CN113698527B - Transparent flame-retardant PMMA resin and preparation method thereof - Google Patents
Transparent flame-retardant PMMA resin and preparation method thereof Download PDFInfo
- Publication number
- CN113698527B CN113698527B CN202111079923.7A CN202111079923A CN113698527B CN 113698527 B CN113698527 B CN 113698527B CN 202111079923 A CN202111079923 A CN 202111079923A CN 113698527 B CN113698527 B CN 113698527B
- Authority
- CN
- China
- Prior art keywords
- reaction
- monomer
- flame
- retardant
- putting
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
Abstract
The invention relates to a transparent flame-retardant PMMA resin and a preparation method thereof, which comprises the steps of synthesizing a flame-retardant monomer, copolymerizing a methyl methacrylate monomer and the flame-retardant monomer, devolatilizing, extruding and granulating to obtain the PMMA resin with stable chemical bonds between a flame retardant and a matrix. The PMMA resin prepared by the invention has high light transmittance and long-acting flame retardant performance.
Description
Technical Field
The invention belongs to the field of high polymers, and particularly relates to a transparent flame-retardant PMMA resin and a preparation method thereof
Background
Polymethyl methacrylate (PMMA) has excellent light transmittance, weather resistance and appearance, is widely applied to the fields of automobiles, displays, electronic and electric appliances, illumination, billboards and the like, has larger development space in the future and has very wide market prospect.
The PMMA resin has good electrical insulation performance, wear resistance and weather resistance, but the PMMA has poor heat resistance, belongs to extremely inflammable materials, and the heat release rate peak value (PHRR) of the PMMA resin in a cone calorimetric test can reach 1058kW/m 2 And the combustion process of PMMA is often accompanied by severe dripping, which can be extremely harmful once burned.
The conventional method for improving the flame retardant property of PMMA is to blend PMMA and a flame retardant to prepare flame retardant PMMA, but the method usually sacrifices the transparency of PMMA, so the application of PMMA in the optical field is obviously limited, and the existing market demand cannot be met; therefore, the problem of how to improve the flame retardant property of PMMA and ensure higher transparency of PMMA needs to be solved urgently.
Disclosure of Invention
The invention aims to provide a transparent and flame-retardant PMMA resin and a preparation method thereof.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a transparent, flame retardant PMMA resin comprising the following structure:
wherein R is selected from: -H, -CH 3 、-OCH 3 、
R 1 Selected from: -NH-, -COO-, -O-;
R 2 selected from: amino, carboxyl, hydroxyl.
In another aspect of the present invention, there is provided a method for preparing the transparent flame-retardant PMMA resin, comprising the steps of:
1) Putting a reaction monomer A, tetrahydrofuran and triethylamine into a reactor, uniformly stirring at normal temperature, slowly adding a reaction monomer B, heating to 40-80 ℃ for reacting for 8-20h, filtering to remove triethylamine hydrochloride after the reaction is finished, carrying out reduced pressure distillation on the residual liquid, concentrating to remove most of residual solvent, adding deionized water, filtering, and separating out white solid to obtain an intermediate C;
wherein the weight proportion relationship of the reaction monomer A, tetrahydrofuran, triethylamine and the reaction monomer B is as follows: 10-30:60-100:5-25:20-60 parts of;
2) Putting the intermediate C, glycidyl methacrylate and the catalyst D into a reaction kettle, uniformly stirring, heating to 30-60 ℃, and reacting for 2-5h to obtain a flame-retardant monomer E;
wherein the weight ratio relation of the intermediate C, the glycidyl methacrylate and the catalyst D is 1-5:2-10:0.01-0.05;
3) Putting methyl methacrylate, a flame-retardant monomer E, a chain transfer agent and an initiator into a reaction kettle, uniformly stirring, and heating to 120-140 ℃ for copolymerization reaction to obtain slurry F;
wherein the weight ratio of the methyl methacrylate, the flame-retardant monomer E, the chain transfer agent and the initiator is 80-120:1-8:0.2-0.4:0.005-0.012;
4) Continuously feeding the obtained slurry F into a devolatilizer, and removing unreacted monomers to obtain a melt G;
5) And feeding the devolatilized melt G into a double-screw extruder for extrusion and granulation to obtain the PMMA resin.
In the method of the invention, the structural formula of the reaction monomer A is as follows:
in the method of the invention, the structural formula of the reaction monomer B is as follows:
in the method, the structural formula of the intermediate C is as follows:
in the method of the present invention, the catalyst D is selected from: iron hydroxide, potassium carbonate, sodium carbonate, preferably iron hydroxide;
in the method of the invention, the structural formula of the flame-retardant monomer E is as follows:
in the method of the present invention, the initiator is selected from the group consisting of: tert-butyl peroxy-3,5,5-trimethylhexanoate, di-tert-butyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile; preferably: tert-butyl peroxy-3,5,5-trimethylhexanoate;
in the process of the present invention, the chain transfer agent is selected from: n-octyl mercaptan, iso-octyl mercaptan, tert-dodecyl mercaptan, n-dodecyl mercaptan; preferably: n-octyl mercaptan.
In the method of the invention, the temperature of the devolatilizer is as follows: 190-240 ℃; preferably: 200-220 ℃.
In the method of the invention, the temperature interval of the screw of the extruder is as follows: a first area: 190-210 ℃; a second zone: 210-230 ℃; and (3) three zones: 220 to 240 ℃; and (4) four areas: 220 to 240 ℃; and a fifth zone: 210-230 ℃; preferably: 200 ℃, 220 ℃, 230 ℃ and 220 ℃;
in the method, the rotating speed of the extruder is 100-300rpm; preferably 200rpm.
The invention has the positive effects that:
the invention uses a chemical method to insert a phosphorus-containing lateral group into a comonomer, and then uses the comonomer to copolymerize with methyl methacrylate to obtain the PMMA resin with high transparency and long-acting flame retardance. The phosphorus-containing flame retardant participates in preparation in the form of monomer structural units and finally exists in the copolymer in the form of molecular chain segments, and the migration of the flame retardant in resin can be effectively avoided due to the existence of a stable chemical bond between the flame retardant and the comonomer, so that the long-acting and lasting flame retardant property of the material is ensured; after the copolymerization of the comonomer with flame retardant property and methyl methacrylate, the great reduction of resin transparency caused by the fact that a large amount of flame retardant is mixed in by a physical method is avoided, the degree of crosslinking of the polymer is increased due to the fact that both ends of the flame retardant monomer have active groups, and meanwhile, the mechanical property of the resin is improved. The PMMA resin obtained by copolymerization in the invention has high transmittance, can be maintained at about 92 percent, and has flame retardant property at V-0 level.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The raw material sources in the following examples and comparative examples of the present invention were obtained commercially, unless otherwise specified.
The following methods were used for the tests in the following examples and comparative examples of the present invention: the transmittance was measured in accordance with JIS K7361-1 GB/T2410; the flame retardant performance is tested according to GB/T2408-2008, and the tensile performance is tested according to GB/T1040.2-2006; HDT was tested according to GB/T15597.1-2009.
In the examples, the extruder screw temperature interval is: a first area: 200 ℃; and a second zone: 220 ℃; and (3) three zones: 230 ℃; and (4) a fourth zone: 230 ℃; and a fifth zone: 220 ℃; the rotating speed of the extruder is 200rpm.
Example 1
Preparation of flame-retardant comonomer: putting 300g of phenyl dichlorophosphate, 800g of tetrahydrofuran and 50g of triethylamine into a three-neck flask with a stirrer, uniformly stirring at normal temperature, slowly dripping 400g of p-phenol, heating to 60 ℃ after dripping is finished, reacting for 12 hours, filtering triethylamine hydrochloride after the reaction is finished, carrying out reduced pressure distillation on the residual liquid, concentrating to remove most of residual solvent, adding deionized water, filtering, and separating out white solid to obtain an intermediate C;
putting 100g of the intermediate C, 500g of glycidyl methacrylate and 1g of potassium hydroxide into a reaction kettle, uniformly stirring, heating to 35 ℃, and reacting for 5 hours to obtain a flame-retardant monomer E;
preparation of PMMA resin: putting 80g of flame-retardant monomer E, 800g of methyl methacrylate, 4g of tert-dodecyl mercaptan and 0.06g of azobisisobutyronitrile into a reaction kettle, uniformly stirring, and heating to 130 ℃ for copolymerization reaction to obtain slurry F; putting the obtained slurry F into a devolatilizer at the temperature of 200 ℃, and removing unreacted monomers to obtain a melt G; and feeding the devolatilized melt G into a double-screw extruder for extrusion and granulation to obtain the PMMA resin.
Example 2
Preparation of flame-retardant comonomer: putting 100g of phenylphosphoryl dichloride, 600g of tetrahydrofuran and 250g of triethylamine into a three-neck flask with a stirrer, uniformly stirring at normal temperature, slowly dripping 200g of 4-aminophenol, heating to 50 ℃ after dripping is finished, reacting for 18 hours, filtering triethylamine hydrochloride after the reaction is finished, carrying out reduced pressure distillation on the residual liquid, concentrating to remove most residual solvent, adding deionized water, filtering, and separating out white solid to obtain an intermediate C;
putting 30g of the intermediate C, 20g of glycidyl methacrylate and 0.5g of ferric hydroxide into a reaction kettle, uniformly stirring, heating to 45 ℃, and reacting for 4 hours to obtain a flame-retardant monomer E;
preparation of PMMA resin: putting 10g of flame-retardant monomer E, 1200g of methyl methacrylate, 3g of n-octyl mercaptan, 0.08g of tert-butyl peroxy-3,5,5-trimethyl hexanoate into a reaction kettle, uniformly stirring, and heating to 135 ℃ for copolymerization reaction to obtain slurry F; putting the obtained slurry F into a devolatilizer at the temperature of 200 ℃, and removing unreacted monomers to obtain a melt G; and feeding the devolatilized melt G into a double-screw extruder for extrusion and granulation to obtain the PMMA resin.
Example 3
Preparation of flame-retardant comonomer: putting 150g of methyl phosphoryl dichloride, 1000g of tetrahydrofuran and 150g of triethylamine into a three-neck flask with a stirrer, uniformly stirring at normal temperature, slowly dripping 600g of p-carboxyphenol, heating to 80 ℃ after finishing dripping, reacting for 10 hours, filtering triethylamine hydrochloride after the reaction is finished, carrying out reduced pressure distillation on the residual liquid, concentrating to remove most of residual solvent, adding deionized water, filtering, and separating out white solid to obtain an intermediate C;
putting 50g of the intermediate C, 100g of glycidyl methacrylate and 0.3g of potassium carbonate into a reaction kettle, uniformly stirring, heating to 55 ℃, and reacting for 2 hours to obtain a flame-retardant monomer E;
preparation of PMMA resin: putting 20g of flame-retardant monomer E, 1000g of methyl methacrylate, 2g of isooctyl mercaptan and 0.12g of di-tert-butyl peroxide into a reaction kettle, uniformly stirring, and heating to 140 ℃ for copolymerization reaction to obtain slurry F; putting the obtained slurry F into a devolatilization device at the temperature of 200 ℃, and removing unreacted monomers to obtain a melt G; and feeding the devolatilized melt G into a double-screw extruder for extrusion and granulation to obtain the PMMA resin.
Example 4
Preparation of flame-retardant comonomer: putting 250g of methyl dichlorophosphate, 700g of tetrahydrofuran and 100g of triethylamine into a three-neck flask with a stirrer, uniformly stirring at normal temperature, slowly dripping 450g of 4-aminophenol, heating to 65 ℃ after dripping, reacting for 14 hours, filtering triethylamine hydrochloride after the reaction is finished, carrying out reduced pressure distillation on the residual liquid, concentrating to remove most residual solvent, adding deionized water, filtering, and separating out white solid to obtain an intermediate C;
putting 40g of the intermediate C, 40g of glycidyl methacrylate and 0.4g of sodium carbonate into a reaction kettle, uniformly stirring, heating to 50 ℃, and reacting for 3 hours to obtain a flame-retardant monomer E;
preparation of PMMA resin: putting 30g of flame-retardant monomer E, 900g of methyl methacrylate, 3.5g of n-dodecyl mercaptan and 0.11g of azodiisoheptanonitrile into a reaction kettle, uniformly stirring, and heating to 138 ℃ for copolymerization reaction to obtain slurry F; putting the obtained slurry F into a devolatilizer at the temperature of 200 ℃, and removing unreacted monomers to obtain a melt G; and feeding the devolatilized melt G into a double-screw extruder for extrusion and granulation to obtain the PMMA resin.
Example 5
Preparation of flame-retardant comonomer: putting 200g of phenyl dichlorophosphate, 750g of tetrahydrofuran and 100g of triethylamine into a three-neck flask with a stirrer, uniformly stirring at normal temperature, slowly dripping 250g of p-phenol, heating to 75 ℃ after dripping is finished, reacting for 9 hours, filtering triethylamine hydrochloride after the reaction is finished, carrying out reduced pressure distillation on the residual liquid, concentrating to remove most of residual solvent, adding deionized water, filtering, and separating out white solid to obtain an intermediate C;
putting 25g of the intermediate C, 70g of glycidyl methacrylate and 0.2g of ferric hydroxide into a reaction kettle, uniformly stirring, heating to 35 ℃, and reacting for 4.5 hours to obtain a flame-retardant monomer E;
preparation of PMMA resin: putting 15g of flame-retardant monomer E, 1050g of methyl methacrylate, 2.5g of isooctyl mercaptan and 0.09g of tert-butyl peroxy-3,5,5-trimethyl hexanoate into a reaction kettle, uniformly stirring, and heating to 125 ℃ for copolymerization reaction to obtain slurry F; putting the obtained slurry F into a devolatilizer at the temperature of 200 ℃, and removing unreacted monomers to obtain a melt G; and feeding the devolatilized melt G into a double-screw extruder for extrusion and granulation to obtain the PMMA resin.
Comparative example 1
Putting 1200g of methyl methacrylate, 3g of n-octyl mercaptan and 0.1g of tert-butyl peroxy-3,5,5-trimethylhexanoate into a reaction kettle, uniformly stirring, and heating to 135 ℃ for copolymerization reaction to obtain slurry; putting the obtained slurry into a devolatilizer at the temperature of 200 ℃, and removing unreacted monomers to obtain a melt; and feeding the devolatilized melt into a double-screw extruder for extrusion and granulation to obtain the PMMA resin.
The performance test is carried out according to the following method:
1) Test specimens were prepared using the PMMA resins prepared in examples 1 to 5 and comparative example, respectively;
2) The specific results of the tests are shown in the following table.
As can be seen from the test results of examples 1-5 and comparative examples, the flame-retardant PMMA resin prepared by the invention has better flame-retardant performance, the transparency is comparable to that of pure PMMA resin, the Heat Distortion Temperature (HDT) tested by using an Instron series CEAST thermomechanical test system is also obviously higher than that of the pure PMMA resin, and the tensile strength is also improved.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (13)
1. A transparent flame-retardant PMMA resin, characterized in that it comprises the following structure:
wherein R is selected from: -H, -CH 3 、-OCH 3 、
R 1 Selected from: -NH-, -COO-, -O-;
R 2 selected from: amino, carboxyl, hydroxyl;
the preparation method of the transparent flame-retardant PMMA resin comprises the following steps:
1) Putting a reaction monomer A, a solvent and triethylamine into a reactor, slowly adding a reaction monomer B, heating for reaction, filtering triethylamine hydrochloride after the reaction is finished, and concentrating the residual liquid to remove most of residual solvent to obtain an intermediate C;
wherein the structural formula of the reaction monomer A is as follows:
The structural formula of the reaction monomer B is as follows:
2) Putting the intermediate C, glycidyl methacrylate and the catalyst D into a reaction kettle, uniformly stirring, and heating for reaction to obtain a flame-retardant monomer E;
3) Putting methyl methacrylate, a flame-retardant monomer E, a chain transfer agent and an initiator into a reaction kettle, and carrying out copolymerization reaction to obtain slurry F;
4) Removing unreacted monomers from the slurry F to obtain a melt G;
5) And extruding and pelletizing the melt G to obtain the PMMA resin.
2. A preparation method of transparent and flame-retardant PMMA resin comprises the following steps:
1) Putting a reaction monomer A, a solvent and triethylamine into a reactor, slowly adding a reaction monomer B, heating for reaction, filtering triethylamine hydrochloride after the reaction is finished, and concentrating the residual liquid to remove most of residual solvent to obtain an intermediate C;
wherein the structural formula of the reaction monomer A is as follows:
The structural formula of the reaction monomer B is as follows:
2) Putting the intermediate C, glycidyl methacrylate and the catalyst D into a reaction kettle, uniformly stirring, and heating for reaction to obtain a flame-retardant monomer E;
3) Putting methyl methacrylate, a flame-retardant monomer E, a chain transfer agent and an initiator into a reaction kettle, and carrying out copolymerization reaction to obtain slurry F;
4) Removing unreacted monomers from the slurry F to obtain a melt G;
5) And extruding and pelletizing the melt G to obtain the PMMA resin.
3. The method as claimed in claim 2, wherein in step 1), the weight ratio of the reaction monomer A, the solvent, the triethylamine and the reaction monomer B is as follows: 10-30:60-100:5-25:20-60.
4. The process of claim 3, wherein in step 1), the solvent is tetrahydrofuran.
5. The method according to any one of claims 2 to 4, wherein in step 1), the temperature is raised to 40 to 80 ℃ for reaction for 8 to 20 hours.
6. The method according to claim 2, wherein in the step 2), the weight ratio of the intermediate C, the glycidyl methacrylate and the catalyst D is 1-5:2-10:0.01-0.05.
7. The method of claim 6, wherein in the step 2), the catalyst D is one or more of ferric hydroxide, potassium carbonate and sodium carbonate.
8. The method according to any one of claims 2 and 6 to 7, wherein in the step 2), the temperature is raised to 30-60 ℃ for reaction for 2-5h.
9. The method as claimed in claim 2, wherein in the step 3), the weight ratio of the methyl methacrylate to the flame-retardant monomer E to the chain transfer agent to the initiator is 80-120:1-8:0.2-0.4:0.005-0.012.
10. The method as claimed in claim 9, wherein in step 3), the chain transfer agent is selected from one or more of n-octyl mercaptan, isooctyl mercaptan, tert-dodecyl mercaptan and n-dodecyl mercaptan, and the initiator is selected from one or more of tert-butyl peroxy-3,5,5-trimethyl hexanoate, di-tert-butyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile.
11. The process according to any one of claims 2 and 9 to 10, wherein in step 3), the reaction temperature is 120 to 140 ℃.
12. The method of claim 2, wherein in step 4), the unreacted monomers are devolatilized using a devolatilizer at a temperature of: 190-240 ℃.
13. The method as claimed in claim 2, wherein, in step 5), the pellets are extruded in a twin-screw extruder having a screw temperature range of: a first area: 190 ℃ -210 ℃, zone two: 210 ℃ -230 ℃, three zones: 220 ℃ to 240 ℃, four zones: 220 ℃ to 240 ℃, five zones: 210-230 ℃; the rotating speed is 100-300rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111079923.7A CN113698527B (en) | 2021-09-15 | 2021-09-15 | Transparent flame-retardant PMMA resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111079923.7A CN113698527B (en) | 2021-09-15 | 2021-09-15 | Transparent flame-retardant PMMA resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113698527A CN113698527A (en) | 2021-11-26 |
| CN113698527B true CN113698527B (en) | 2022-11-08 |
Family
ID=78660538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111079923.7A Active CN113698527B (en) | 2021-09-15 | 2021-09-15 | Transparent flame-retardant PMMA resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113698527B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101460511A (en) * | 2006-06-09 | 2009-06-17 | 昭和高分子株式会社 | Process for production of aminated phosphoric acid ester compound, flame-retardant resin, and flame-retardant resin composition |
| US20120165444A1 (en) * | 2010-12-22 | 2012-06-28 | Cheil Industries Inc. | Novel Phosphorus Compound, Method of Preparing the Same and Flame Retardant Thermoplastic Resin Composition Including the Same |
| CN103172906A (en) * | 2011-12-20 | 2013-06-26 | 威海市泓淋电子有限公司 | Organic phosphate fire retardant |
| CN107936170A (en) * | 2017-12-04 | 2018-04-20 | 万华化学集团股份有限公司 | A kind of heat-resistant polymethyl methacrylate and preparation method thereof |
| CN109206600A (en) * | 2017-07-03 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of preparation method of phosphorous copolymerization flame-proof polylactic acid fiber |
| CN111909302A (en) * | 2020-06-01 | 2020-11-10 | 浙江华帅特新材料科技有限公司 | Phosphorus/silicon-containing flame-retardant transparent acrylic resin and preparation method thereof |
-
2021
- 2021-09-15 CN CN202111079923.7A patent/CN113698527B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101460511A (en) * | 2006-06-09 | 2009-06-17 | 昭和高分子株式会社 | Process for production of aminated phosphoric acid ester compound, flame-retardant resin, and flame-retardant resin composition |
| US20120165444A1 (en) * | 2010-12-22 | 2012-06-28 | Cheil Industries Inc. | Novel Phosphorus Compound, Method of Preparing the Same and Flame Retardant Thermoplastic Resin Composition Including the Same |
| CN103172906A (en) * | 2011-12-20 | 2013-06-26 | 威海市泓淋电子有限公司 | Organic phosphate fire retardant |
| CN109206600A (en) * | 2017-07-03 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of preparation method of phosphorous copolymerization flame-proof polylactic acid fiber |
| CN107936170A (en) * | 2017-12-04 | 2018-04-20 | 万华化学集团股份有限公司 | A kind of heat-resistant polymethyl methacrylate and preparation method thereof |
| CN111909302A (en) * | 2020-06-01 | 2020-11-10 | 浙江华帅特新材料科技有限公司 | Phosphorus/silicon-containing flame-retardant transparent acrylic resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113698527A (en) | 2021-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0251445B2 (en) | ||
| CN106589215B (en) | Organic silicon modified polymethyl methacrylate and preparation method thereof | |
| JPH0254364B2 (en) | ||
| EP3947486A1 (en) | Impact resistant hydrophobic high heat optical acrylic copolymers | |
| EP3947485A1 (en) | Hydrophobic high heat optical acrylic copolymers | |
| CN113698527B (en) | Transparent flame-retardant PMMA resin and preparation method thereof | |
| EP0097948B1 (en) | Information recording substrate | |
| CN108359061B (en) | Graft copolymer containing acid anhydride group and preparation method and application thereof | |
| KR101211341B1 (en) | Thermoplastic resin | |
| JP4519421B2 (en) | Resin composition and vehicle lamp lens using the same | |
| JP3215719B2 (en) | Polymer composition | |
| CN1171917C (en) | Polymethyl methacrylate as molding material and its prepn | |
| JPS58455B2 (en) | Method for manufacturing solvent-resistant acrylic resin | |
| JPH0246605B2 (en) | ||
| CN113527606B (en) | Antifogging polymethyl methacrylate and preparation method thereof | |
| KR100587649B1 (en) | Continous Polymerization Process of Rubber-Modified Styrenic Resin with Super High Impact Property | |
| JPH0662694B2 (en) | Method for producing copolymer having excellent heat resistance | |
| JPS61141715A (en) | Heat-resistant copolymer resin, its production and optical element comprising the same | |
| CN114957626B (en) | Acid-alcohol modified thermoplastic acrylic copolymer and preparation method thereof | |
| CN112795164B (en) | PC/PBA alloy material and preparation method thereof | |
| CN115703863B (en) | Flame-retardant acrylate rubber and preparation method and application thereof | |
| CN114456303A (en) | Methyl methacrylate terpolymer and preparation method and application thereof | |
| JPH0425303B2 (en) | ||
| JP3434050B2 (en) | Method for producing methacrylic polymer | |
| CN114479331A (en) | Preparation method of antibacterial flame-retardant acrylic bathroom panel |
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 |