CN110041527A - A kind of high viscosity containing hydrogen silicone oil and preparation method thereof - Google Patents
A kind of high viscosity containing hydrogen silicone oil and preparation method thereof Download PDFInfo
- Publication number
- CN110041527A CN110041527A CN201910342006.XA CN201910342006A CN110041527A CN 110041527 A CN110041527 A CN 110041527A CN 201910342006 A CN201910342006 A CN 201910342006A CN 110041527 A CN110041527 A CN 110041527A
- Authority
- CN
- China
- Prior art keywords
- silicone oil
- containing hydrogen
- preparation
- hydrogen silicone
- high viscosity
- 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
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
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- 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
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- 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
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention belongs to chemical technology fields more particularly to a kind of high viscosity containing hydrogen silicone oil and preparation method thereof.A kind of preparation method of high viscosity containing hydrogen silicone oil, this method includes the following steps: 1) using high hydrogen content polysiloxanes and cyclosiloxane as reaction monomers, and organic solvent is added, and polymerization reaction is carried out under acidic catalyst effect, polymerization reaction time is 1-20 hours, and temperature is 20-60 DEG C；2) after polymerization reaction, obtained reaction solution is neutralized to neutrality and filters out solid salt；3) solvent and low-boiling-point substance therein are sloughed at high temperature, and the removing vacuum degree for removing low-boiling-point substance is -0.01MPa~-0.098MPa, and temperature is 100-180 DEG C, and high viscosity containing hydrogen silicone oil can be obtained.The hydrogen content of high viscosity containing hydrogen silicone oil of the invention, which is 0.1-0.8wt% as the crosslinking agent of addition-type silicon rubber and silicone resin, can be improved the mechanical property of addition-type silicon rubber and silicone resin, and hardness can be adjusted, and its raw material is easy to get, simple production process, it is with short production cycle, it is suitble to industrialized production.
Description
Technical field
The invention belongs to chemical technology fields more particularly to a kind of high viscosity containing hydrogen silicone oil and preparation method thereof.
Background technique
Containing hydrogen silicone oil is one of extremely important product in silicone oil product, contains reactive group in its siloxane main chain
Hydrogen, activity is higher, and can react with various active group, and this unique performance has obtained containing hydrogen silicone oil extensively in many fields
General application is such as used as antifouling, the grease proofing, waterproof finishing agent of building；Prepare the raw material of modified silicon oil；In addition, in catalyst
Under effect, it can react with other chemical substances containing double bond, hydroxyl isoreactivity group, also can be used as the friendship of liquid silastic
Join agent.
With the development of organosilicon auxiliary agent industry, the performances such as the surface property of auxiliary agent, feel, foam stabilizing are proposed higher
It is required that；In addition demand of the addition-type silicon rubber product to the promotion of mechanical property and hardness adjustment is also to the polynary of containing hydrogen silicone oil
Change has more requirements；Therefore, highly viscous containing hydrogen silicone oil has many demands.However, due to the limitation of production technology,
The containing hydrogen silicone oil of commercialization is mostly the product of low viscosity.
Summary of the invention
It is an object of the present invention to provide a kind of preparation method of high viscosity containing hydrogen silicone oil, this method includes step below
It is rapid:
1) using high hydrogen content polysiloxanes and cyclosiloxane as reaction monomers, and organic solvent is added, makees in acidic catalyst
Polymerization reaction is carried out under, polymerization reaction time is 1-20 hours, and temperature is 20-60 DEG C；
2) after polymerization reaction, obtained reaction solution is neutralized to neutrality and filters out solid salt；
3) solvent and low-boiling-point substance therein are sloughed at high temperature, remove low-boiling-point substance removing vacuum degree be -0.01MPa~-
0.098MPa, temperature are 100-180 DEG C, and high viscosity containing hydrogen silicone oil can be obtained.
As a preferred option, the high hydrogen containing siloxane is the group of one or more of high containing hydrogen silicone oil
It closes；A kind of specific embodiment, high containing hydrogen silicone oil is as shown in following general structure:
；
The cyclosiloxane is hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane, ten diformazans
The combination of one or more of six siloxanes of basic ring.
As a preferred option, the mass ratio of the high hydrogen containing siloxane and cyclosiloxane is 1:20-2:1；Further preferably,
The mass ratio of the high hydrogen containing siloxane and cyclosiloxane is 1:15-5:1.
As a preferred option, the reaction monomers of the containing hydrogen silicone oil further include end-capping reagent, and end-capping reagent is two silicon oxygen of hexamethyl
Alkane, tetramethyl disiloxane, low viscosity dimethyl silicone oil a combination of one or more.
As a preferred option, the organic solvent be petroleum ether, n-hexane, toluene, dimethylbenzene, acetone, ethyl acetate,
The combination of one or more of butyl acetate, chloroform, ether, dimethylformamide, methylene chloride, methanol, ethyl alcohol, and its
Additive amount is 0.1-10 times of high hydrogen content polysiloxanes and cyclosiloxane gross mass.
As a preferred option, the acidic catalyst be concentration be 98wt% sulfuric acid, concentration be 36-37wt% salt
One or both of acid, methanesulfonic acid, p-methyl benzenesulfonic acid, trifluoromethanesulfonic acid, storng-acid cation exchange resin and Emathlite
Above combination, and dosage is the 1%-10% of high hydrogen content polysiloxanes and cyclosiloxane gross mass.
As a preferred option, the neutralizer is sodium carbonate, in sodium bicarbonate, calcium carbonate, magnesium carbonate, aluminium hydroxide
A combination of one or more.
As a preferred option, the time of the polymerization reaction is 2-5 hours, and polymeric reaction temperature is 30-50 DEG C；It is described
The removing vacuum degree for removing low-boiling-point substance is -0.098MPa, and temperature is 120-150 DEG C.
Another object of the present invention is to provide the high viscosity containing hydrogen silicone oil adopted and be made with the aforedescribed process, and described is hydrogeneous
The viscosity of silicone oil is in 100-80000mPas, hydrogen content 0.1-0.8wt%.
As a preferred option, the viscosity of the containing hydrogen silicone oil is in 500-10000mPas, hydrogen content 0.2-
0.7wt%。
The present invention due to the adoption of the above technical solution, has the beneficial effect that containing for high viscosity containing hydrogen silicone oil of the invention
Hydrogen amount is 0.1-0.8wt%, and as the crosslinking agent of addition-type silicon rubber and silicone resin, addition-type silicon rubber and silicone resin can be improved
Mechanical property, and hardness can be adjusted, and its raw material is easy to get, simple production process is with short production cycle, is suitble to industrialized production.
Specific embodiment
Below by way of specific embodiment, specific embodiments of the present invention will be described in further detail.
Embodiment 1
A kind of high viscosity containing hydrogen silicone oil the preparation method is as follows:
1. the dimethyl siloxane mixed methylcyclosiloxane that the high containing hydrogen silicone oil and quality that are 100g using quality are 100g is as reaction monomers,
And the dimethylbenzene that quality is 100g is added, polymerization reaction, polymerization reaction are carried out under the concentrated sulfuric acid catalyst effect that quality is 8g
Time is 6 hours, and reaction temperature is 40 DEG C.
2. after polymerization reaction, sodium carbonate is added into obtained reaction solution, stood after stirring 2h, supernatant liquor passes through
After filter, dimethylbenzene is removed under the conditions of vacuum degree is -0.08MPa, temperature is 100 DEG C, then in -0.098MPa, temperature 130
Low-boiling-point substance is removed under the conditions of DEG C, obtains high viscosity containing hydrogen silicone oil.
The high viscosity containing hydrogen silicone oil reactive hydrogen component content prepared after tested is 0.76wt%, viscosity 120mPa.s.
Embodiment 2
A kind of high viscosity containing hydrogen silicone oil the preparation method is as follows:
1. the dimethyl siloxane mixed methylcyclosiloxane that the high containing hydrogen silicone oil and quality that are 100g using quality are 900g is as reaction monomers,
And the toluene that quality is 1000g is added, polymerization reaction, polymerization reaction are carried out under the methanesulfonic acid catalyzed agent effect that quality is 80g
Time is 6 hours, and reaction temperature is 40 DEG C.
2. after polymerization reaction, sodium carbonate is added into obtained reaction solution, stood after stirring 2h, supernatant liquor passes through
After filter, toluene is removed under the conditions of vacuum degree is -0.08MPa, temperature is 70 DEG C, is then 130 DEG C in -0.098MPa, temperature
Under the conditions of remove low-boiling-point substance, obtain high viscosity containing hydrogen silicone oil.
The high viscosity containing hydrogen silicone oil reactive hydrogen component content prepared after tested is 0.16wt%, viscosity 3300mPa.s.
Embodiment 3
A kind of high viscosity containing hydrogen silicone oil the preparation method is as follows:
1. the dimethyl siloxane mixed methylcyclosiloxane that the high containing hydrogen silicone oil and quality that are 100g using quality are 400g is as reaction monomers,
And the toluene that quality is 500g is added, polymerization reaction is carried out under the triflate catalyst effect that quality is 5g, polymerization is anti-
It is 6 hours between seasonable, reaction temperature is 40 DEG C.
2. after polymerization reaction, sodium bicarbonate is added into obtained reaction solution, stood after stirring 2h, supernatant liquor warp
After filtering, toluene is removed under the conditions of vacuum degree is -0.08MPa, temperature is 70 DEG C, then in -0.098MPa, temperature 130
Low-boiling-point substance is removed under the conditions of DEG C, obtains high viscosity containing hydrogen silicone oil.
The high viscosity containing hydrogen silicone oil reactive hydrogen component content prepared after tested is 0.31wt%, viscosity 1000mPa.s.
Embodiment 4
A kind of high viscosity containing hydrogen silicone oil the preparation method is as follows:
1. the octamethylcy-clotetrasiloxane that the high containing hydrogen silicone oil and quality that are 55g using quality are 970g is as reaction monomers, quality
For 5g hexamethyldisiloxane as end-capping reagent, and be added quality be 500g toluene, quality be 40g sulphuric acid catalysis
Agent effect is lower to carry out polymerization reaction, and polymerization reaction time is 6 hours, and reaction temperature is 40 DEG C.
2. after polymerization reaction, sodium bicarbonate is added into obtained reaction solution, stood after stirring 2h, supernatant liquor warp
After filtering, toluene is removed under the conditions of vacuum degree is -0.08MPa, temperature is 70 DEG C, then in -0.098MPa, temperature 130
Low-boiling-point substance is removed under the conditions of DEG C, obtains high viscosity containing hydrogen silicone oil.
The high viscosity containing hydrogen silicone oil reactive hydrogen component content prepared after tested is 0.08wt%, viscosity 990mPa.s.
In conclusion high viscosity containing hydrogen silicone oil hydrogen content of the invention is 0.1-0.8wt%, as addition-type silicon rubber and
The mechanical property of addition-type silicon rubber and silicone resin can be improved in the crosslinking agent of silicone resin；Using this high viscosity containing hydrogen silicone oil as raw material
Modified silicon oil obtained has better surface property and feel as auxiliary agent；And its raw material is easy to get, simple production process, production week
Phase is short, is suitble to industrialized production.
The above are the descriptions to the embodiment of the present invention to keep this field special by the foregoing description of the disclosed embodiments
Industry technical staff can be realized or using the present invention.Various modifications to these embodiments carry out those skilled in the art
Saying will be apparent.The general principles defined herein can be the case where not departing from the spirit or scope of the present invention
Under, it realizes in other embodiments.Therefore, the present invention is not intended to be limited to these implementation columns shown in this article, but to accord with
Close the widest scope consistent with principles disclosed herein and novel point.
Claims (10)
1. a kind of preparation method of high viscosity containing hydrogen silicone oil, this method include the following steps:
1) using high hydrogen content polysiloxanes and cyclosiloxane as reaction monomers, and organic solvent is added, makees in acidic catalyst
Polymerization reaction is carried out under, polymerization reaction time is 1-20 hours, and temperature is 20-60 DEG C；
2) after polymerization reaction, obtained reaction solution is neutralized to neutrality and filters out solid salt；
3) solvent and low-boiling-point substance therein are sloughed at high temperature, remove low-boiling-point substance removing vacuum degree be -0.01MPa~-
0.098MPa, temperature are 100-180 DEG C, and high viscosity containing hydrogen silicone oil can be obtained.
2. preparation method according to claim 1, which is characterized in that the high hydrogen containing siloxane is high containing hydrogen silicone oil
One or more of combination；The cyclosiloxane is hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, ten
The combination of one or more of methyl cyclopentasiloxane, ten diformazan basic rings, six siloxanes.
3. preparation method according to claim 1, which is characterized in that the matter of the high hydrogen containing siloxane and cyclosiloxane
Amount is than being 1:20-2:1；It is preferred that the mass ratio of the high hydrogen containing siloxane and cyclosiloxane is 1:15-5:1.
4. preparation method according to claim 1, which is characterized in that the reaction monomers of the containing hydrogen silicone oil further include sealing end
Agent, end-capping reagent are one or more kinds of groups of hexamethyldisiloxane, tetramethyl disiloxane, low viscosity dimethyl silicone oil
It closes.
5. preparation method according to claim 1, which is characterized in that the organic solvent is petroleum ether, n-hexane, first
Benzene, dimethylbenzene, acetone, ethyl acetate, butyl acetate, chloroform, ether, dimethylformamide, methylene chloride, methanol, in ethyl alcohol
A combination of one or more, and its additive amount is 0.1-10 times of high hydrogen content polysiloxanes and cyclosiloxane gross mass.
6. preparation method according to claim 1, which is characterized in that the acidic catalyst is the sulphur that concentration is 98wt%
Acid, hydrochloric acid, methanesulfonic acid, p-methyl benzenesulfonic acid, trifluoromethanesulfonic acid, storng-acid cation exchange resin and the acid that concentration is 36-37wt%
Property one or more of carclazyte combination, and dosage is the 1%- of high hydrogen content polysiloxanes and cyclosiloxane gross mass
10%。
7. preparation method according to claim 1, which is characterized in that the neutralizer is sodium carbonate, sodium bicarbonate, carbonic acid
The combination of one or more of calcium, magnesium carbonate, aluminium hydroxide.
8. preparation method according to claim 1, which is characterized in that the time of the polymerization reaction is 2-5 hours, polymerization
Reaction temperature is 30-50 DEG C；The removing vacuum degree of the removing low-boiling-point substance is -0.098MPa, and temperature is 120-150 DEG C.
9. the high viscosity containing hydrogen silicone oil that preparation method described in claim 1 ~ 8 any one claim is prepared；It is described
Containing hydrogen silicone oil viscosity in 100-80000mPas, hydrogen content 0.1-0.8wt%.
10. high viscosity containing hydrogen silicone oil according to claim 9, which is characterized in that the viscosity of the containing hydrogen silicone oil exists
500-10000mPas, hydrogen content 0.2-0.7wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910342006.XA CN110041527A (en) | 2019-04-26 | 2019-04-26 | A kind of high viscosity containing hydrogen silicone oil and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910342006.XA CN110041527A (en) | 2019-04-26 | 2019-04-26 | A kind of high viscosity containing hydrogen silicone oil and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110041527A true CN110041527A (en) | 2019-07-23 |
Family
ID=67279460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910342006.XA Pending CN110041527A (en) | 2019-04-26 | 2019-04-26 | A kind of high viscosity containing hydrogen silicone oil and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110041527A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112300731A (en) * | 2019-08-01 | 2021-02-02 | 广州天疆高新材料有限公司 | PC tackifier for addition type liquid silicone rubber and preparation method thereof |
| CN116217938A (en) * | 2023-03-20 | 2023-06-06 | 浙江润禾有机硅新材料有限公司 | Long-chain alkyl fluorine-containing vinyl silicone oil and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524743A (en) * | 2013-07-01 | 2014-01-22 | 江苏天辰硅材料有限公司 | Preparation method of hydrogen-containing silicone oil with terminal hydrogen group |
| CN104861168A (en) * | 2015-05-05 | 2015-08-26 | 深圳新宙邦科技股份有限公司 | Phenyl hydrogen silicone oil for LED (Light Emitting Diode) encapsulation adhesive and preparation method thereof |
| CN105229056A (en) * | 2013-03-28 | 2016-01-06 | 道康宁公司 | Organosiloxane composition and coating, finished product, method and purposes |
| CN105384934A (en) * | 2015-09-21 | 2016-03-09 | 江西蓝星星火有机硅有限公司 | Preparation method of terminal hydrogen-containing silicone oil |
| CN105820340A (en) * | 2016-04-22 | 2016-08-03 | 上海应用技术学院 | High-velocity phenylmethyl silicone oil and preparation method thereof |
| CN107400241A (en) * | 2017-09-06 | 2017-11-28 | 江苏天辰新材料股份有限公司 | A kind of preparation method of containing hydrogen silicone oil |
-
2019
- 2019-04-26 CN CN201910342006.XA patent/CN110041527A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105229056A (en) * | 2013-03-28 | 2016-01-06 | 道康宁公司 | Organosiloxane composition and coating, finished product, method and purposes |
| CN103524743A (en) * | 2013-07-01 | 2014-01-22 | 江苏天辰硅材料有限公司 | Preparation method of hydrogen-containing silicone oil with terminal hydrogen group |
| CN104861168A (en) * | 2015-05-05 | 2015-08-26 | 深圳新宙邦科技股份有限公司 | Phenyl hydrogen silicone oil for LED (Light Emitting Diode) encapsulation adhesive and preparation method thereof |
| CN105384934A (en) * | 2015-09-21 | 2016-03-09 | 江西蓝星星火有机硅有限公司 | Preparation method of terminal hydrogen-containing silicone oil |
| CN105820340A (en) * | 2016-04-22 | 2016-08-03 | 上海应用技术学院 | High-velocity phenylmethyl silicone oil and preparation method thereof |
| CN107400241A (en) * | 2017-09-06 | 2017-11-28 | 江苏天辰新材料股份有限公司 | A kind of preparation method of containing hydrogen silicone oil |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112300731A (en) * | 2019-08-01 | 2021-02-02 | 广州天疆高新材料有限公司 | PC tackifier for addition type liquid silicone rubber and preparation method thereof |
| CN112300731B (en) * | 2019-08-01 | 2022-05-24 | 广州天疆高新材料有限公司 | PC tackifier for addition type liquid silicone rubber and preparation method thereof |
| CN116217938A (en) * | 2023-03-20 | 2023-06-06 | 浙江润禾有机硅新材料有限公司 | Long-chain alkyl fluorine-containing vinyl silicone oil and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US12122876B2 (en) | Method for preparing reactive sealant resin | |
| JP4972103B2 (en) | Method for producing silicone resin | |
| CN100500675C (en) | Synthesis method of multi-amino polyhedral oligomeric silsesquioxanes | |
| CN104387546A (en) | Phenyl organic silicon modified polyurethane resin, preparation method and application thereof | |
| CN109608640A (en) | A kind of high molecular weight MQ silicone resin and its synthetic method, application | |
| RU2012104397A (en) | METHOD FOR PRODUCING SILICONE ADHESIVE BONDING UNDER PRESSURE | |
| CN110041527A (en) | A kind of high viscosity containing hydrogen silicone oil and preparation method thereof | |
| CN105647189B (en) | A kind of organic foamed silastic | |
| CN106750312A (en) | Phenyl DT silicones and preparation method thereof | |
| CN116063681B (en) | Preparation method of divinyl-terminated polysiloxane | |
| CN104610549A (en) | Modified fluorine-containing silicone oil and preparation method thereof | |
| CN108034051A (en) | A kind of vinyl polysiloxane and preparation method and application | |
| CN107189071B (en) | Preparation method of platinum catalyst for liquid silicone rubber | |
| CN103554500A (en) | UV photocurable polysiloxane and preparation method thereof | |
| CN110283315B (en) | Method for producing hydroxyl silicone oil by using methyl chlorosilane by-product | |
| CN109012198A (en) | A kind of infiltrating and vaporizing membrane and its preparation and application | |
| CN100344636C (en) | Synthesis method for substituting sesquialter siloxane by non-functional alkyl | |
| CN112876684B (en) | Micron-level high-crosslinking-degree organic silicon polymer microspheres with controllable particle sizes and preparation method thereof | |
| CN107057068A (en) | A kind of end epoxy silicon oil and preparation method thereof and its as adhesion promoters purposes | |
| CN107033351B (en) | Preparation process of ultralow-viscosity dimethyl silicone oil | |
| CN101072811A (en) | Preparation method of high-purity polyhedral oligomeric silsesquioxane monomer | |
| CN107400238B (en) | Multi-arm siloxane bridged ladder-shaped polysiloxane copolymer and preparation method and application thereof | |
| CN110684199A (en) | Organic siloxane-polyoxypropylene segmented copolymer and preparation method thereof, and prepared bi-component LED (light-emitting diode) pouring sealant and preparation method thereof | |
| CN103172866B (en) | The preparation method of the hydroxyl endblocked polydimethylsiloxane that a kind of viscosity is controlled | |
| CN105482121A (en) | Synthesis method of polyvinyl silicon oil |
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: 20190723 |