CN114316123B - Method for polymerizing photoresist resin by using supercritical carbon dioxide - Google Patents
Method for polymerizing photoresist resin by using supercritical carbon dioxide Download PDFInfo
- Publication number
- CN114316123B CN114316123B CN202111627112.6A CN202111627112A CN114316123B CN 114316123 B CN114316123 B CN 114316123B CN 202111627112 A CN202111627112 A CN 202111627112A CN 114316123 B CN114316123 B CN 114316123B
- Authority
- CN
- China
- Prior art keywords
- reaction
- initiator
- reaction vessel
- carbon dioxide
- polymerizing
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention discloses a method for polymerizing photoresist resin by using supercritical carbon dioxide, which comprises the following steps: step S01: preparing a reaction vessel, and charging methacrylic acid monomer and an initiator into the reaction vessel; step S02: the air in the reaction vessel is discharged by a vacuum pump, and CO is replenished 2 Repeating for three times to make the CO in the kettle fully 2 An atmosphere; step S03: heating the reaction vessel to 60-100 deg.c and adding CO at 0-20MPa pressure 2 Carrying out polymerization reaction; step S04: at the end of the reaction, the reaction vessel was cooled, carbon dioxide was vented, and the product was subjected to GPC. The method can effectively avoid the interference of the solvent.
Description
Technical Field
The invention belongs to the technical field of high molecular polymerization, and particularly relates to a method for polymerizing photoresist resin by using supercritical carbon dioxide.
Background
Methacrylates have been extensively studied in Arf photoresists due to their high transparency. In order to satisfy the characteristics of the photoresist, it is necessary to prepare a methacrylic resin with a controllable molecular weight. The traditional polymerization mode is free radical polymerization, and a large amount of solvent, a long reaction time and a large amount of precipitant are needed; finally, the methacrylic resin is prepared by multiple precipitation and purification, the defects of the method are obvious, a large amount of solvent and precipitant are needed, and the reaction time is long.
Disclosure of Invention
Based on the problems existing in the prior art, the technical problem to be solved by the invention is to provide a method for utilizing supercritical CO 2 The method for preparing the photoresist resin in a polymerization mode can effectively avoid the interference of a solvent.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
the invention provides a method for polymerizing photoresist resin by using supercritical carbon dioxide, which is characterized by comprising the following steps:
step S01: preparing a reaction vessel, and charging methacrylic acid monomer and an initiator into the reaction vessel;
step S02: the air in the reaction vessel is discharged by a vacuum pump, and CO is replenished 2 Repeating for three times to make the CO in the kettle fully 2 An atmosphere;
step S03: heating the reaction vessel to 60-100 deg.c and adding CO at 0-20MPa pressure 2 Polymerization is carried out.
Step S04: at the end of the reaction, the reaction vessel was cooled, carbon dioxide was vented, and the product was subjected to GPC.
As a further improvement of the invention, in the step S01, the reaction vessel is a high-pressure reaction kettle.
As a further improvement of the invention, the initiator accounts for 1-10wt% of the total mass of the monomer in percentage by mass.
As a further improvement of the present invention, the initiator is at least one selected from the group consisting of azobisisobutyronitrile, azobisisovaleronitrile and dimethyl azobisisobutyrate.
As a further improvement of the invention, the initiator is azobisisobutyronitrile.
Methyl methacrylate, methyladamantane methacrylate and butyrolactone methacrylate are selected for the three monomers: 193nm photoresist host resin, methacrylic resin has high light transmittance at 193nm wavelength, and is suitable for 193nm photoresist host resin.
The initiator is the percentage of the total mass of the monomers, the dosage is 1-10wt%, and the initiator has the function of accelerating the polymerization reaction. If the amount is too small, the initiation effect is not achieved, and if the amount is too large, the reaction system has too large specific weight, the cost is high, and the reaction is insufficient.
The method for polymerizing photoresist resin by using supercritical carbon dioxide provided by the invention comprises the steps of adding monomers and an initiator into a high-pressure reaction kettle, and supplementing CO by pumping air 2 And (5) replacing the air in the kettle. Then CO with different pressure is added through heating 2 To carry out the polymerization of the monomers; the method has the advantages of no need of a large amount of solvents, no toxicity, no side reaction and the like. CO is treated by high pressure and temperature 2 Liquefaction serves as a solvent to carry out solvothermal reaction, and interference of the solvent is removed compared with conventional reaction.
Supercritical CO 2 The principle is that the atmosphere in the high-pressure reaction kettle is replaced by CO 2 Atmosphere and then introducing CO 2 Heating, thus CO in the kettle 2 Can liquefy under the influence of pressure and temperature, the common temperature is 31.6 ℃, the liquefaction effect can be achieved under the pressure of 7.5Mpa, the solubility after liquefaction is good, and the catalyst can be used as a solvent, and an initiator is added to perform free radical polymerization reaction. Cooling after reaction, releasing pressure, CO 2 And is vaporized and discharged, thus avoiding the interference of the solvent. CO 2 Is a nontoxic and harmless substance, and in the supercritical state, the substance is formed into liquid and is used as a solvent, and the solvent is vaporized and discharged after the pressure is released, so that the problem of a large amount of solvents in the traditional polymerization mode is effectively solved.
In addition, in the conventional polymerization method, a plurality of polymerization methods such as reversible addition-fragmentation free radical polymerization, atom free radical polymerization, anion-cation polymerization and the like are adopted, and a large amount of solvents such as tetrahydrofuran, toluene, dichloro and the like are not required, and the solvents have great toxicity. At the same time, various chain transfer agents, such as thio compounds, or catalysts, such as CuBr, butyllithium, etc., are required to be added, and these are also toxic. Furthermore, after the reaction is finished, a large amount of solvents such as linear alkane with smaller polarity, diethyl ether and methanol are added for precipitation treatment, and the personnel environment is greatly influenced. The supercritical carbon dioxide post-liquefaction is adopted as the solvent, and toxic solvents and even additives are not needed, so that the method is more environment-friendly.
Detailed Description
The invention provides a method for utilizing supercritical CO by the specific embodiment 2 The method for preparing the photoresist resin by polymerization mode is further described in more detail:
example 1
The supercritical CO utilization of the present embodiment 2 A method for preparing a photoresist resin by polymerization, comprising the steps of:
(1) According to the mass percentage, 35.87 weight percent of methyl methacrylate, 33.57 weight percent of methyladamantane methacrylate and 30.55 weight percent of methacrylic butyrolactone are put into a high-pressure reaction kettle, and a certain amount of azodiisobutyronitrile initiator is added, wherein the use amount of the initiator is 1% of the total mass of the monomers;
(2) Pumping out the air in the kettle by a vacuum pump, and adding CO 2 Repeating for three times to replace the air in the kettle with CO 2 ；
(3) Heating the reaction kettle to 60 ℃, and simultaneously adding CO of 5MPa 2 Carrying out polymerization reaction;
(4) After the reaction is finished for 4 hours, the reaction kettle is cooled, and CO is pumped out 2 The reaction was subjected to GPC testing.
Example 2
The supercritical CO utilization of the present embodiment 2 A method for preparing a photoresist resin by polymerization, comprising the steps of:
(1) According to the mass percentage, 35.87 weight percent of methyl methacrylate, 33.57 weight percent of methyladamantane methacrylate and 30.55 weight percent of methacrylic butyrolactone are put into a high-pressure reaction kettle, and a certain amount of azodiisobutyronitrile initiator is added, wherein the use amount of the initiator is 1% of the total monomer;
(2) Pumping out the air in the kettle by a vacuum pump, and adding CO 2 Repeating for three times to replace the air in the kettle with CO2;
(3) Heating the reaction kettle to 60 ℃, and simultaneously adding 10MPa of CO 2 Carrying out polymerization reaction;
(4) After the reaction is finished for 4 hours, the reaction kettle is cooled, and CO is pumped out 2 The reaction was subjected to GPC testing.
Example 3
The method for preparing photoresist resin by using the supercritical CO2 polymerization mode in the embodiment comprises the following steps:
(1) According to mass percent, 35.87 weight percent of methyl methacrylate, 33.57 weight percent of methyladamantane methacrylate and 30.55 weight percent of methacrylic butyrolactone are put into a high-pressure reaction kettle, a certain amount of azodiisobutyronitrile initiator is added, and the initiator dosage is 1% of the total monomer weight;
(2) Pumping out the air in the kettle by a vacuum pump, and adding CO 2 Repeating for three times to replace the air in the kettle with CO 2 ；
(3) Heating the reaction kettle to 60 ℃, and simultaneously adding CO of 15MPa 2 Carrying out polymerization reaction;
(4) After the reaction is finished for 4 hours, the reaction kettle is cooled, and CO is pumped out 2 The reaction was subjected to GPC testing.
Example 4
The supercritical CO utilization of the present embodiment 2 A method for preparing a photoresist resin by polymerization, comprising the steps of:
according to the mass percentage, 35.87 weight percent of methyl methacrylate, 33.57 weight percent of methyladamantane methacrylate and 30.55 weight percent of methacrylic butyrolactone are put into a high-pressure reaction kettle, and a certain amount of azodiisobutyronitrile initiator is added, wherein the use amount of the initiator is 5% of the total monomer;
(2) Pumping out the air in the kettle by a vacuum pump, and adding CO 2 Repeating for three times to replace the air in the kettle with CO 2 ；
(3) Heating the reaction kettle to 60 ℃, and simultaneously adding CO of 5MPa 2 Carrying out polymerization reaction;
(4) After the reaction is finished for 4 hours, the reaction kettle is cooled, and CO is pumped out 2 The reaction was subjected to GPC testing.
Example 5
The method for preparing photoresist resin by using the supercritical CO2 polymerization mode in the embodiment comprises the following steps:
(1) According to mass percent, 35.87 weight percent of methyl methacrylate, 33.57 weight percent of methyladamantane methacrylate and 30.55 weight percent of methacrylic butyrolactone are put into a high-pressure reaction kettle, a certain amount of azodiisobutyronitrile initiator is added, and the initiator dosage is 5% of the total monomer dosage according to mass percent;
(2) Pumping out the air in the kettle by a vacuum pump, and adding CO 2 Repeating for three times to replace the air in the kettle with CO 2 ；
(3) Heating the reaction kettle to 60 ℃, and simultaneously adding 10MPa of CO 2 Carrying out polymerization reaction;
(4) After the reaction is finished for 4 hours, the reaction kettle is cooled, and CO is pumped out 2 The reaction was subjected to GPC testing.
Example 6
The supercritical CO utilization of the present embodiment 2 A method for preparing a photoresist resin by polymerization, comprising the steps of:
(1) According to mass percent, 35.87 weight percent of methyl methacrylate, 33.57 weight percent of methyladamantane methacrylate and 30.55 weight percent of methacrylic butyrolactone are put into a high-pressure reaction kettle, a certain amount of azodiisobutyronitrile initiator is added, and the initiator dosage is 5% of the total monomer dosage according to mass percent;
(2) Pumping out the air in the kettle by a vacuum pump, and adding CO 2 Repeating for three times to replace the air in the kettle with CO2;
(3) Heating the reaction kettle to 60 ℃, and simultaneously adding CO of 15MPa 2 Carrying out polymerization reaction;
(4) After the reaction is finished for 4 hours, the reaction kettle is cooled, and CO is pumped out 2 The reaction was subjected to GPC testing.
Example 7
The supercritical CO utilization of the present embodiment 2 A method for preparing a photoresist resin by polymerization, comprising the steps of:
(1) According to mass percent, 35.87 weight percent of methyl methacrylate, 33.57 weight percent of methyladamantane methacrylate and 30.55 weight percent of methacrylic butyrolactone are put into a high-pressure reaction kettle, a certain amount of azodiisobutyronitrile initiator is added, and the initiator is 10 percent of the total monomer according to mass percent;
(2) Pumping out the air in the kettle by a vacuum pump, and adding CO 2 Repeating for three times to replace the air in the kettle with CO 2 ；
(3) Heating the reaction kettle to 60 ℃,simultaneously adding CO of 5MPa 2 Carrying out polymerization reaction;
(4) After the reaction is finished for 4 hours, the reaction kettle is cooled, and CO is pumped out 2 The reaction was subjected to GPC testing.
Example 8
The supercritical CO utilization of the present embodiment 2 A method for preparing a photoresist resin by polymerization, comprising the steps of:
(1) According to the mass percentage, 35.87 weight percent of methyl methacrylate, 33.57 weight percent of methyladamantane methacrylate and 30.55 weight percent of methacrylic butyrolactone are put into a high-pressure reaction kettle, and a certain amount of azodiisobutyronitrile initiator is added, wherein the use amount of the initiator is 10 percent of the total monomer;
(2) Pumping out the air in the kettle by a vacuum pump, and adding CO 2 Repeating for three times to replace the air in the kettle with CO2;
(3) Heating the reaction kettle to 60 ℃, and simultaneously adding 10MPa of CO 2 Carrying out polymerization reaction;
(4) After the reaction is finished for 4 hours, the reaction kettle is cooled, and CO is pumped out 2 The reaction was subjected to GPC testing.
Example 9
The supercritical CO utilization of the present embodiment 2 A method for preparing a photoresist resin by polymerization, comprising the steps of:
(1) According to mass percent, 35.87 weight percent of methyl methacrylate, 33.57 weight percent of methyladamantane methacrylate and 30.55 weight percent of methacrylic butyrolactone are put into a high-pressure reaction kettle, a certain amount of azodiisobutyronitrile initiator is added, and the initiator is 10 percent of the total monomer according to mass percent;
(2) Pumping out the air in the kettle by a vacuum pump, and adding CO 2 Repeating for three times to replace the air in the kettle with CO2;
(3) Heating the reaction kettle to 60 ℃, and simultaneously adding CO of 15MPa 2 Carrying out polymerization reaction;
(4) After the reaction is finished for 4 hours, the reaction kettle is cooled, and CO is pumped out 2 The reaction was subjected to GPC testing.
Comparative example 1
The preparation method of the traditional photoresist resin comprises the following steps:
(1) According to mass percent, 35.87 weight percent of methyl methacrylate, 33.57 weight percent of methyladamantane methacrylate and 30.55 weight percent of methacrylic acid butyrolactone are placed in a four-neck flask containing THF solvent, and stirred until the monomers are uniformly mixed, wherein the total usage amount of the THF solvent for dissolving the monomers is 6 times of the total mass of the monomers;
(2) After the monomer is dissolved, adding azodiisobutyronitrile, stirring until the azodiisobutyronitrile is dissolved, wherein the initiator is used in an amount of 1wt% of the total mass of the monomer;
(3) Air in the reaction vessel was replaced with nitrogen and heated to 66 ℃ with stirring;
(4) After the reaction was carried out for 4 hours, the reaction solution was cooled, and the reaction solution was poured into n-hexane to carry out precipitation treatment.
(5) After solid-liquid separation, the resin was weighed and tested for GPC.
Comparative example 2
The preparation method of the traditional photoresist resin comprises the following steps:
(1) According to mass percent, 35.87 weight percent of methyl methacrylate, 33.57 weight percent of methyladamantane methacrylate and 30.55 weight percent of methacrylic acid butyrolactone are placed in a four-neck flask containing THF solvent, and stirred until the monomers are uniformly mixed, wherein the total usage amount of the THF solvent for dissolving the monomers is 6 times of the total mass of the monomers;
(2) After the monomer is dissolved, adding azodiisobutyronitrile, stirring until the azodiisobutyronitrile is dissolved, wherein the initiator is 5wt% of the total mass of the monomer;
(3) Air in the reaction vessel was replaced with nitrogen and heated to 66 ℃ with stirring;
(4) After the reaction was carried out for 4 hours, the reaction solution was cooled, and the reaction solution was poured into n-hexane to carry out precipitation treatment.
(5) After solid-liquid separation, the resin was weighed and tested for GPC.
Comparative example 3
The preparation method of the traditional photoresist resin comprises the following steps:
(1) According to mass percent, 35.87 weight percent of methyl methacrylate, 33.57 weight percent of methyladamantane methacrylate and 30.55 weight percent of methacrylic acid butyrolactone are placed in a four-neck flask containing THF solvent, and stirred until the monomers are uniformly mixed, wherein the total usage amount of the THF solvent for dissolving the monomers is 6 times of the total mass of the monomers;
(2) After the monomer is dissolved, adding azodiisobutyronitrile, stirring until the azodiisobutyronitrile is dissolved, wherein the initiator is 10wt% of the total mass of the monomer;
(3) Air in the reaction vessel was replaced with nitrogen and heated to 66 ℃ with stirring;
(4) After the reaction was carried out for 4 hours, the reaction solution was cooled, and the reaction solution was poured into n-hexane to carry out precipitation treatment.
(5) After solid-liquid separation, the resin was weighed and tested for GPC.
Experimental results: TABLE 1 polymerization results under different conditions
The molecular weight distribution of the polymer is mainly related to the solubility of the monomer in the solvent and the initiator concentration, so the same initiator and concentration comparison is used in the comparative example, so the experiment mainly uses CO2, and the influence of the components is not examined, so the components are fixed. In addition, the conventional free radical polymerization used in the comparative examples requires a solvent, which is also selected to match the optimum reflux temperature of the initiator for the reaction.
The results of the experiments are shown in Table 1. First, the process of the present invention does accelerate the polymerization of monomers relative to conventional radical polymerization, as compared to the comparative examples. The molecular weight of the traditional method is reduced along with the increase of the initiator, and the molecular weight distribution is wider, which is caused by the fact that the amount of the initiator is increased, so that the concentration of free radicals in the system is overlarge, the chain termination reaction is overlarge, and short-chain substances are more. With the process according to the invention, the chain growth reaction is markedly favored, and with CO 2 The pressure of (2) increases and the molecular weight distribution decreases, indicating a high monomer conversion. And a corresponding increase in the initiator amount will result in an increase in the concentration of free radicals in the system, resulting in a smaller molecule. Overall, the process of the present invention is more efficient than conventional processes and does not require complex precipitation purification processes. To sum up, use is made of this critical CO 2 A method of polymerizing a photoresist host resin is possible.
It should be understood that these examples are for the purpose of illustrating the invention only and are not intended to limit the scope of the invention. Furthermore, it is to be understood that various changes, modifications and/or variations may be made by those skilled in the art after reading the technical content of the present invention, and that all such equivalents are intended to fall within the scope of protection defined in the claims appended hereto. It will be appreciated by those skilled in the art that the present invention can be carried out in other embodiments without departing from the spirit or essential characteristics thereof. Accordingly, the above disclosed embodiments are illustrative in all respects, and not exclusive. All changes that come within the scope of the invention or equivalents thereto are intended to be embraced therein.
Claims (5)
1. A method for polymerizing a photoresist resin using supercritical carbon dioxide, comprising the steps of:
step S01: preparing a reaction vessel, and charging methacrylic acid monomer and an initiator into the reaction vessel; the methacrylic acid monomer is a mixture of methyl methacrylate, methyladamantane methacrylate and methacrylic acid butyrolactone;
step S02: the air in the reaction vessel is discharged by a vacuum pump, and CO is replenished 2 Repeating for three times to make the CO in the kettle fully 2 An atmosphere;
step S03: heating the reaction vessel to 60-100 deg.c and adding CO at 0-20MPa pressure 2 Polymerization is carried out.
Step S04: at the end of the reaction, the reaction vessel was cooled, carbon dioxide was vented, and the product was subjected to GPC.
2. The method for polymerizing a resist resin using supercritical carbon dioxide according to claim 1, wherein in the step S01, the reaction vessel is an autoclave.
3. The method for polymerizing a resist resin using supercritical carbon dioxide according to claim 1, wherein the initiator is 1 to 10% by mass based on the total mass of the monomers.
4. The method for polymerizing a resist resin using supercritical carbon dioxide according to claim 1, wherein the initiator is at least one selected from the group consisting of azobisisobutyronitrile, azobisisovaleronitrile and dimethyl azobisisobutyrate.
5. The method for polymerizing a resist resin with supercritical carbon dioxide according to claim 4, wherein the initiator is azobisisobutyronitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111627112.6A CN114316123B (en) | 2021-12-28 | 2021-12-28 | Method for polymerizing photoresist resin by using supercritical carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111627112.6A CN114316123B (en) | 2021-12-28 | 2021-12-28 | Method for polymerizing photoresist resin by using supercritical carbon dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114316123A CN114316123A (en) | 2022-04-12 |
| CN114316123B true CN114316123B (en) | 2023-04-21 |
Family
ID=81014671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111627112.6A Active CN114316123B (en) | 2021-12-28 | 2021-12-28 | Method for polymerizing photoresist resin by using supercritical carbon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114316123B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1079099C (en) * | 1998-11-26 | 2002-02-13 | 中国科学院广州化学研究所 | Method for preparing polyacrylic acid in supercritical carbon dioxide medium |
| US6914105B1 (en) * | 1999-11-12 | 2005-07-05 | North Carolina State University | Continuous process for making polymers in carbon dioxide |
| CN1424335A (en) * | 2002-12-20 | 2003-06-18 | 中国科学院广州化学研究所 | Preparation for acrylic ester thickener |
| CN112778449B (en) * | 2020-12-29 | 2022-04-29 | 宁波南大光电材料有限公司 | Methacrylic resin, preparation method thereof and photoresist |
-
2021
- 2021-12-28 CN CN202111627112.6A patent/CN114316123B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114316123A (en) | 2022-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS59226011A (en) | Manufacture of cis-1,4-polybutadiene | |
| CN112778449B (en) | Methacrylic resin, preparation method thereof and photoresist | |
| CN114316123B (en) | Method for polymerizing photoresist resin by using supercritical carbon dioxide | |
| CN1279693A (en) | Continuous bulk polymerization process | |
| CN103946270B (en) | Nonmetal initiator is used to synthesize high molecular PEO | |
| EP0590988B1 (en) | Process for producing crosslinked polymer containing carboxyl group | |
| JP3084485B2 (en) | Production of macromonomer | |
| CA1076295A (en) | Process for the continuous preparation of reactive copolymers | |
| KR101275741B1 (en) | Method for Preparing High Molecular Weight Poly(methacrylic acid) by Solution Polymerization | |
| CN112011050B (en) | Ultrahigh-performance water reducing agent and preparation method thereof | |
| CN100465196C (en) | Method for preparing high molecular compound adopting novel ion liquid polymerization initiation system | |
| US4600755A (en) | Free radical initiated polymerization of polymerizable ethylenically unsaturated monomer component in the presence of hydrogen peroxide | |
| CN112694558A (en) | Method for regulating and controlling molecular weight of methacrylic resin | |
| CN113956392B (en) | Photoresist resin and preparation method thereof | |
| KR20000040715A (en) | Method for preparing styrene/acrylic water-soluble resin by continuous bulk polymerization | |
| Huynh et al. | Synthesis and characterization of star‐shaped PMMA using low‐ppm ARGET ATRP approach and changing to rigid powder for bone cement | |
| CN113265052B (en) | Preparation method of vinyl MT resin with good stability | |
| CN114836088B (en) | Coating composition and preparation method thereof | |
| CN110746523A (en) | Lignin-based macromolecular photoinitiator and preparation method and application thereof | |
| CN118165261A (en) | Preparation method of high-viscosity photoresist resin | |
| CN109160973B (en) | Aqueous phase ultrasonic synthesis method of maleic anhydride/alpha-arene copolymer | |
| KR20160140707A (en) | Alkylene oxide polymer production method | |
| JP3495382B2 (en) | Acrylic resin and method for producing the same | |
| CN1387946A (en) | Bimetal cyanide catalyst and its prepn and application | |
| CN114163550A (en) | Multifunctional macromolecular photoinitiator and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |