CN112225839B - Method for synthesizing ultra-high molecular weight polymethyl methacrylate - Google Patents
Method for synthesizing ultra-high molecular weight polymethyl methacrylate Download PDFInfo
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- CN112225839B CN112225839B CN202011000833.XA CN202011000833A CN112225839B CN 112225839 B CN112225839 B CN 112225839B CN 202011000833 A CN202011000833 A CN 202011000833A CN 112225839 B CN112225839 B CN 112225839B
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- 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
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
- C08F2/02—Polymerisation in bulk
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/69—Chromium, molybdenum, tungsten or compounds thereof
Abstract
A method for synthesizing ultra-high molecular weight polymethyl methacrylate (PMMA): mixing 28320-188800 parts by weight of methyl methacrylate, 1-53 parts by weight of a metal carbonyl catalyst and 20-277 parts by weight of an organic bromide initiator uniformly, reacting for 10-48 h under the protection of inert gas at 75-85 ℃, and then carrying out post-treatment to obtain the ultrahigh molecular weight PMMA; the polymerization reaction has the advantages of simple process, high product purity, colorless and transparent product and the like, and the molecular weight of PMMA obtained by polymerization is larger than 1.0 multiplied by 106And D, dalton.
Description
Technical Field
The invention belongs to the field of preparation of polymethyl methacrylate (PMMA) polymer materials, and relates to a novel method for preparing PMMA with ultrahigh molecular weight by initiating a bulk polymerization reaction of Methyl Methacrylate (MMA) monomers by organic bromides under the catalytic action of carbonyl metal.
Background
Polymethyl methacrylate (PMMA) is obtained by performing addition polymerization reaction on methyl Methacrylate Monomer (MMA), is commonly called organic glass, is an important thermoplastic organic polymer, and has the characteristics of light weight, toughness, high light transmittance, good processability and the like. The common PMMA has poor heat resistance, wear resistance and organic solvent resistance, low use temperature, easy surface roughening, low impact resistance and poor creep resistance, and can cause stress cracking under the action of long-time heavy load, thereby limiting the application range of the PMMA.
The characteristics of PMMA such as heat resistance, wear resistance and room temperature creep resistance are enhanced along with the increase of the molecular weight of PMMA, and the PMMA with ultrahigh molecular weight (the molecular weight is more than 100 ten thousand) can also keep certain mechanical strength at the high temperature of 200 ℃. The PMMA with the ultra-high molecular weight also has strong toughness, wear resistance, impact resistance, good electrical insulation, excellent arc resistance, weather resistance and the like, so that the PMMA with the ultra-high molecular weight has very wide application prospect in a plurality of fields such as aviation, aerospace, military, medicine, sanitation, automobiles, buildings and the like.
At present, the synthesis methods of the PMMA with the ultra-high molecular weight mainly comprise free radical emulsion polymerization, free radical suspension polymerization and low-temperature plasma polymerization. Suspension polymerization and emulsion polymerization can produce a large amount of waste water containing suspending agent and emulsifier in the production process, thereby bringing environmental protection problems, the post-treatment cost is high, and the polymer product has poor transparency and low purity due to the suspending agent and the emulsifier. The low-temperature plasma polymerization has the problems of unknown reaction mechanism, high-power radio frequency equipment required for production, difficult industrialization, long reaction time consumption, low production efficiency, complex structure of a polymerization product and the like.
Disclosure of Invention
The invention provides a novel method for preparing ultra-high molecular weight polymethyl methacrylate (PMMA) by initiating the bulk polymerization reaction of Methyl Methacrylate (MMA) through carbonyl metal catalysis and organic bromide.
The technical scheme of the invention is as follows:
a synthetic method of PMMA with ultra-high molecular weight comprises the following steps:
mixing 28320-188800 parts by weight of methyl methacrylate, 1-53 parts by weight of a metal carbonyl catalyst and 20-277 parts by weight of an organic bromide initiator uniformly, reacting for 10-48 h (preferably 24h) under the protection of inert gas at 75-85 ℃, and then carrying out post-treatment to obtain the PMMA with the ultrahigh molecular weight;
the metal carbonyl catalyst is molybdenum hexacarbonyl or chromium hexacarbonyl;
the organic bromide initiator is 2-bromoisobutyric acid ethyl ester, alpha-bromobenzene acetic acid or 2-bromopropionic acid ethyl ester;
the inert gas is one or more of nitrogen, argon, helium and neon;
the post-treatment may be carried out by conventional means known in the art, for example: after the reaction is finished, taking out the reactant, and carrying out vacuum drying at 60 ℃ to obtain a final product;
the polymerization product PMMA prepared according to the process of the invention has a molecular weight of 1.0X 106～6.8×106Dalton, preferably molecular weight of 3.0X 10 6～5.0×106And D, dalton.
The invention has the beneficial effects that: provide aA novel method for preparing PMMA with ultrahigh molecular weight by using a trace amount of carbonyl metal as a catalyst and initiating MMA bulk polymerization reaction by using an organic bromide. The polymerization reaction has the advantages of simple process, high product purity, colorless and transparent product and the like, and the PMMA obtained by polymerization has ultrahigh molecular weight (the molecular weight is more than 1.0 multiplied by 10)6Daltons).
Detailed Description
The invention is further described below by means of specific examples, without restricting its scope to these.
The materials, instrumentation and test characterization methods used in the practice were as follows.
Reagent materials: methyl methacrylate (99%, aladin), molybdenum hexacarbonyl (98%, Macklin), chromium hexacarbonyl (99%, aladin), ethyl 2-bromoisobutyrate (98%, Sigma-Aldrich), alpha-bromophenylacetic acid 97%, aladin), ethyl 2-bromopropionate (98%, aladin).
Molecular weight test method of polymethyl methacrylate: the number average molecular weight (M) of PMMA was determined using a Markov Viscotek 270Max Gel Permeation Chromatograph (GPC) systemn) Weight average molecular weight (M)w) And molecular weight distribution polydispersity index PDI (PDI ═ M)w/Mn). The system was configured with a Viscotek VE1122 solvent transport unit, a Viscotek VE 3580 refractive index detector, a Viscotek 270 laser light scattering-differential viscometer dual detector, a Viscotek VE2585 column oven, and a Viscotek T6000M GPC column. And (3) testing conditions are as follows: mobile phase, tetrahydrofuran; column temperature, 35 ℃; flow rate of mobile phase: 1.0 mL/min.
Method for testing the conversion rate of polymethyl methacrylate: the reaction conversion of polymethyl methacrylate was measured using a Bruker Avance III500MHz NMR spectrometer. And (3) testing conditions: deuterated reagent CDCl3(ii) a Internal standard: tetramethylsilane (TMS); and (3) testing temperature: and (4) room temperature.
Example 1
The raw material composition formula of the polymerization reaction is as follows: methyl methacrylate: 2.832 g; chromium hexacarbonyl: 5.0 mg; ethyl 2-bromoisobutyrate: 13.5 mg.
According to the formula, methyl methacrylate, chromium hexacarbonyl and ethyl 2-bromoisobutyrate are uniformly mixed, the mixture is reacted for 23 hours under the conditions of inert gas protection and 80 ℃, and after the reaction is finished, reactants are taken out and dried in vacuum at the temperature of 60 ℃ to obtain the ultra-high molecular weight polymethyl methacrylate.
The test characterization results show that: the conversion of the polymerization reaction was 78.0%. The number average molecular weight of the PMMA polymer was 141 ten thousand, the weight average molecular weight was 551 ten thousand, and PDI was 3.91.
Example 2
The synthesis method is the same as example 1. The raw material composition formula of the polymerization reaction is as follows: methyl methacrylate: 2.832 g; molybdenum hexacarbonyl: 1.0 mg; ethyl 2-bromopropionate: 12.2 mg; reaction temperature: 80 ℃; reaction time: for 21 hours.
The test characterization results show that: the conversion of the polymerization reaction was 54.1%. The number average molecular weight of the PMMA polymer was 134 ten thousand, the weight average molecular weight was 322 ten thousand, and PDI was 2.40.
Example 3
The synthesis method is the same as example 1. The raw material composition formula of the polymerization reaction is as follows: methyl methacrylate: 18.880 g; molybdenum hexacarbonyl: 3.0 mg; ethyl 2-bromoisobutyrate: 2.7 mg; reaction temperature: 80 ℃; reaction time: for 24 hours.
The test characterization results show that: the conversion of the polymerization reaction was 70.3%. The number average molecular weight of the PMMA polymer was 388 ten thousand, the weight average molecular weight was 1407 ten thousand, and PDI was 3.63.
Example 4
The synthesis method is the same as example 1. The raw material composition formula of the polymerization reaction is as follows: methyl methacrylate: 18.880 g; molybdenum hexacarbonyl: 0.3 mg; ethyl 2-bromoisobutyrate: 6.8 mg; reaction temperature: 80 ℃; reaction time: for 48 hours.
The test characterization results show that: the conversion of the polymerization reaction was 47.2%. The PMMA polymer had a number average molecular weight of 675 ten thousand, a weight average molecular weight of 2316 ten thousand, and PDI of 3.43.
Example 5
The synthesis method is the same as example 1. The raw material composition formula of the polymerization reaction is as follows: methyl methacrylate: 9.440 g; molybdenum hexacarbonyl: 5.3 mg; ethyl 2-bromoisobutyrate: 27.7 mg; reaction temperature: 80 ℃; reaction time: for 10 hours.
The test characterization results show that: the conversion of the polymerization reaction was 57.0%. The number average molecular weight of the PMMA polymer was 264 ten thousand, the weight average molecular weight was 832 ten thousand, and PDI was 3.15.
Example 6
The synthesis method is the same as example 1. The raw material composition formula of the polymerization reaction is as follows: methyl methacrylate: 9.440 g; molybdenum hexacarbonyl: 0.5 mg; α -bromophenylacetic acid: 3.0 mg; reaction temperature: 80 ℃; reaction time: for 24 hours.
The test characterization results show that: the conversion of the polymerization reaction was 95.8%. The number average molecular weight of the PMMA polymer was 102 ten thousand, the weight average molecular weight was 430 ten thousand, and PDI was 4.22.
Example 7
The synthesis method is the same as example 1. The raw material composition formula of the polymerization reaction is as follows: methyl methacrylate: 9.440 g; molybdenum hexacarbonyl: 0.3 mg; α -bromophenylacetic acid: 2.0 mg; reaction temperature: 80 ℃; reaction time: for 24 hours.
The test characterization results show that: the conversion of the polymerization reaction was 56.3%. The number-average molecular weight of the PMMA polymer was 269 ten thousand, the weight-average molecular weight was 1188 ten thousand, and PDI was 4.42.
Comparative example
(novel chemical materials, 2007,35 (12): 42-43) and MgCO using polyvinylpyrrolidone and polyvinyl alcohol as dispersing agents for suspension polymerization3The powder was used as a suspension polymerization protectant and peroxide was used as an initiator to prepare polymethyl methacrylate having a viscosity average molecular weight of 20 to 150 ten thousand by suspension polymerization (methyl methacrylate: water in a mass ratio of 1: 5) at a reaction temperature of 65 to 70 ℃ with a monomer conversion of about 80%. The polymerization reaction system only accounts for 16.6 percent of methyl methacrylate, the production efficiency is low, the maximum molecular weight of the obtained methyl methacrylate polymer is only 150 ten thousand, and the polymer contains impurities such as a dispersing agent, a protective agent and the like.
Claims (2)
1. A synthetic method of ultra-high molecular weight polymethyl methacrylate is characterized by comprising the following steps:
28320-188800 parts by weight of methyl methacrylate, 1-53 parts by weight of a metal carbonyl catalyst and 20-277 parts by weight of an organic bromide initiator are uniformly mixed, and the mixture is reacted for 10-48 hours under the protection of inert gas at 75-85 ℃, and then post-treated to obtain the ultrahigh molecular weight polymethyl methacrylate;
the metal carbonyl catalyst is molybdenum hexacarbonyl or chromium hexacarbonyl;
the organic bromide initiator is 2-bromoisobutyric acid ethyl ester, alpha-bromobenzene acetic acid or 2-bromopropionic acid ethyl ester;
the molecular weight of the ultra-high molecular weight polymethyl methacrylate is between 1.0 and 106～6.8×106And D, dalton.
2. The method for synthesizing ultra-high molecular weight polymethyl methacrylate according to claim 1, wherein the reaction time is 24 hours.
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| CN112940160B (en) * | 2021-03-03 | 2022-09-27 | 威海金合思化工有限公司 | Method for synthesizing ultra-high molecular weight polymethyl methacrylate |
| CN114262400B (en) * | 2022-01-24 | 2023-04-07 | 长春市兆兴新材料技术有限责任公司 | Linear controllable ultrahigh molecular weight poly (alkyl methacrylate) and synthesis method thereof |
| CN115746185B (en) * | 2022-12-13 | 2024-04-26 | 丽水学院 | Preparation method of polymethyl methacrylate with ultrahigh molecular weight |
Citations (5)
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|---|---|---|---|---|
| GB877109A (en) * | 1957-02-04 | 1961-09-13 | Montedison Spa | Process for the production of chromium hexacarbonyl |
| US4051172A (en) * | 1971-01-08 | 1977-09-27 | Institut Francais Du Petrole, Des Carburants Et Lubrifiants | Molybdenum and tungsten compounds, their manufacture and their use as catalysts in the stereospecific polymerization of unsaturated organic compounds |
| BE886452A (en) * | 1979-12-03 | 1981-06-02 | Dow Corning | OXYGEN CURABLE COMPOSITIONS CATALYZED BY METAL-CARBONYL COMPOUNDS |
| WO1981001558A1 (en) * | 1979-12-03 | 1981-06-11 | Dow Corning | Oxygen-curable mercapto-functional organic compound compositions catalyzed by metal carbonyl compounds and method of forming higher molecular weight products therefrom |
| CN1050028A (en) * | 1989-09-04 | 1991-03-20 | 英国石油化学品有限公司 | Contain the chromic compound polymerizing catalyst |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB877109A (en) * | 1957-02-04 | 1961-09-13 | Montedison Spa | Process for the production of chromium hexacarbonyl |
| US4051172A (en) * | 1971-01-08 | 1977-09-27 | Institut Francais Du Petrole, Des Carburants Et Lubrifiants | Molybdenum and tungsten compounds, their manufacture and their use as catalysts in the stereospecific polymerization of unsaturated organic compounds |
| BE886452A (en) * | 1979-12-03 | 1981-06-02 | Dow Corning | OXYGEN CURABLE COMPOSITIONS CATALYZED BY METAL-CARBONYL COMPOUNDS |
| WO1981001558A1 (en) * | 1979-12-03 | 1981-06-11 | Dow Corning | Oxygen-curable mercapto-functional organic compound compositions catalyzed by metal carbonyl compounds and method of forming higher molecular weight products therefrom |
| CN1050028A (en) * | 1989-09-04 | 1991-03-20 | 英国石油化学品有限公司 | Contain the chromic compound polymerizing catalyst |
Non-Patent Citations (2)
| Title |
|---|
| MMA的原子转移自由基聚合新体系;阎庆玲等;《弹性体》(第01期);全文 * |
| 超高相对分子质量聚(甲基)丙烯酸酯的制备及应用;刘易成等;《化工生产与技术》;20151225(第06期);全文 * |
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