CN101724120B - Preparation method of (methyl) acrylic polymer - Google Patents
Preparation method of (methyl) acrylic polymer Download PDFInfo
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- CN101724120B CN101724120B CN2008102248260A CN200810224826A CN101724120B CN 101724120 B CN101724120 B CN 101724120B CN 2008102248260 A CN2008102248260 A CN 2008102248260A CN 200810224826 A CN200810224826 A CN 200810224826A CN 101724120 B CN101724120 B CN 101724120B
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Abstract
The invention relates to a preparation method of (methyl) acrylic polymer, comprising the following steps of: adopting a serial circulating pipe type reactor, a straight pipe type reactor and a vented-type extruder, and/or adding styrene monomer to initiate the polymerization of (methyl) acrylic monomer to obtain (methyl) acrylic acid methyl ester homopolymer, copolymer containing (methyl) acrylic acid methyl ester and (methyl) acrylic acid alkyl ester or (methyl) acrylic acid alkyl ester homopolymer; wherein in the circulating pipe type reactor, the polymerization temperature is 140-160 DEG C, the material circulating velocity is 30-100 times of the feeding velocity, and the polymer content is controlled to 35-50 percent; in the straight pipe type reactor, the polymer content is controlled within the range of 40-80 percent; and in the vented extruder, volatile substances are removed at the temperature of 200-240 DEG C and the pressure of 50-300mmHg. The preparation method can control the continuous polymerization process and the devolatilization of the system stably and prepares the polymer which is excellent in performance, colorless and transparent and has the light transmittance up to 90-92 percent.
Description
Technical field:
The present invention relates to a kind of method of continuous bulk polymerization method preparation (methyl) acrylic polymer, can stably prepare purified (methyl) esters of acrylic acid moulding compound product by this method.
Background technology:
(methyl) acrylic polymer (being called PMMA) is widely used in fields such as the splinter-proof glass of various illuminating equipments, optical element, various instrument dial plate, case, scale card, Commdity advertisement show window, billboard, aircraft cockpit glass, aircraft and automobile, various medical, military glass as the transparent material of excellent performance more.In recent years, PMMA is widely used in the above-mentioned field except replacing glass, and various extraordinary PMMA obtain increasing the application in fields such as medicine, architectural shape, communication, electronic apparatuss, and become the focus of investment.
On polymerization technique, though the suspension polymerization technique maturation, it is convenient to change kind, is that maximum traditional technologys is adopted in countries in the world.But contain more impurity in the polymkeric substance because the adding of auxiliary agents such as suspension dispersive agent makes, cause degradation such as printing opacity, Application Areas is restricted.In addition, owing to numerous and diverse operations such as manufacturing processed needs to filter, washs, drying reduce productivity.And that the principal feature of continuous bulk polymerization is production serialization, quality product height, production technology advanced person, product is pure, can make the transmittance height, have (methyl) acrylic acid polymer of excellent properties.
Japanese patent gazette NO.32665/1977 discloses a kind of continuous bulk polymerization method, wherein uses a kind of tank reactor, carries out homogeneous reaction under the low situation of monomer conversion, and separates continuously and remove unreacted monomer.In the method, residual in the polymerization system have a large amount of unreacted monomers, in order to recycle unreacted monomer and refining resulting polymers, needs to consume big energy in the devolatilization operation.
Japanese patent gazette NO.7845/1980 provides a kind of benzene or alkylbenzene as the solution polymerization process of solvent, can realize the stable polymerization reaction under the higher relatively monomer conversion.But, in last handling process, remove these volatile matters and will consume lot of energy owing to use a large amount of solvents.In addition, the residual solvent in the polymkeric substance will damage the heat-resisting degradation property of polymkeric substance, reduce the purity of polymkeric substance.
In order to reduce solvent load, the preparation purified polymer realizes the stable polymerization reaction under the relative higher conversion simultaneously again, and it is the solution polymerization process of solvent that MIT discloses in CN1106026 with methyl alcohol.Set forth the some advantages of methyl alcohol as solvent in the patent: methyl alcohol has high volatile volatile, is easy to separate from polymerisate; Little in sticking of polymeric kettle internal surface, agitator and tubing system internal surface; Can reduce the painted of polymkeric substance; Under same concentrations, adopt methyl alcohol to make system viscosity lower as solvent, help suppressing the generation of gel effect in the bulk polymerisation process.But methyl alcohol has also brought difficulty to the Separation and Recovery operation after the devolatilization as the introducing of solvent.Reclaim to contain in the liquid and be reaction monomers and methyl alcohol as main body, also contain other impurity, for example the formaldehyde of by product that is come by monomer derived such as oligopolymer, methanol oxidation generation, superoxide are as main peroxyformic acid that is come by formaldehyde-derived and unreacted chain-transfer agent etc.In the separation and recovery method that provides,, in tower, introduce minor amounts of oxygen in order to prevent unreacted monomer polymerization in distillation tower.Meanwhile also to discharge the gas that contains oxygen, the formaldehyde that forms to prevent methanol oxidation deposition by the condenser of cat head.Also in tower, add antioxidant, to prevent the formation of monomer polymerization and some superoxide.In the Separation and Recovery process, need to increase many operations, consider it is disadvantageous from the economy angle of producing.
In disclosed patent, no matter be to adopt mass polymerization or solution polymerization process prepares acrylic polymer, all cause free radical reaction and realize by in polymerization system, adding initiator.Yet, the use of radical initiator also can bring negative influence to polymer properties, to increase the polymer ends double bond content as radical initiator, residual initiator can reduce the heat-resisting degradation property of polymkeric substance, also can be in the transparency that influences product in varying degrees.Especially mention in some patents, under the lower situation of polymer solids level, stop polyreaction, enter the devolatilization treatment process.Remaining initiator can continue initiated polymerization in the devolatilization process, generate a large amount of dipolymers, and the increase of dipolymer causes the transparency of polymkeric substance, resistance toheat to descend the color and luster of impact polymer.
Summary of the invention:
The purpose of this invention is to provide a kind of employing series circulation tubular reactor, straight tubular reactor and vented extruder device, add vi-ny l aromatic monomers, cause the polymerization of (methyl) acrylic ester monomer, obtain the preparation method of (methyl) methyl acrylate polymer of (methyl) acrylic polymer.
The present invention adopts series circulation tubular reactor, straight tubular reactor and vented extruder device, by adding the vi-ny l aromatic monomers alternative initiator of easy formation hot radical, causes the polymerization of (methyl) acrylic ester monomer.
Step is as follows:
(1) at first by charging into nitrogen, dissolved oxygen level in (methyl) acrylic ester monomer or its mixture is reduced to 1-3ppm;
(2) in the circulation tubular reactor, supply with the vi-ny l aromatic monomers of the easy formation hot radical contain (methyl) methyl acrylate that accounts for monomer weight 90-99.9 quality %, the monomer that contains methyl methacrylate and alkyl acrylate or alkyl methacrylate (except that methyl methacrylate) and/or 0.1-10 quality % continuously, polymerization temperature is controlled in the 140-160 ℃ of scope, and polymer content is controlled at 35-50%;
(3) reaction mass is sent into continuously further polymerization in the tubular reactor, its temperature is set in the 140-160 ℃ of scope, polymer content is brought up to 40-80%;
(4) reaction mixture that obtains is delivered in the vented extruder, separated continuously at this and remove volatile matter.
Preferred (methyl) methacrylate monomer is as main monomer in multiple (methyl) acrylic ester monomer, and the content in monomer mixture is 90-100 quality %.
The monomer of described easy formation hot radical is selected vinylbenzene for use, and its content is in 0-10 quality % scope.
In the described circulation tubular reactor, control material cycle rate is the 30-100 scope doubly of feeding rate.
In this patent, as (methyl) acrylic ester monomer, have no particular limits, for example can use to have carbonatoms (methyl) alkyl acrylate, as (methyl) methyl acrylate, (methyl) ethyl propenoate as the alkyl of 1-8.(methyl) vinylformic acid n-propyl, (methyl) n-butyl acrylate, (methyl) 2-EHA etc.These (methyl) acrylic ester monomers may be used alone, can also be used in combination.It is that main monomer carries out polymerization that this patent is selected with the methyl methacrylate.
In this patent, monomer remained in 5-20 ℃ the head tank preferred 10-15 ℃ of scope before entering the circulation tubular reactor.The existence that is dissolved in the oxygen in the raw material can cause the change and the product variable color of transformation efficiency, especially works as polymer application in optical articles.In this patent, rare gas element (for example nitrogen) is introduced in (methyl) acrylic ester monomer mixture, the content of dissolved oxygen is reduced to 2ppm or lower.Before polyreaction, in the circulation tubular reactor, feed nitrogen and replace, in reactor, supply with monomer mixture solution again.
For the molecular weight of telomerized polymer, also can use chain-transfer agent.The mercaptan compound that is used for this patent can be selected from the mercaptan of 3-18 carbon atom, comprise the alkyl group that has alkyl group or replacement primary, the second month in a season and uncle's mercaptan, as normal-butyl mercaptan, isobutyl-mercaptan, n-octyl mercaptan, uncle's lauryl mercaptan, sec-butyl mercaptan, secondary lauryl mercaptan and tert-butyl mercaptan; Aryl mercaptan, as phenyl mercaptan, the thiocresol and the 4-tertiary butyl, o-toluene thiophenol; And THIOGLYCOL.Spendable chain-transfer agent comprises normal-butyl mercaptan, isobutyl-mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, uncle's lauryl mercaptan and tert-butyl mercaptan.Chain-transfer agent can use separately, or two or more are used in combination.In these mercaptan, be more preferably and use tert-butyl mercaptan, normal-butyl mercaptan, n-octyl mercaptan and uncle's lauryl mercaptan.What this patent was selected for use is uncle's lauryl mercaptan.The consumption of the mercaptan that uses as chain-transfer agent in this patent is in the 0.01-1.0mol% scope.When its consumption was less than 0.01mol%, molecular weight can't be effectively controlled, and caused polymerization system viscosity excessive, can't stablize and carry out.The mercaptan consumption is excessive, and the polymer polymerizing that obtains is spent low, causes the polymer machinery degradation.In addition, add too much mercaptan, cause burden for the Separation and Recovery operation, the residual meeting of mercaptan in polymkeric substance causes problems such as product is painted.
The polymerizing reactor of this patent adopts the mode of two kinds of reactors in series, i.e. straight tubular reactor of a circulation tubular type reactors in series.The circulation tubular reactor mainly is made of the ring main road of a sealing, and the cross section of endless tube is circular and uniform structure.During the reactor operation, material is full of endless tube, and the mixture of reaction is promoted to flow in the endless tube high speed by the high-speed gear pump, and making everywhere, material reaches thorough mixing.The circulation tubular reactor has chuck, by thermal oil reactor temperature is mediated in the chuck.With respect to tank reactor, the circulation tubular reactor has increased the heat transfer area of polymerization system, can effectively remove reaction heat, stablizes hierarchy of control temperature and viscosity.In addition,, reach uniform admixture, help forming the polymkeric substance of homogeneous component, obtain the product of excellent performance by the high speed circulation of material in the circulation tubular reactor.Material carries out the initial stage polymerization in the circulation tubular reactor, when polymerization system reaches certain polymerisation conversion, by toothed gear pump material is sent into the further polymerization of straight tubular reactor continuously, improves polymerisation conversion.In straight tubular reactor, the mixed with polymers system is mixed effectively stable mass transfer and the heat transfer of guarantee system by the interior static mixer of establishing.
Polymerization temperature is a polymerization factor very important in this patent, because this patent is by thermal-initiated polymerization reaction, so the polymerization temperature of whole polymerization process will be controlled in 140-170 ℃ the high temperature range.Do not require in the circulation tubular reactor polymerization temperature always with straight tubular reactor in identical.When polymerization temperature was lower than 140 ℃, cinnamic thermal initiation efficient reduced, and the rate of polymerization of system is very low, influences carrying out smoothly of polymerization process.In addition, when reaction reached certain transformation efficiency, system concentration increased gradually, can't guarantee the steady running of polymeric system.When polymerization temperature surpasses 170 ℃, though system viscosity can further reduce, help stable operation, will generate a large amount of oligopolymer in the polymerization system, the molecular weight distribution of polymkeric substance is broadened, cause corresponding mechanical property, optical property to descend.On the other hand, along with the rising working pressure of temperature is also wanted corresponding increase, the manufacturing cost of reactor increases, and is disadvantageous for the Financial cost of producing.
The polymer content of final controlled polymerization system is in the 50-80% scope in the reactor.When polymer concentration is lower than 50%, the load that reclaims the volatile matter operation will be increased.When polymer content surpassed 80%, polymerization system viscosity was too high, for stable control reaction brings difficulty.In addition, polymer content is too high, and system can't uniform mixing, causes molecular weight distribution to broaden, thus the impact polymer performance.So will in the polymer content scope that is fit to, carry out polymerization.
In this patent, for the polymkeric substance of the molecular weight that reaches higher polymerisation conversion and be fit to, the mean residence time in the circulation tubular reactor remains in 2-6 hour scope, preferred 4-5 hour.Polymerization time is too short, reacts insufficient, can not get the polymkeric substance of enough molecular weight, is difficult to satisfy the mechanical property requirements of product.Polymerization time is long, not only causes production efficiency to descend, and will generate too much dipolymer, especially reacts for high temperature polymerization.In tubular reactor, polymerization time is controlled in 10-60 minute scope, is more preferably 20-40 minute.
In this patent, the polymeric blends that adopts vented extruder that reaction is finished carries out continuous devolatilization to be handled.The number of outlet orifice has no particular limits, but considers that from the angle of volatilization effect and operating cost the forcing machine device with 2-4 outlet orifice is suitable.The devolatilization forcing machine that uses in this patent is the different temperature province of branch plurality of sections between each outlet orifice, and whole devolatilization temperature is controlled in the 200-240 ℃ of scope.Carrying out polymerisate devolatilization process under comparatively high temps will finish in setting-up time, to prevent polymerisate generation thermal destruction or to form more oligopolymer.Enter behind the forcing machine through every section regional temperature raise gradually.And each outlet orifice is controlled at respectively under the different vacuum degree condition.Each venting port near devolatilization outlet of extruder place keeps higher vacuum tightness.Wherein pressure remains on 50-300mmHg, is more preferably 80-200mmHg, and most of volatile substances is removed by preceding several venting ports in the polymeric blends.In order to make polymkeric substance have good light transmittance, mechanical property and good mobility, the weight-average molecular weight of the polymkeric substance that obtains with this patent method is controlled at 50, and 000-15 is in 0000 scope.
Embodiment:
Embodiment 1
In having the material-compound tank of chuck, raw materials such as methyl methacrylate, vinylbenzene and uncle's lauryl mercaptan are tentatively mixed, send into tundish more temporarily to store, to guarantee the fixed inlet amount.The polymerization single polymerization monomer mixing solutions is remained under 10 ℃ of conditions.The composition of mixing solutions is: 95 parts of methyl methacrylates, 5 parts of vinylbenzene and 0.05 part of uncle's lauryl mercaptan (being equivalent to polymerization single polymerization monomer total amount).Charge into nitrogen (passing through nitrogen system) in material-compound tank and tundish, remove the oxygen of sneaking in the monomer mixture solution, control oxygen level wherein is at 2ppm.Reactor also will be replaced discharge oxygen with nitrogen before feeding monomer.Feed monomer in the circulation tubular reactor by the speed of volume pump with 1.2kg/h, material circulates in reactor by recycle pump, and the material cycle rate is controlled to be 80:1 with the ratio of feeding rate.Polymerization temperature in the circulation tubular reactor is 150 ℃.Reach 45.7% to polymerisation conversion, be delivered in the straight tubular reactor of series connection with it by the polyblend of toothed gear pump with circulation tubular type reactor bottom, the polymerization temperature in the straight tubular reactor is 150 ℃.When polymerisation conversion reaches 75.5%, polymeric blends sent into carry out devolatilization in the vented extruder and separate, divide differing temps regional control temperature in the forcing machine in 200-230 ℃ of scope.The volatiles of collecting in a plurality of venting ports of forcing machine carries out Separation and Recovery through recovery system, and the unreacted monomer that obtains is sent into recycle in the material-compound tank.Above-mentioned polymerizing condition and test result are listed in the table 1.The result shows, cinnamic introducing has caused the Polymerization of Methyl reaction effectively, and suppressed the generation of inherent gel effect in the MMA polymerization process effectively, polyreaction has been stablized carried out, can access water white transparency polymkeric substance with excellent properties.
Embodiment 2
Use the method identical with embodiment 1, different is has adjusted the ratio of the ratio of polymerization single polymerization monomer and recycle stock and feeding rate.The composition of mixing solutions is: 90 parts of methyl methacrylates, 10 parts of vinylbenzene and 0.05 part of uncle's lauryl mercaptan.Control material cycle rate is 40:1 with the ratio of feeding rate in the circulation tubular reactor, and polymerization temperature is 150 ℃.Polymerisation conversion in circulation tubular reactor and the straight tubular reactor is respectively 47.3% and 77.1%.Question response finishes, and polymeric blends is sent into carried out the devolatilization separation in the vented extruder.Polymerizing condition and test result are listed in the table 1.Can stablize the continuous polymerization process and the devolatilization operation of the hierarchy of control with this understanding, obtain the water white transparency polymkeric substance of excellent performance.
Embodiment 3
Use the method identical with embodiment 1, different is the polymerization temperature that has reduced system.After 95 parts of methyl methacrylates, 5 parts of vinylbenzene and 0.05 part of uncle's lauryl mercaptan removed dissolved oxygen in the monomer through nitrogen, send in the circulation tubular reactor, polymerization temperature is 140 ℃.Control material cycle rate is 80:1 with the ratio of feeding rate in the circulation tubular reactor.Polymerisation conversion in circulation tubular reactor and the straight tubular reactor is respectively 38.1% and 58.7%.Question response finishes polymeric blends sent into and carries out devolatilization in the vented extruder and separate.Polymerizing condition and test result are listed in the table 1.Can stablize the continuous polymerization process and the devolatilization operation of the hierarchy of control with this understanding, obtain the water white transparency polymkeric substance of excellent performance.
Embodiment 4
Use the method identical with embodiment 1, different is has adjusted the ratio of the polymerization temperature of system and recycle stock and feeding rate.After 95 parts of methyl methacrylates, 5 parts of vinylbenzene and 0.05 part of uncle's lauryl mercaptan removed dissolved oxygen in the monomer through nitrogen, send in the circulation tubular reactor, polymerization temperature is 155 ℃.Control material cycle rate is 100:1 with the ratio of feeding rate in the circulation tubular reactor.Polymerisation conversion in circulation tubular reactor and the straight tubular reactor is respectively 48% and 76.9%.Question response finishes, and polymeric blends is sent into carried out the devolatilization separation in the vented extruder.Polymerizing condition and test result are listed in the table 1.Can stablize the continuous polymerization process and the devolatilization operation of the hierarchy of control with this understanding, obtain the water white transparency polymkeric substance of excellent performance.
Embodiment 5
Use the method identical with embodiment 1, the composition of different is mixing solutions is: 90 parts of methyl methacrylates, 10 parts of vinylbenzene and 0.05 part of uncle's lauryl mercaptan.Control material cycle rate is 30:1 with the ratio of feeding rate in the circulation tubular reactor, and polymerization temperature is 160 ℃.Polymerisation conversion in circulation tubular reactor and the straight tubular reactor is respectively 50.0% and 77.5%.Question response finishes, and polymeric blends is sent into carried out the devolatilization separation in the vented extruder.Polymerizing condition and test result are listed in the table 1.Can stablize the continuous polymerization process and the devolatilization operation of the hierarchy of control with this understanding, obtain the water white transparency polymkeric substance of excellent performance.
Comparative example 1
Use the method identical with embodiment 1.Different is to be 100 parts of methyl methacrylates and 0.05 part of uncle's lauryl mercaptan in the monomer mixture solution.Polymerization temperature is 150 ℃, and the material cycle rate is controlled to be 100:1 with the ratio of feeding rate.Polymerisation conversion in circulation tubular reactor and the straight tubular reactor is respectively 30.4% and 43.5%.Polymerizing condition and test result are listed in the table 1.Test shows that the activity of MMA is very low, carries out polymerization by thermal initiation under the polymerizing condition of setting, and speed of reaction is slow, and polymerization reaction time is long, and the polymkeric substance transformation efficiency that obtains is low, is unfavorable for industrial production.
Comparative example 2
Use the method identical with embodiment 1.Different is to be 85 parts of methyl methacrylates, 15 parts of vinylbenzene and 0.05 part of uncle's lauryl mercaptan in the monomer mixture solution.Polymerization temperature is 160 ℃.The material cycle rate is controlled to be 80:1 with the ratio of feeding rate.Polymerisation conversion in circulation tubular reactor and the straight tubular reactor is respectively 52.0% and 76.0%.Polymerizing condition and test result are listed in the table 1.The increase of vinylbenzene add-on reduces rate of polymerization.In polyreaction, vinylbenzene adds as playing initiation, and its add-on is moderate.Preferred effective initiated polymerization can not reduce the amount of MMA rate of polymerization again too much.
Comparative example 3
Use the method identical with embodiment 1.Different is that monomer mixture solution consists of 95 parts of methyl methacrylates, 5 parts of vinylbenzene and 0.05 part of uncle's lauryl mercaptan.Polymerization temperature is 170 ℃, and the material cycle rate is controlled to be 40:1 with the ratio of feeding rate.Polymerisation conversion in circulation tubular reactor and the straight tubular reactor is respectively 43.0% and 73.1%.Polymerizing condition and test result are listed in the table 1.Improve the control that polymerization temperature helps the raising of speed of reaction and reduces system viscosity, polymericular weight is reduced, molecular weight distribution broadens, and light transmission decreases.
Comparative example 4
Use the method identical with embodiment 1.Different is to change the circulation tubular reactor into have chuck and stirring the tank reactor of mixing fully, connects with straight tubular reactor and carries out polyreaction.After 95 parts of methyl methacrylates, 5 parts of vinylbenzene and 0.05 part of uncle's lauryl mercaptan removed dissolved oxygen in the monomer through nitrogen, send into and mix fully in the tank reactor, polymerization temperature is 150 ℃.When polymerisation conversion reaches 43%, be delivered in the straight tubular reactor of series connection with it by the polyblend of toothed gear pump circulation tubular type reactor bottom, polymerization temperature is 150 ℃, and the control residence time is 30 minutes, and wherein polymerisation conversion reaches 73.1%.Question response finishes, and polymeric blends is sent into carried out the devolatilization separation in the vented extruder.Volatiles is through Separation and Recovery, with the unreacted monomer recycle that obtains.Polymerizing condition and test result are listed in the table 1.Mixing fully in the tank reactor, through 3 hours polymerization, system viscosity was significantly increased.Think because unfavorable system local superheating, the reaction rate accelerates of causing of heat and mass.The molecular weight distribution of the polymkeric substance that obtains broadens, and light transmission decreases.
Claims (1)
1. the preparation method of a methacrylate based polymers is characterized in that: adopt series circulation tubular reactor, straight tubular reactor and vented extruder;
Step is as follows:
(1) at first by charging into nitrogen, dissolved in the methyl methacrylate monomer is contained the oxygen quality reduce to 1-3ppm;
(2) in the circulation tubular reactor, supply with continuously and account for the methyl methacrylate monomer of monomer total mass 90-99.9% and the styrene monomer of 0.1-10%, polymerization temperature is controlled at 140-160 ℃, control material cycle rate is 30-100 a times of feeding rate, and polymer quality content is controlled at 35-50%;
(3) reaction mass is sent into continuously further polymerization in the tubular reactor, its temperature is set in 140-160 ℃, reaction time was controlled at 10-60 minute, and polymer quality content is brought up to 40-80%;
(4) reaction mixture that obtains is delivered in the vented extruder, the devolatilization temperature is controlled at 200-240 ℃ of scope, and pressure remains on 50-300mmHg, separates continuously and removes volatile matter;
The consumption of mercaptan is the 0.01-1.0% of monomer total mass.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102311518B (en) * | 2010-06-29 | 2013-09-04 | 中国石油天然气股份有限公司 | Method for preparing (methyl) acrylate polymer |
| CN102850481B (en) * | 2011-06-30 | 2014-04-02 | 中国石油天然气股份有限公司 | Preparation method for branched-structure (methyl) acrylate polymer |
| CN103539887A (en) * | 2012-07-12 | 2014-01-29 | 中国石油天然气股份有限公司 | Method for continuously preparing optical-grade polymethyl methacrylate |
| CN103172780A (en) * | 2013-03-23 | 2013-06-26 | 云南熙乐科技有限公司 | Process for synthesizing and processing solid acrylic resin |
| CN103497267A (en) * | 2013-09-04 | 2014-01-08 | 南京理工大学 | Narrow-distribution middle-low-molecular-weight sodium polyacrylate preparation method |
| CN104558388B (en) * | 2015-01-23 | 2017-01-18 | 湖州展望药业股份有限公司 | Continuous bulk polymerization method of medicinal polyacrylic resin |
| CN107556419B (en) * | 2017-09-08 | 2019-06-04 | 广东龙湖科技股份有限公司 | Continuous extrusion process prepares the method for water-based acrylic resin and realizes the production equipment of this method |
| CN110423304B (en) * | 2019-07-29 | 2021-10-15 | 成都优威易比应用技术有限公司 | Photo-thermal free radical polymerization preparation method and application of vinyl polymer |
| CN112979859A (en) * | 2019-12-16 | 2021-06-18 | 中国石油天然气股份有限公司 | (methyl) acrylate polymer, preparation method thereof and light guide plate |
| CN112011244B (en) * | 2020-09-02 | 2021-09-14 | 合肥工业大学 | Continuous production method of GMA acrylic resin powder coating |
| CN114989340A (en) * | 2022-06-28 | 2022-09-02 | 杭州双安科技有限公司 | Olefin polymerization method |
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| US4529787A (en) * | 1982-06-15 | 1985-07-16 | S. C. Johnson & Son, Inc. | Bulk polymerization process for preparing high solids and uniform copolymers |
| CN1102833A (en) * | 1993-11-05 | 1995-05-24 | 住友化学工业株式会社 | Process for production of methacrylate polymers |
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| US4529787A (en) * | 1982-06-15 | 1985-07-16 | S. C. Johnson & Son, Inc. | Bulk polymerization process for preparing high solids and uniform copolymers |
| US4529787B1 (en) * | 1982-06-15 | 1987-07-07 | ||
| CN1102833A (en) * | 1993-11-05 | 1995-05-24 | 住友化学工业株式会社 | Process for production of methacrylate polymers |
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