactant residence time in the polymeric kettle wherein make polyreaction after unreacted methyl cyclosiloxane be less than 12-14%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100681441A CN100348646C (en) | 2005-04-29 | 2005-04-29 | Method for catalytic synthesis of alpha, omega-dihydroxy polydimethylsiloxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100681441A CN100348646C (en) | 2005-04-29 | 2005-04-29 | Method for catalytic synthesis of alpha, omega-dihydroxy polydimethylsiloxane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1854171A CN1854171A (en) | 2006-11-01 |
| CN100348646C true CN100348646C (en) | 2007-11-14 |
Family
ID=37194654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100681441A Expired - Fee Related CN100348646C (en) | 2005-04-29 | 2005-04-29 | Method for catalytic synthesis of alpha, omega-dihydroxy polydimethylsiloxane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100348646C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210074B (en) * | 2007-12-24 | 2010-11-10 | 中昊晨光化工研究院 | Method for producing alpha, omega-dihydroxy polydimethyl siloxane |
| CN102127227B (en) * | 2010-12-27 | 2013-03-13 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | Low viscosity hydroxyl terminated polysiloxane and preparation method thereof |
| CN102093561B (en) * | 2010-12-27 | 2013-05-29 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | High-efficiency catalyst used for preparing high ring 107 glue and preparation method thereof |
| CN103059303B (en) * | 2012-12-25 | 2015-05-06 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | Preparation method of hydroxyl blocking polydimethylsiloxane |
| CN103122069B (en) * | 2013-02-28 | 2015-06-24 | 浙江大学 | Telomerization-free method and device for continuously preparing polysiloxane from cyclosiloxane |
| CN104140529A (en) * | 2014-07-10 | 2014-11-12 | 何少云 | Preparation method of high-viscosity silicone oil |
| CN110606953A (en) * | 2019-09-26 | 2019-12-24 | 唐山三友硅业有限责任公司 | Low-viscosity hydroxyl-terminated vinyl methyl silicone oil and continuous preparation method thereof |
| CN110655049B (en) * | 2019-10-09 | 2022-02-01 | 新纳奇材料科技江苏有限公司 | Preparation method of phosphonitrile chloride catalyst and application of phosphonitrile chloride catalyst in preparation of alkoxy-terminated polysiloxane |
| CN112831049A (en) * | 2021-03-09 | 2021-05-25 | 浙江新安化工集团股份有限公司 | Preparation method of alpha, omega-dihydroxy polydimethylsiloxane |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1292260A (en) * | 1999-09-29 | 2001-04-25 | 欧莱雅 | Detergent composition made from keratin material |
-
2005
- 2005-04-29 CN CNB2005100681441A patent/CN100348646C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1292260A (en) * | 1999-09-29 | 2001-04-25 | 欧莱雅 | Detergent composition made from keratin material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1854171A (en) | 2006-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100348646C (en) | Method for catalytic synthesis of alpha, omega-dihydroxy polydimethylsiloxane | |
| CN101967226B (en) | Method for synthesizing high-activity high molecular weight polyether polyalcohol | |
| CN102940982B (en) | High-efficiency defoaming agent for biological fermentation system and preparation process thereof | |
| CN102453253A (en) | Preparation process of polyether polyol with high primary hydroxyl | |
| CN101173044A (en) | Method for producing 107 adhesive by comprehensive utilization of organosilicon hydrolyzation material loop separation | |
| CN105778104B (en) | A kind of add-on type liquid fluorine silicon rubber base glue and preparation method thereof | |
| CN107936241A (en) | Polyethers for defoamer and preparation method thereof | |
| CN102504239A (en) | Catalyst for preparing polycarboxylate water reducing agent macromonomer and preparation method thereof | |
| CN105384936A (en) | Polyvinylsilicone oil preparation method | |
| CN107177034A (en) | A kind of allyl alcohol polyethenoxy ether and preparation method thereof | |
| CN102532379B (en) | Polymerization method for preparing rare earth isoprene rubber | |
| CN1278838A (en) | Process for preparing polyether polyols and polyols prepared therewith | |
| CN101220156B (en) | Process for producing polyvinyl chloride polymerization organosilicon inarch polyether antifoam agent | |
| CN102924705A (en) | Preparation method of dimethylallyl polyether | |
| CN203794820U (en) | Hydrolyzing loop system for continuously producing high-hydrogen-content silicone oil | |
| CN109161011A (en) | A kind of production method of butylene glycol polyoxyethylene ether | |
| CN106749973B (en) | Continuous production equipment and production method of polycarboxylate superplasticizer | |
| CN106633030B (en) | Preparation method of high molecular weight narrow distribution esterification terminated allyl alcohol polyether | |
| CN114672012A (en) | Method for preparing polyether polyol based on micro mixer and micro-channel reactor | |
| CN110041527A (en) | A kind of high viscosity containing hydrogen silicone oil and preparation method thereof | |
| CN103665381B (en) | Synthesis method of hydroxyl capped polydimethylsiloxane | |
| CN116239453A (en) | Synthesis method of pentaerythritol triallyl ether | |
| CN105482121A (en) | Synthesis method of polyvinyl silicon oil | |
| CN101747162A (en) | Synthesis process of p-methoxystyrene | |
| CN116323754A (en) | Novel defoaming agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071114 |