CN104761668B - A kind of bulk polymerization of microwave heating non-polar monomer - Google Patents
A kind of bulk polymerization of microwave heating non-polar monomer Download PDFInfo
- Publication number
- CN104761668B CN104761668B CN201510130554.8A CN201510130554A CN104761668B CN 104761668 B CN104761668 B CN 104761668B CN 201510130554 A CN201510130554 A CN 201510130554A CN 104761668 B CN104761668 B CN 104761668B
- Authority
- CN
- China
- Prior art keywords
- polymerization
- method described
- microwave heating
- polar monomer
- microwave
- 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.)
- Active
Links
Abstract
The invention discloses a kind of bulk polymerizations of microwave heating non-polar monomer comprising step：A kind of bulk polymerization of microwave heating non-polar monomer, which is characterized in that the method includes the steps：Neon SiC powder and non-polar monomer are stirred until homogeneous unanimously；It adds free radical thermal initiator and obtains uniformly mixed mixture；The mixture is de-gassed；Microwave heating polymerization is carried out, composite material is obtained.The bulk polymerization of the present invention makes nonpolar molecule also can carry out bulk polymerization by microwave heating；The temperature of heating systems is monitored in real time using microwave reaction instrument, to overcome the problems, such as that polymerization system is easy implode；Simultaneous reactions system is heated evenly, easily controllable, obtains haveing excellent performance for material, the problems such as reducing the bubble easily occurred in reaction, change colour；The polymer that the bulk polymerization of the present invention obtains has higher degree of crosslinking, and at the same time keeping large volume, pattern uniform, has excellent mechanical property.
Description
Technical field
The present invention relates to a kind of bulk polymerizations, and it is poly- to relate more particularly to a kind of ontology of microwave heating non-polar monomer
Conjunction method.
Background technology
Bulk polymerization is monomer under conditions of not solubilizer and other dispersants, in initiator or heat, light, radiation
Under effect, it is not added with the polymerization process of other media progress.Its main feature is that product purity is high, it is not required to complicated separation, purification, operation
Relatively simple, production equipment utilization rate is high.But there is also many defects for bulk polymerization itself：For example technique fuel factor is opposite
It is larger, since system viscosity is continuously increased with polymerization, system mixing and heat transfer difficult；In free radical polymerization, sometimes
There is rate of polymerization autoacceleration effect, have bubble so as to cause material, changes colour；If control is improper, implode is easily caused, makes material
Expect that difficulty up to standard increases；Molecular weight of product distribution is wide, and unreacted monomer is difficult to eliminate, products machinery degradation etc..In addition,
The crosslinked polymer degree that common bulk polymerization obtains on the market is not high, for example crosslinked polystyrene, the degree of cross linking are general
2% or so, if improving its degree of cross linking, since the reaction of bulk polymerization is more difficult to control, it is uniform to be hardly formed large volume pattern
Product, the product of acquisition can not be applied, here large volume pattern it is uniform refer to i.e. volume 100mm × 100mm ×
20mm or more, flawless inside and outside material, bubble-free, no emulsification white point, color are uniform.
Microwave refers to radio frequency electromagnetic of the wavelength between infrared ray and superfrequency (UHF).The wave-length coverage of microwave is big
About in 1mm between 1m, corresponding frequency range is 0.3GHz to 300GHz.There are two main features for microwave heating：One, should
Heating belongs to body heating, and heat results from inside substance, and microwave has very strong penetration power to photographed object, and playing deep layer to reactant adds
Heat effect, for condensed state matter, microwave is mainly heated by polarization and transmission mechanism；Two, microwave keeps system heated equal
It is even, heating speed is fast, the thermal efficiency is high, material everywhere property (molecular weight, degree of reaction etc.) than more uniform；Three, using microwave reaction
Instrument can real-time control temperature, the property of can be chosen heating, automation control easy to implement.A large amount of experiment confirms microwave technology not
The rate of some chemical reactions can be only greatlyd improve, the reaction time is reduced, simplifies post-processing, improves yield and reactivity,
And the progress that is swift in response that some can also be made to be not easy to carry out at typical condition.Applying for microwave can drop in Chemical Industries
Low energy expenditure reduces pollution, improvement product property, therefore is known as " Green Chemistry ", there is huge application prospect.
The advantages of in view of microwave heating, microwave heating is applied in bulk polymerization by those skilled in the art.But micro-
Reactant is related to the absorption of microwave energy and the polarity of molecule in wave chemistry.Polar molecule due to intramolecule distribution of charges not
Uniformly, energy is absorbed under microwave radiation, fuel factor, referred to as dielectric loss is generated by the dipole effect of molecule.From microwave plus
From the point of view of in the principle of heat, the ability of material absorbing microwave is mainly determined that dielectric dissipation factor is got over by its dielectric dissipation factor
Big substance is stronger to the absorbability of microwave.Therefore, at present applied to the microwave technology of bulk polymerization mainly for polarity
The monomer of molecule, such as：Methacrylic acid, polarity maleic anhydride etc., have microwave strong absorption, can be directly micro-
Bulk polymerization is carried out under wave radiation.Microwave technology makes the time of the bulk polymerization and energy consumption all substantially reduce, and improves
Polymerization rate, yield.But nonpolar molecule internal charge is evenly distributed, and polarization is not likely to produce under microwave radiation,
So microwave is smaller to substance of this kind heat effect.It is less than 15 nonpolar molecule especially for dielectric constant, due to its suction
It is very weak to receive microwave ability, microwave heating can be carried out to carry out bulk polymerization to the nonpolar molecule currently without method.
Invention content
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of ontologies of microwave heating non-polar monomer to gather
Conjunction method comprising step：Neon SiC powder and non-polar monomer are stirred until homogeneous unanimously；Free radical heat is added to draw
It sends out agent and obtains uniformly mixed mixture；The mixture is de-gassed；Microwave heating polymerization is carried out, composite wood is obtained
Material.
Further, mass fraction of the free radical thermal initiator in the mixture is 0.2%-1%.
Further, mass fraction of the free radical thermal initiator in the mixture is 0.3%-0.6%.
Further, the free radical thermal initiator includes：Cyclohexanone peroxide, dibenzoyl peroxide, tertiary butyl mistake
Hydrogen oxide, the benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, peroxidating two acyl, azodiisobutyronitrile or azobisisoheptonitrile.
Further, wherein the mass ratio of the non-polar monomer and the silicon carbide powder is 500:1-5000:1.
Further, the grain size of the Neon SiC powder is between 10-50 nanometers.
Further, the dielectric constant of the non-polar monomer is less than 15.
Further, the non-polar monomer includes α-methylstyrene, acrylic acid, 2- methyl-1s, 3- butadiene, benzene second
Or mixtures thereof alkene, styrene derivative.
Further, the microwave heating polymerization includes prepolymerization and solidification.
Further, the prepolymerized condition is：Heating temperature be 50 DEG C -95 DEG C, prepolymerization time be 30 minutes -
180 minutes.
Further, the cured condition is：Heating temperature is 45 DEG C -70 DEG C, and hardening time is -25 hours 5 hours.
Further, the polymerization further includes that internal crosslinker is added in the compound resin obtained after prepolymerization, before solidification.
Further, the internal crosslinker is divinylbenzene.
Further, the mass ratio of the internal crosslinker and compound resin is 1:50-1:5.
Further, the degassing process is Fruit storage.
Compared with prior art, the beneficial effects of the present invention are：
1) bulk polymerization of the invention makes nonpolar molecule also can carry out bulk polymerization by microwave heating；
2) it utilizes the heating temperature of microwave reaction instrument highly controllable, the temperature of heating systems is monitored in real time, to overcome
Polymerization system is easy the problem of implode；Simultaneous reactions system is heated evenly, easily controllable, obtains haveing excellent performance for material, is reduced
The problems such as bubble that easily occurs in reaction, discoloration；
3) polymer that bulk polymerization of the invention obtains can have the higher degree of cross linking, and at the same time keeping substantially
Product, pattern are uniform, have excellent mechanical property.
Specific implementation mode
Embodiment 1
The styrene of 154g after purification is weighed, 0.125g nanometer silicon carbide powder is weighed and is added into above-mentioned styrene,
And ultrasonic disperse is carried out to soilless sticking state.Then 0.76g dibenzoyl peroxides are added, are sufficiently mixed, obtain uniform mix
Close object.Deoxygenation is de-gassed to above-mentioned mixture.Using microwave heating instrument (Xinyi Microwave Chemistry Tech Co., Ltd.,
UWave-1000 heating pre-polymerization) is carried out, wherein：Microwave power is 350W；Heating temperature is 85 DEG C；The pre-polymerization time is 90 minutes；
Obtain combined styrene resin.Above-mentioned combined styrene resin is heating and curing using microwave heating instrument, wherein：Microwave work(
Rate is 300W；Heating temperature is 60 DEG C；Hardening time is 10 hours.Obtain composite material final product
Embodiment 2
The styrene of 140g after purification is weighed, 0.113g nanometer silicon carbide powder is weighed and is added into above-mentioned styrene,
And ultrasonic disperse is carried out to soilless sticking state.Then 0.7g dibenzoyl peroxides are added, is sufficiently mixed, obtains uniform mixing
Object.Deoxygenation is de-gassed to above-mentioned mixture.Above-mentioned mixture is subjected to heating pre-polymerization using microwave heating instrument, wherein：
Microwave power is 350W；Heating temperature is 90 DEG C；The pre-polymerization time is 120 minutes；Obtain combined styrene resin.It is pure to weigh 9.3g
Divinylbenzene after change is slowly added drop-wise in above-mentioned combined styrene resin, is stirred, is de-gassed deoxygenation.Using micro-
Wave heating instrument is heating and curing, wherein：Microwave power is 350W；Heating temperature is 45 DEG C；Hardening time is 20 hours.It obtains
The uniform composite material final product of large volume pattern, volume flawless inside and outside 100mm × 100mm × 20mm or more, material,
Bubble-free, no emulsification white point, color are uniform.
The degree of cross linking of obtained composite material is measured with swelling equilibrium measuring method, the degree of cross linking of the composite material is 6.32%.
Embodiment 3
The acrylic acid of 150g after purification is weighed, 0.3g nanometer silicon carbide powder is weighed and is added into above-mentioned acrylic acid, and
Ultrasonic disperse is carried out to soilless sticking state.Then 0.3g cyclohexanone peroxides are added, is sufficiently mixed, obtains uniform mixture.
Deoxygenation is de-gassed to above-mentioned mixture.Heating pre-polymerization is carried out using microwave heating instrument, wherein：Heating temperature is 50 DEG C；In advance
The poly- time is 180 minutes；Obtain composite acrylic resin.The divinylbenzenes of 3.01g after purification are weighed, are slowly added drop-wise to above-mentioned
It in composite acrylic resin, is stirred, deaerate deoxygenation.It is heating and curing using microwave heating instrument, wherein：Heating temperature is
70℃；Hardening time is 5 hours.Obtain composite material final product.
Embodiment 4
The α-methylstyrenes of 150g after purification are weighed, 0.03g nanometer silicon carbide powder is weighed and is added to above-mentioned α-first
In base styrene, and ultrasonic disperse is carried out to soilless sticking state.Then 1.515g tert-butyl hydroperoxide is added, is sufficiently mixed,
Obtain uniform mixture.Deoxygenation is de-gassed to above-mentioned mixture.Heating pre-polymerization is carried out using microwave heating instrument, wherein：
Heating temperature is 95 DEG C；The pre-polymerization time is 30 minutes；Obtain compound α-methylstyrene resin.Weigh two of 30.3g after purification
Vinyl benzene is slowly added drop-wise in above-mentioned compound α-methylstyrene resin, is stirred, and deaerate deoxygenation.Utilize microwave heating
Instrument is heating and curing, wherein：Heating temperature is 70 DEG C；Hardening time is 5 hours.Obtain composite crosslinking α-methylstyrene tree
Fat.Obtain composite material final product.
Embodiment 5
The α-methylstyrenes of 150g after purification are weighed, 0.03g nanometer silicon carbide powder is weighed and is added to above-mentioned α-first
In base styrene, and ultrasonic disperse is carried out to soilless sticking state.Then 1.515g tert-butyl hydroperoxide is added, is sufficiently mixed,
Obtain uniform mixture.Deoxygenation is de-gassed to above-mentioned mixture.Heating pre-polymerization is carried out using microwave heating instrument, wherein：
Heating temperature is 95 DEG C；The pre-polymerization time is 30 minutes；Obtain compound α-methylstyrene resin.Weigh two of 30.3g after purification
Vinyl benzene is slowly added drop-wise in above-mentioned compound α-methylstyrene resin, is stirred, and deaerate deoxygenation.Utilize microwave heating
Instrument is heating and curing, wherein：Heating temperature is 70 DEG C；Hardening time is 5 hours.Obtain composite crosslinking α-methylstyrene tree
Fat.Obtain composite material final product.
Embodiment 6
The 2- methyl-1s of 150g after purification are weighed, 3- butadiene weighs 0.2g nanometer silicon carbide powder and is added to above-mentioned
2- methyl-1s, 3- butadiene, and ultrasonic disperse is carried out to soilless sticking state.Then the 0.45g benzoyl peroxide tert-butyl esters are added,
It is sufficiently mixed, obtains uniform mixture.Deoxygenation is de-gassed to above-mentioned mixture.Using microwave heating instrument heat pre-
It is poly-, wherein：Heating temperature is 95 DEG C；The pre-polymerization time is 30 minutes；Obtain compound 2- methyl-1s, 3- butadiene resins.Weigh 10g
Divinylbenzene after purification, is slowly added drop-wise to above-mentioned compound 2- methyl-1s, in 3- butadiene resins, is stirred, degassing removes
Oxygen.It is heating and curing using microwave heating instrument, wherein：Heating temperature is 45 DEG C；Hardening time is 25 hours.Obtain compound friendship
Join 2- methyl-1s, 3- butadiene resins.Obtain composite material final product.
Embodiment 7
75g styrene and 75g acrylic acid after purification are weighed, 0.2g nanometer silicon carbide powder is weighed and is added to above-mentioned 2- first
Base -1,3-butadiene, and ultrasonic disperse is carried out to soilless sticking state.Then 0.9g methyl ethyl ketone peroxides are added, is sufficiently mixed, obtains
To uniform mixture.Deoxygenation is de-gassed to above-mentioned mixture.Heating pre-polymerization is carried out using microwave heating instrument, wherein：Add
Hot temperature is 95 DEG C；The pre-polymerization time is 30 minutes；Obtain compound resin.The divinylbenzenes of 10g after purification are weighed, are slowly added dropwise
It into above-mentioned compound resin, is stirred, deaerate deoxygenation.It is heating and curing using microwave heating instrument, wherein：Heating temperature is
45℃；Hardening time is 25 hours.Obtain composite material final product.
Comparative example
With prior art preparation crosslinked polystyrene：
4.63g styrene, 0.28g divinylbenzenes, 0.0058g dibenzoyl peroxides, mixture process are weighed respectively
Degassing, under nitrogen protection 65 DEG C of prepolymerizations are heated 2 hours.Under nitrogen protection, mold is injected the mixture into, is heated at 75 DEG C
Solidification 12 hours obtains crosslinked polystyrene, and it is 6.18% to measure its degree of cross linking with swelling equilibrium measuring method.In this experimentation
In, by carefully controlling reaction, the higher polystyrene product of the degree of cross linking is obtained, but its is small-sized, it can not be into traveling
The application of one step.
The composite material final product that testing example 1, embodiment 2 and comparative example 1 obtain, by the glass transition of acquisition
Temperature, storage modulu and loss modulus are compared in table 1.
Table 1
As can be seen from Table 1, the glass transition temperature of embodiment 2 is higher than the glass transition of embodiment 1 and comparative example
Temperature.The storage modulu of embodiment 2 at normal temperatures is 3065.5MPa, and the storage modulu at 100 DEG C is 1771.5MPa, is more than real
Apply the 3060.0MPa and 822.6MPa of example 1 and 2828.0MPa and 15.4MPa much larger than comparative example.About loss modulus,
The storage modulu of embodiment 2 at normal temperatures is the 131.6 of a little higher than embodiments of 136.1MPa 1, is 220.3MPa at 100 DEG C,
The 219.8 of a little higher than embodiment 1, although the storage modulu of embodiment 2 is slightly less than the 138.6MPa of comparative example under room temperature,
At 100 DEG C, it is much larger than the 11.6MPa of comparative example.It is therefore found that (one) mixes the polystyrene of silicon carbide in equivalent
In composite material (embodiment 1 and embodiment 2), the raising of the degree of cross linking can be such that the heat resistance of composite material and mechanical property obtains
Largely optimize；(2) it is connect very much even if crosslinking agent mole percent is 6% and obtains the degree of cross linking of product
In the case of close (embodiment 2 and comparative example), the heat resistance and mechanical property of the composite material that the present processes prepare
Also all it is much better than the composite material of prior art preparation acquisition.
It should be appreciated that be only intended to clearly illustrate institute of the invention for example for above-described embodiment, and it is not to the present invention
Embodiment restriction.For those of ordinary skill in the art, it can also be made on the basis of the above description
Its various forms of variation or variation.Here all embodiments can not be exhaustive.Every technology for belonging to the present invention
Row of the obvious variation or change that scheme is amplified out still in protection scope of the present invention.
Claims (11)
1. a kind of bulk polymerization of microwave heating non-polar monomer, which is characterized in that the method includes the steps：
Neon SiC powder and non-polar monomer are stirred until homogeneous unanimously；
It adds free radical thermal initiator and obtains uniformly mixed mixture；
The mixture is de-gassed；
Microwave heating polymerization is carried out, composite material is obtained；The microwave heating polymerization includes prepolymerization and solidification；
The non-polar monomer includes acrylic acid, 2- methyl-1s, or mixtures thereof 3- butadiene, styrene, styrene derivative；
The prepolymerized condition is：Heating temperature is 50 DEG C -95 DEG C, and prepolymerization time is -180 minutes 30 minutes；It is described solid
The condition of change is：Heating temperature is 45 DEG C -70 DEG C, and hardening time is -25 hours 5 hours.
2. according to the method described in claim 1, it is characterized in that, the styrene derivative is α-methylstyrene.
3. according to the method described in claim 1, it is characterized in that, matter of the free radical thermal initiator in the mixture
Amount score is 0.2%-1%.
4. according to the method described in claim 3, it is characterized in that, matter of the free radical thermal initiator in the mixture
Amount score is 0.3%-0.6%.
5. according to the method described in claim 1, it is characterized in that, the free radical thermal initiator includes：Cyclohexanone peroxide,
Dibenzoyl peroxide, tert-butyl hydroperoxide, the benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, azodiisobutyronitrile or
Azobisisoheptonitrile.
6. according to the method described in claim 1, it is characterized in that, the wherein described non-polar monomer and the silicon carbide powder
Mass ratio is 500:1-5000:1.
7. according to the method described in claim 1, it is characterized in that, the grain size of the Neon SiC powder is at 10-50 nanometers
Between.
8. according to the method described in claim 1, it is characterized in that, the polymerization further includes being obtained after prepolymerization, before solidification
Compound resin in be added internal crosslinker.
9. according to the method described in claim 8, it is characterized in that, the internal crosslinker is divinylbenzene.
10. according to the method described in claim 8, it is characterized in that, the mass ratio of the internal crosslinker and compound resin is 1:
50-1:5。
11. according to the method described in claim 1, it is characterized in that, the degassing process is Fruit storage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510130554.8A CN104761668B (en) | 2015-03-24 | 2015-03-24 | A kind of bulk polymerization of microwave heating non-polar monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510130554.8A CN104761668B (en) | 2015-03-24 | 2015-03-24 | A kind of bulk polymerization of microwave heating non-polar monomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104761668A CN104761668A (en) | 2015-07-08 |
| CN104761668B true CN104761668B (en) | 2018-10-26 |
Family
ID=53643795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510130554.8A Active CN104761668B (en) | 2015-03-24 | 2015-03-24 | A kind of bulk polymerization of microwave heating non-polar monomer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104761668B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104238296B (en) * | 2014-08-06 | 2018-12-11 | 湖北鼎龙控股股份有限公司 | The method that microwave irradiation auxiliary prepares colored carbon powder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1493608A (en) * | 2003-09-02 | 2004-05-05 | 华东理工大学 | Nano-ferroferric oxide/polystyrene magnetic composite material and its preparation method |
| US20070191536A1 (en) * | 2005-01-26 | 2007-08-16 | Fina Technology, Inc. | Branched ionomers |
-
2015
- 2015-03-24 CN CN201510130554.8A patent/CN104761668B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1493608A (en) * | 2003-09-02 | 2004-05-05 | 华东理工大学 | Nano-ferroferric oxide/polystyrene magnetic composite material and its preparation method |
| US20070191536A1 (en) * | 2005-01-26 | 2007-08-16 | Fina Technology, Inc. | Branched ionomers |
Non-Patent Citations (3)
| Title |
|---|
| In situ radical transfer addition polymerization of styrene from silica nanoparticles;Peng Liu;《European Polymer Journal》;20041031;第40卷;全文 * |
| Thermal stabilities of polystyrene/silica hybrid nanocomposites via microwave-assisted in situ polymerization;Peng Liu;《Materials Chemistry and Physics》;20051231;第94卷;第415页右栏第2.3节，第414页Fig.5 * |
| 交联聚苯乙烯及其玻纤增强复合材料的制备及性能研究;吴飞;《中国优秀硕士论文全文数据库·工程科技Ⅰ辑》;20101215(第12期);第2章第15-21页，第3章第26-27页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104761668A (en) | 2015-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7447015B2 (en) | Polar monomer-grafted polypropylene resin, its manufacturing method and application | |
| CN103421206B (en) | A kind of preparation method of Acrylonitrile/Methacylic Acid Copolymer Foam | |
| CN102399390B (en) | Preparation method of radiation-crosslinked polypropylene | |
| CN108997525B (en) | Polymethacrylimide foam with uniform pores and preparation method thereof | |
| CN109054166A (en) | A kind of preparation method of heat-proof impact-resistant polypropylene material | |
| CN105111655B (en) | A kind of light guide plate fabrication processing system | |
| CN111848873A (en) | Functional monomer grafted polypropylene and preparation method thereof | |
| US20190211124A1 (en) | Improving the properties in pmma foams by using methacrylic amides | |
| CN110551248A (en) | Preparation method of thermal expansibility microsphere with controllable particle size | |
| CN104761668B (en) | A kind of bulk polymerization of microwave heating non-polar monomer | |
| CN107298737A (en) | A kind of polyacrylic preparation method of Three-Dimensional Dynamic | |
| CN102336872B (en) | Method of preparing cross-linking type polystyrene material with low dielectric properties assisted by ultraviolet light | |
| CN102633928B (en) | Method for manufacturing crosslinked polystyrene | |
| CN113733680A (en) | Wave-absorbing polymethacrylimide foam composite material | |
| CN108774380B (en) | Preparation method of additive type flame retardant for resin-based composite material | |
| CN1493600A (en) | Preparation method and application of modified double maleimide resin | |
| CN114230952A (en) | PMI block foam material and preparation method thereof | |
| CN113501907A (en) | Method for regulating and controlling modulus change range of thermal response ionic liquid gel and thermal response ionic liquid gel | |
| CN108102143A (en) | A kind of method that graphene modified powder is removed with polymer wrapped liquid phase | |
| CN108767174A (en) | A kind of preparation method of Organic-inorganic composite lithium battery diaphragm | |
| CN111983745B (en) | Optical film, polarizing plate and liquid crystal display device | |
| US9950340B2 (en) | Transparent and heat-insulating material including polymer capsule and method for preparing the same | |
| JPH04126726A (en) | Production of modified polyethylene-based resin granule having improved weatherability | |
| CN100457797C (en) | Preparation for smart water gel responding microwave | |
| CN107513196B (en) | Method for efficiently heating high-molecular polymer by using microwaves |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wu Jingshen Inventor after: Lv Dong Inventor after: Liang Kanyi Inventor after: Zhang Zheming Inventor after: He Jiaxi Inventor before: Wu Jingshen Inventor before: Lv Dong Inventor before: Liang Kanyi Inventor before: Zhang Zheming |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |