CN108178834A - A kind of preparation method of graft modification silicone oil - Google Patents
A kind of preparation method of graft modification silicone oil Download PDFInfo
- Publication number
- CN108178834A CN108178834A CN201711282562.XA CN201711282562A CN108178834A CN 108178834 A CN108178834 A CN 108178834A CN 201711282562 A CN201711282562 A CN 201711282562A CN 108178834 A CN108178834 A CN 108178834A
- Authority
- CN
- China
- Prior art keywords
- silicone oil
- graft modification
- preparation
- catalyst
- buffer
- 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.)
- Pending
Links
- 0 CC(CC(C)(C)O*)N Chemical compound CC(CC(C)(C)O*)N 0.000 description 1
Classifications
-
- 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Silicon Polymers (AREA)
Abstract
The present invention relates to a kind of preparation methods of graft modification silicone oil, and silicon oil of low hydrogen content, allyl polyether, catalyst and buffer are passed through in microreactor, and 20 ~ 1000 seconds graft modification silicone oil for being made described is reacted under 60 ~ 160 DEG C, 0 ~ 20bar.The present invention by the improvement to preparation method, not only by level of residual monomers be reduced to 5% hereinafter, and solve the problems, such as that polymer molecular weight is wide, polymer molecular weight profile exponent is<1.2, while the reaction time is greatly shortened, effectively avoid the generation of side reaction.The production technology improve product quality, easy to operate, waste is few, low energy consumption environmental protection.
Description
Technical field
The present invention relates to a kind of preparation methods of graft modification silicone oil.
Background technology
At present, based on batch method, this method is generally first low by reactant for the production of domestic grafted-organosilicon copolymer
Containing hydrogen silicone oil, allyl polyether, buffer, solvent etc. are first added in reaction kettle and are stirred, after heating heating (80 DEG C~100 DEG C),
After long-time heating (3-5h), by adding in catalyst (generally platinum catalyst) directly in kettle, insulation reaction is certain
Time (3-5h) completes the processes such as reaction, cooling filtering and completes production.
The above method has the following disadvantages：
1) monomer and catalyst impurities residual quantity are high；
2) polymer molecular weight distribution is wide, molecular weight distribution Index>1.2；
3) there are side reactions in polymerization process；
4) reaction time is long, and energy consumption is high；
5) complex procedures, efficiency are low；
6) equipment investment is big, takes up an area also bigger；
7) product needs cleaning equipment, generates a large amount of solvents and waste water；
8) from lab scale, pilot scale and last big production there is enlarge-effect in product.
Invention content
The technical problems to be solved by the invention be to provide it is a kind of it is simple for process, low energy consumption, efficient, high income, rear place
Reason is easy, the preparation method of the graft modification silicone oil of narrow molecular weight distribution.
For solution more than technical problem, the present invention adopts the following technical scheme that：
A kind of preparation method of graft modification silicone oil, silicon oil of low hydrogen content, allyl polyether, catalyst and buffer are passed through
In microreactor, 20~1000 seconds graft modification silicone oil for being made described is reacted under 60~160 DEG C, 0~20bar, and control
Flow velocity of the material in the microreactor is 5~400g/min.
Preferably, the reaction temperature be 90~140 DEG C, further preferably 100~130 DEG C, most preferably 110~
120℃。
Preferably, the reaction pressure is 6~10bar, further preferably 6~8bar.
Preferably, the reaction time is 20~600 seconds, further preferably 100~300 seconds.
Preferably, the flow velocity is 5~100g/min.
In the present invention, the material refer to silicon oil of low hydrogen content, allyl polyether, catalyst and buffer mixture or
Mixed material after reaction.
In the present invention, the structural formula of the low content hydrogen silicone oil is:
The structural formula of the allyl polyether is:
Wherein, m, n, x, y independently are 1~100 integer.The present invention reaction equation be：
Preferably, the molar ratio of the silicon oil of low hydrogen content and the allyl polyether is 1：1~1.8.
Preferably, the quality that feeds intake of the catalyst is the silicon oil of low hydrogen content, allyl polyether, described
Catalyst and the buffer gross mass of feeding intake 0.1~100ppm, further preferably 20~100ppm, more preferably
For 30~50ppm.
Preferably, the quality that feeds intake of the buffer is the silicon oil of low hydrogen content, allyl polyether, described
Catalyst and the buffer gross mass of feeding intake 0.1~1000ppm, further preferably 50~800ppm.
Preferably, the catalyst is the ethyl alcohol of the methanol solution of chloroplatinic acid, the methanol solution of chloroplatinous acid, chloroplatinic acid
Solution, the propanol solution of chloroplatinic acid, chloroplatinic acid one or more of isopropanol alcoholic solution combination and/or block this Taide and urge
Agent, the buffer is sodium formate, sodium acetate, sodium propionate, sodium butyrate, diethanol amine, dimethylethanolamine, diethyl second
The combination of one or more of hydramine, dibutylethanolamine or triethylamine, Tri-n-Propylamine, tri-n-butylamine.
Preferably, the microreactor is the G1-G4 microreactors of Corning Incorporated, and microwell array declines channel reactor
Or the material of the bold and generous Chemical Engineering Technology Co., Ltd of AFR-G1-G4 reactors or Shandong that material is stainless steel, glass or SiC is
316L, FFKM, Du Pont Kalrez0040,304, PEEK, PTFE, fluorine silicone rubber, 6061-T6, carbon steel nickel plating, PTFE, ABS, EVA
MRSS120 reactors.
Preferably, the microreactor is included for by the silicon oil of low hydrogen content, allyl polyether, described
The warm-up block that catalyst and the buffer are mixed and preheated is connected and is sequentially connected in series with the warm-up block
The first heat transfer module, the second heat transfer module, third heat transfer module, the 4th heat transfer module, the 5th heat transfer module, the 6th heat transfer mould
Block, the 7th heat transfer module, the material discharging module being connected with the 7th heat transfer module；Or
The microreactor is included for by the silicon oil of low hydrogen content, the allyl polyether, the catalyst
The reactive moieties for being exchanged heat, preheated, mixed, reacting and being controlled with the buffer.
Preferably, the mass tranfer coefficient of the microreactor is 1~30Ka, and exchange capability of heat is more than 1700KW/m2*k。
Preferably, first the catalyst, the buffer are added in the silicon oil of low hydrogen content and form mixture,
Then the mixture and the allyl polyether are delivered to respectively in the microreactor.
Due to the implementation of above technical scheme, the present invention has the following advantages that compared with prior art：
Level of residual monomers is not only reduced to 5% hereinafter, and solving polymerization by the improvement to preparation method by the present invention
The problem of object molecular weight is wide, polymer molecular weight profile exponent are reduced to 1.2 and hereinafter, when reaction being greatly shortened simultaneously
Between, effectively avoid the generation of side reaction.The production technology improves product quality, easy to operate, waste is few, low energy consumption ring
It protects.
Description of the drawings
Structure diagram of the attached drawing 1 for the micro passage reaction of the Corning Incorporated used in the present invention；
Structural representation of the attached drawing 2 for bold and generous 120 reactors of Chemical Engineering Technology Co., Ltd MRSS in Shandong used in the present invention
Figure, wherein, 1, installation frame；2nd, reactor；3rd, heat exchanging pipe.
Specific embodiment
With reference to specific embodiment, the present invention will be further described in detail, but the present invention is not limited to following implementations
Example.The implementation condition used in embodiment can do further adjustment according to specifically used different requirements, the implementation being not specified
Condition is the normal condition in the industry.
Embodiment 1 to 7：
Silicon oil of low hydrogen content shown in formula 1 added with catalyst and buffer and the allyl polyether shown in formula are used
Differential responses delivery pump is respectively delivered to be mixed and preheated in the warm-up block of the G1-G4 microreactors of Corning Incorporated, so
Afterwards followed by the first heat transfer module, the second heat transfer module, third heat transfer module, the 4th heat transfer module, the 5th heat transfer module,
Six heat transfer modules, the 7th heat transfer module are reacted, and are finally flow to material discharging module and are entered collecting tank after discharging after cooling down and collect
Obtain graft modification silicone oil；Or it is transported to the 120 reactor (technical data sheets of MRSS of the bold and generous Chemical Engineering Technology Co., Ltd in Shandong
It is shown in Table and 2) is exchanged heat, preheated, mixed, reacted and control obtains graft modification silicone oil.
Wherein, the technological parameter of each embodiment and experimental data are referring to table 1.
Table 1
Table 2
Comparative example 1 to 3：It is prepared by batch method
By reactant silicon oil of low hydrogen content, allyl polyether, buffer is first added in reaction kettle and is stirred, heating heating, by 4
After hour heating, by directly adding in catalyst in kettle, insulation reaction certain time completes reaction, and production is obtained by filtration in cooling
Product.
Other technological parameters and experimental data of comparative example 1 to 3 are shown in Table 3.
Table 3
The present invention is described in detail above, its object is to allow the personage for being familiar with this field technology that can understand this
The content of invention is simultaneously implemented, and it is not intended to limit the scope of the present invention, all Spirit Essence institutes according to the present invention
The equivalent change or modification of work should all cover within the scope of the present invention.
Claims (10)
1. a kind of preparation method of graft modification silicone oil, it is characterised in that：By silicon oil of low hydrogen content, allyl polyether, catalyst and
Buffer is passed through in microreactor, and 20~1000 seconds graft modification silicon for being made described is reacted under 60~160 DEG C, 0~20bar
Oil, and flow velocity of the control material in the microreactor is 5~400g/min.
2. the preparation method of graft modification silicone oil according to claim 1, it is characterised in that：The low content hydrogen silicone oil
Structural formula be:
The structural formula of the allyl polyether is:
Wherein, m, n, x, y independently are 1~100 integer.
3. the preparation method of graft modification silicone oil according to claim 1 or 2, it is characterised in that：The low Silicon Containing Hydrogen
The oily molar ratio with the allyl polyether is 1：1~1.8.
4. the preparation method of graft modification silicone oil according to claim 1, it is characterised in that：The catalyst feeds intake
Quality is total matter that feeds intake of the silicon oil of low hydrogen content, the allyl polyether, the catalyst and the buffer
0.1~100ppm of amount.
5. the preparation method of graft modification silicone oil according to claim 1, it is characterised in that：The buffer feeds intake
Quality is total matter that feeds intake of the silicon oil of low hydrogen content, the allyl polyether, the catalyst and the buffer
0.1~1000ppm of amount.
6. the preparation method of the graft modification silicone oil according to claim 1 or 4 or 5, it is characterised in that：The catalyst
The methanol solution of methanol solution, chloroplatinous acid, the ethanol solution of chloroplatinic acid, the propanol solution of chloroplatinic acid, chlorine platinum for chloroplatinic acid
The combination of one or more of the isopropanol alcoholic solution of acid and/or block this Taide catalyst, the buffer is sodium formate,
Sodium acetate, sodium propionate, sodium butyrate, diethanol amine, dimethylethanolamine, diethyl ethylene diamine, dibutylethanolamine or three second
The combination of one or more of amine, Tri-n-Propylamine, tri-n-butylamine.
7. the preparation method of graft modification silicone oil according to claim 1, it is characterised in that：The microreactor is health
The G1-G4 microreactors of Ning companies, microwell array decline the AFR-G1- that channel reactor or material are stainless steel, glass or SiC
The material of the bold and generous Chemical Engineering Technology Co., Ltd of G4 reactors or Shandong for 316L, FFKM, Du Pont Kalrez0040,304, PEEK,
PTFE, fluorine silicone rubber, 6061-T6, carbon steel nickel plating, PTFE, ABS, EVA MRSS120 reactors.
8. the preparation method of the graft modification silicone oil according to claim 1 or 7, it is characterised in that：The microreactor
Including being used to mix the silicon oil of low hydrogen content, the allyl polyether, the catalyst and the buffer
And preheat warm-up block, the first heat transfer module for being connected and being sequentially connected in series with the warm-up block, the second heat transfer module,
Third heat transfer module, the 4th heat transfer module, the 5th heat transfer module, the 6th heat transfer module, the 7th heat transfer module, with the described the 7th
The material discharging module that heat transfer module is connected；Or
The microreactor is included for by the silicon oil of low hydrogen content, the allyl polyether, the catalyst and institute
The reactive moieties that the buffer stated is exchanged heat, preheated, mixed, react and controlled.
9. the preparation method of the graft modification silicone oil according to claim 1 or 7, it is characterised in that：The microreactor
Mass tranfer coefficient for 1~30Ka, exchange capability of heat is more than 1700KW/m2*k。
10. the preparation method of graft modification silicone oil according to claim 1, it is characterised in that：First by the catalyst,
The buffer adds in the silicon oil of low hydrogen content and forms mixture, then by the mixture and the pi-allyl
Polyethers is delivered to respectively in the microreactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711282562.XA CN108178834A (en) | 2017-12-07 | 2017-12-07 | A kind of preparation method of graft modification silicone oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711282562.XA CN108178834A (en) | 2017-12-07 | 2017-12-07 | A kind of preparation method of graft modification silicone oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108178834A true CN108178834A (en) | 2018-06-19 |
Family
ID=62545809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711282562.XA Pending CN108178834A (en) | 2017-12-07 | 2017-12-07 | A kind of preparation method of graft modification silicone oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108178834A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358095A (en) * | 2019-08-05 | 2019-10-22 | 江西麦豪化工科技有限公司 | A kind of method of continuity method production organic silicon surfactant |
| CN111004396A (en) * | 2019-12-27 | 2020-04-14 | 江苏美思德化学股份有限公司 | Tertiary amino modified organic silicon polyether copolymer and preparation method and application thereof |
| CN111040176A (en) * | 2019-12-27 | 2020-04-21 | 江苏美思德化学股份有限公司 | Organic silicon polyether copolymer and preparation method and application thereof |
| CN111548500A (en) * | 2020-05-29 | 2020-08-18 | 广州星粤新材料有限公司 | Method for preparing polyether grafted polysiloxane by using microchannel reactor |
| CN111875802A (en) * | 2020-06-19 | 2020-11-03 | 上海抚佳精细化工有限公司 | Application of amine stabilizer in preparation of hydrophilic silicone oil with stable viscosity and preparation method of hydrophilic silicone oil |
| CN112661965A (en) * | 2020-12-22 | 2021-04-16 | 埃夫科纳聚合物股份有限公司 | Preparation method of organic silicon auxiliary agent |
| CN112759764A (en) * | 2020-12-30 | 2021-05-07 | 深圳市安品有机硅材料有限公司 | Improved organopolysiloxane synthesis |
| CN113416310A (en) * | 2021-05-31 | 2021-09-21 | 南京林业大学 | Preparation method of organic silicon modified acrylate |
| CN115386080A (en) * | 2021-05-25 | 2022-11-25 | 江西蓝星星火有机硅有限公司 | Method for preparing polyether modified siloxane |
| CN115466396A (en) * | 2022-10-19 | 2022-12-13 | 江苏盛普高新材料有限责任公司 | Synthesis of polyester modified polydimethylsiloxane by micro-channel method |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101637708A (en) * | 2009-09-01 | 2010-02-03 | 陕西科技大学 | Method for preparing solvent-free polyether grafting organosilico/diamide compound emulsion defoamer |
| CN102031697A (en) * | 2010-11-05 | 2011-04-27 | 辽宁科隆精细化工股份有限公司 | Method for preparing polyester and polyether modified silicone oil ternary copolymer textile finishing agent |
| CN102089355A (en) * | 2008-07-08 | 2011-06-08 | 比克化学股份有限公司 | Polyhydroxyfunctional polysiloxanes for increasing the surface energy of thermoplastics, method for production and use thereof |
| US20110185947A1 (en) * | 2008-07-08 | 2011-08-04 | Byk-Chemie Gmbh | Polyhydroxyfunctional polysiloxane as anti-adhesive and dirt-repellant additives in coatings polymeric moulded masses and thermoplastics, method for production and use thereof |
| CN102977377A (en) * | 2012-12-04 | 2013-03-20 | 昆山市张浦彩印厂 | Solvent-free method for preparing polyether modified polysiloxane antifoaming agent |
| CN104592802A (en) * | 2013-10-30 | 2015-05-06 | 上海飞凯光电材料股份有限公司 | Preparation method of polyether modified organic silicon |
| CN105504286A (en) * | 2015-12-21 | 2016-04-20 | 上海麦浦新材料科技有限公司 | Low-hydro silicone oil, organosilicon surfactant and preparation method and application thereof |
| CN106397106A (en) * | 2015-07-28 | 2017-02-15 | 浙江省化工研究院有限公司 | Method for performing olefin addition reaction by using microchannel reactor |
-
2017
- 2017-12-07 CN CN201711282562.XA patent/CN108178834A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102089355A (en) * | 2008-07-08 | 2011-06-08 | 比克化学股份有限公司 | Polyhydroxyfunctional polysiloxanes for increasing the surface energy of thermoplastics, method for production and use thereof |
| US20110185947A1 (en) * | 2008-07-08 | 2011-08-04 | Byk-Chemie Gmbh | Polyhydroxyfunctional polysiloxane as anti-adhesive and dirt-repellant additives in coatings polymeric moulded masses and thermoplastics, method for production and use thereof |
| CN101637708A (en) * | 2009-09-01 | 2010-02-03 | 陕西科技大学 | Method for preparing solvent-free polyether grafting organosilico/diamide compound emulsion defoamer |
| CN102031697A (en) * | 2010-11-05 | 2011-04-27 | 辽宁科隆精细化工股份有限公司 | Method for preparing polyester and polyether modified silicone oil ternary copolymer textile finishing agent |
| CN102977377A (en) * | 2012-12-04 | 2013-03-20 | 昆山市张浦彩印厂 | Solvent-free method for preparing polyether modified polysiloxane antifoaming agent |
| CN104592802A (en) * | 2013-10-30 | 2015-05-06 | 上海飞凯光电材料股份有限公司 | Preparation method of polyether modified organic silicon |
| CN106397106A (en) * | 2015-07-28 | 2017-02-15 | 浙江省化工研究院有限公司 | Method for performing olefin addition reaction by using microchannel reactor |
| CN105504286A (en) * | 2015-12-21 | 2016-04-20 | 上海麦浦新材料科技有限公司 | Low-hydro silicone oil, organosilicon surfactant and preparation method and application thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358095A (en) * | 2019-08-05 | 2019-10-22 | 江西麦豪化工科技有限公司 | A kind of method of continuity method production organic silicon surfactant |
| CN111004396A (en) * | 2019-12-27 | 2020-04-14 | 江苏美思德化学股份有限公司 | Tertiary amino modified organic silicon polyether copolymer and preparation method and application thereof |
| CN111040176A (en) * | 2019-12-27 | 2020-04-21 | 江苏美思德化学股份有限公司 | Organic silicon polyether copolymer and preparation method and application thereof |
| CN111004396B (en) * | 2019-12-27 | 2022-07-05 | 江苏美思德化学股份有限公司 | Tertiary amino modified organic silicon polyether copolymer and preparation method and application thereof |
| CN111548500A (en) * | 2020-05-29 | 2020-08-18 | 广州星粤新材料有限公司 | Method for preparing polyether grafted polysiloxane by using microchannel reactor |
| CN111875802A (en) * | 2020-06-19 | 2020-11-03 | 上海抚佳精细化工有限公司 | Application of amine stabilizer in preparation of hydrophilic silicone oil with stable viscosity and preparation method of hydrophilic silicone oil |
| CN112661965A (en) * | 2020-12-22 | 2021-04-16 | 埃夫科纳聚合物股份有限公司 | Preparation method of organic silicon auxiliary agent |
| CN112759764A (en) * | 2020-12-30 | 2021-05-07 | 深圳市安品有机硅材料有限公司 | Improved organopolysiloxane synthesis |
| CN115386080A (en) * | 2021-05-25 | 2022-11-25 | 江西蓝星星火有机硅有限公司 | Method for preparing polyether modified siloxane |
| CN115386080B (en) * | 2021-05-25 | 2023-09-19 | 江西蓝星星火有机硅有限公司 | Method for preparing polyether modified siloxane |
| CN113416310A (en) * | 2021-05-31 | 2021-09-21 | 南京林业大学 | Preparation method of organic silicon modified acrylate |
| CN115466396A (en) * | 2022-10-19 | 2022-12-13 | 江苏盛普高新材料有限责任公司 | Synthesis of polyester modified polydimethylsiloxane by micro-channel method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108178834A (en) | A kind of preparation method of graft modification silicone oil | |
| WO2021022832A1 (en) | Method for continuously producing organosilicon surfactant | |
| CN108178833A (en) | A kind of preparation method of silicone oil | |
| WO2022135443A1 (en) | Preparation method for organosilicon auxiliary agent | |
| CN102977377A (en) | Solvent-free method for preparing polyether modified polysiloxane antifoaming agent | |
| CN103804689B (en) | A kind of silicone oligomer of the special resistance to anti-soil of polyureas and preparation method thereof | |
| CN105778104B (en) | A kind of add-on type liquid fluorine silicon rubber base glue and preparation method thereof | |
| CN111548500A (en) | Method for preparing polyether grafted polysiloxane by using microchannel reactor | |
| CN110776641A (en) | Preparation method of amino polyether modified polysiloxane | |
| CN101531367B (en) | Process for producing silicane | |
| CN101220156B (en) | Process for producing polyvinyl chloride polymerization organosilicon inarch polyether antifoam agent | |
| CN109575293A (en) | A kind of preparation method of high polymerization degree backbone chain type organic silicon modified by polyether foam stabilizer | |
| CN112028926B (en) | Separation device and separation method for removing silicon tetrachloride in organosilicon monomer azeotrope | |
| CN111484610A (en) | Preparation method of polycarbonate-polyether diol | |
| CN100588670C (en) | Process of preparing alkyl dead-end polyether by polyether with parahydroxyl at molecular chain end | |
| CN112979952B (en) | High-hydrogen-content silicone oil production system with low waste acid discharge and preparation method | |
| CN111393629B (en) | Method for continuous production of polypropylene carbonate by preheating liquid phase method in pipeline manner | |
| CN114672012A (en) | Method for preparing polyether polyol based on micro mixer and micro-channel reactor | |
| CN105693759B (en) | The method for preparing chloropropyl alkylalkoxy silane using pathway reaction device | |
| CN107055550A (en) | A kind of method for preparing dichlororosilane eiectronic grade | |
| CN220684694U (en) | Polysilicon cold hydrogenation process system | |
| CN211384957U (en) | Continuous production device for trimethyl allyl ammonium chloride | |
| CN105418668A (en) | Preparation method for 3-acryloyloxy propyl trimethoxysilane | |
| CN114426667B (en) | Continuous preparation system and process method for MQ resin with narrow molecular weight distribution | |
| CN109364869A (en) | A kind of device of gas-liquid countercurrent method continuous production chloro thing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180619 |