CN103539887A - Method for continuously preparing optical-grade polymethyl methacrylate - Google Patents
Method for continuously preparing optical-grade polymethyl methacrylate Download PDFInfo
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- CN103539887A CN103539887A CN201210241387.0A CN201210241387A CN103539887A CN 103539887 A CN103539887 A CN 103539887A CN 201210241387 A CN201210241387 A CN 201210241387A CN 103539887 A CN103539887 A CN 103539887A
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Abstract
The invention relates to a method for continuously preparing optical-grade polymethyl methacrylate. The method comprises the following steps of: continuously supplying (meth)acrylate monomer or the solution containing not more than 5% of inert solvent into a circulating tube type reactor for polymerization, wherein the polymerization temperature is controlled within the range of 130-160 DEG C and the polymer content is controlled within the range of 40-65%; continuously sending the reaction material into a heater for further polymerization, wherein the polymerization temperature is set within the range of 140-170 DEG C, and the content of the polymer is increased to 55-80%; sending the obtained reaction mixture into a devolatilization extruder to continuously remove a volatile substance by separation, wherein the ratio of material circulation rate to feeding rate inside the circulating tube type reactor is controlled within the range of 40:1-120:1. A highly-pervious pure polymethyl methacrylate molding compound product can be stably prepared by adopting the method provided by the invention.
Description
Technical field
The present invention relates to prepare by mass polymerization or solution polymerization the method for polymkeric substance.The continuous production that is particularly useful for optical-grade polymethylmethacrylacontinuous moulding compound.
Background technology
(methyl) acrylic polymer (being called PMMA) is widely used in the 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 except replacing glass to be widely used in above-mentioned field, and various extraordinary PMMA get more and more applications in fields such as medicine, architectural shape, communication, electronic apparatuss, and become the focus of investment.
On polymerization technique, although suspension polymerization technique is ripe, change kind convenient, owing to making to contain more impurity in polymkeric substance adding of the auxiliary agents such as suspension dispersive agent, cause the degradation such as printing opacity, Application Areas is restricted.In addition, because numerous and diverse operations such as manufacturing processed needs to filter, washs, is dried reduce productivity.So this technology is eliminated gradually.Continuous bulk polymerization is the optimum technology of producing (methyl) acrylic polymer.Its principal feature is production serialization, good product quality, production technology is advanced, product is pure, can make (methyl) acrylic acid polymer that transmittance is high, have excellent properties.But continuous bulk polymerization requires higher to polymerization unit and technology controlling and process.Solution polymerization has improved the control of polymerization technique by the introducing of solvent, be conducive to stable polymerization operation, but dissolvent residual can reduce the optical property of material, the key of this patent is to reduce as far as possible adding of solvent and the stable raising of controlling polyreaction and postorder devolatilization processing power.
Japanese patent gazette NO.32665/1977 discloses a kind of continuous bulk polymerization method, wherein uses a kind of tank reactor, in the lower situation of monomer conversion, carries out homogeneous reaction, and continuous separate from remove unreacted monomer.In the method, in polymerization system, remain a large amount of unreacted monomers, in order to recycle unreacted monomer and refining resulting polymers, in devolatilization operation, need lot of energy.
The eighties, U.S. PTI company proposed solution polymerization technique, by adding solvent to realize polyreaction steady running.As the polymerization process of US Patent No. 4728701 disclosed a kind of acrylate, US Patent No. 4933400 discloses a kind of continuous solution polymerization method of methyl methacrylate.This technique exists following shortcoming: the quantity of solvent ratio that polymerization process is used is up to 60% of inlet amount, and speed of reaction is excessively slow.Polymeric reaction temperature is lower than 100 ℃, uses relative the increasing of amount of initiator and molecular weight regulator, and it is residual will affect the purity of polymkeric substance, the load of increase refine and reclaim.Owing to adopting a large amount of solvents, in Devolatilization device, the low heats of the heat transfer coefficient of well heater is not good, causes well heater huge, polymeric solution therein the residence time long, easily produce oligopolymer, have a strong impact on quality product.
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 relatively high monomer conversion.But owing to using a large amount of solvents, in last handling process, remove these volatile matters and will consume a large amount of energy.In addition, the residual solvent in polymkeric substance, by the heat-resisting degradation property of infringement polymkeric substance, reduces the purity of polymkeric substance.
Summary of the invention
The object of the invention is to propose a kind of optical-grade polymethylmethacrylacontinuous method of continuous production, be particularly useful for the continuous production of optical-grade polymethylmethacrylacontinuous moulding compound.Adopt method and apparatus provided by the invention, can realize the steady running of continuous bulk polymerization, and reach higher polymerisation conversion, obtain high-quality moulding compound product.
The invention provides a kind of optical-grade polymethylmethacrylacontinuous method of continuous production, it is the solution polymerization of carrying out high temperature continuous bulk polymerization or add no more than 5% inert solvent in circulating tube type reactor, after reaching certain polymer content, polymer melt is delivered to well heater and makes it continue polymerization.Finally by devolatilization forcing machine, remove volatile matter, through tablets press, obtain moulding compound.The step that this method comprises is as follows: the oxygen level of dissolving in (methyl) acrylic ester monomer or its mixture is down to 1-3ppm; In circulating tube type reactor, supply with (methyl) acrylic ester monomer continuously, polymerization temperature is controlled within the scope of 130-160 ℃, and polymer content is controlled at 40-65%; Reaction mass is sent in well heater to further polymerization continuously, by its Temperature Setting within the scope of 140-170 ℃.Polymer content is brought up to 55-80%; The reaction mixture obtaining is delivered in devolatilization forcing machine, this continuously separation remove volatile matter.
In circulating tube type reactor of the present invention, control the ratio of Matter Transfer speed and feeding rate in the scope of 40:1～120:1.
Well heater of the present invention is in series by 3 sections of tubular unit with chuck built-in detachable static mixer.
Devolatilization forcing machine of the present invention is at least provided with four venting ports.One of them venting port is in the rear end of polymkeric substance inlet, and can carry out nitrogen purging, and its excess-three is located between inlet and extruder die head successively, and each venting port arranges different pressures.From inlet rear end to die head direction, the absolute pressure of each venting port is controlled within the scope of 100-150KPa, 40-100KPa, 10-30KPa and 0.5-20KPa successively.
In the preparation method of polymkeric substance of the present invention, residual monomer content is no more than 1000-3000ppm.
The weight-average molecular weight of the polymkeric substance that the inventive method obtains is controlled at 50,000-15, in 0000 scope, to meet polymer molding compounds, has good light transmission, mechanical property and good mobility.
In the present invention, as (methyl) acrylic ester monomer, have no particular limits, for example, can use (methyl) alkyl acrylate with the alkyl that carbonatoms is 1-8, as (methyl) methyl acrylate, (methyl) ethyl propenoate.(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.The present invention selects take methyl methacrylate to carry out polymerization as main monomer.
For the molecular weight of telomerized polymer, also can use chain-transfer agent.For mercaptan compound of the present invention, can be selected from the mercaptan of 3-18 carbon atom, comprise the primary, secondary and tertiary mercaptan with the alkyl group of alkyl group or replacement, as normal-butyl mercaptan, isobutyl-mercaptan, n-octyl mercaptan, tertiary lauryl mercaptan, sec-butyl mercaptan, secondary lauryl mercaptan and tert-butyl mercaptan; Aryl mercaptan, as phenyl mercaptan, 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, tertiary lauryl mercaptan and tert-butyl mercaptan.Chain-transfer agent can be used separately, or two or more are combined with.In these mercaptan, be more preferably and use tert-butyl mercaptan, normal-butyl mercaptan, n-octyl mercaptan and tertiary lauryl mercaptan.What the present invention selected is tertiary lauryl mercaptan.The consumption of the mercaptan using as chain-transfer agent is in the present invention within the scope of 0.01-1.0mol%.When its consumption is less than 0.01mol%, molecular weight cannot be effectively controlled, and causes polymerization system viscosity excessive, cannot stablize and carry out.Mercaptan consumption is excessive, and the polymer polymerizing obtaining is spent low, causes polymer machinery degradation.In addition, add too much mercaptan, cause burden to Separation and Recovery operation, the residual meeting of mercaptan in polymkeric substance causes the problems such as product is painted.
Employing of the present invention be circulating tube type reactor.Reactor mainly consists of the ring main road of a sealing, and the cross section of endless tube is circular and uniform structure.During reactor operation, material is full of endless tube, and the mixture of reaction is promoted to flow in endless tube high speed by high speed gear pump, makes material everywhere reach abundant mixing.Circulating tube type reactor, with chuck, is mediated to reactor temperature by thermal oil in chuck.With respect to tank reactor, circulating tube type reactor has increased the heat transfer area of polymerization system, can effectively remove reaction heat, stablizes hierarchy of control temperature and viscosity.In addition, the high-speed circulating by material in circulating tube type reactor, reaches uniform admixture, is conducive to form the polymkeric substance of homogeneous components, obtains the product of excellent performance.Material carries out initial stage polymerization in circulating tube type reactor, when polymerization system reaches certain polymerisation conversion, by toothed gear pump, material is sent into the further polymerization of well heater continuously, improves polymerisation conversion.The internal structure of well heater is in series by 3 sections of tubular unit with chuck built-in detachable static mixer, to mixed with polymers system, provides sufficient heat transfer condition, effectively stable mass transfer and the heat transfer of guarantee system.By the linking of well heater, be both conducive to improve the transformation efficiency of polymkeric substance in circulating tube type reactor, for entering vacuum volatilization system, polymkeric substance carries out preheating again.
Polymerization temperature is polymerization factor very important in the present invention, because the present invention reacts by thermal-initiated polymerization, so the polymerization temperature of whole polymerization process will be controlled in the high temperature range of l30～170 ℃.When polymerization temperature is during lower than l30 ℃, polymerization reaction time is longer, is uneconomic in industrial production.In addition, when reaction reaches certain transformation efficiency, system concentration increases gradually, cannot guarantee the steady running of polymeric system.When polymerization temperature surpasses 170 ℃, although system viscosity can further reduce, be conducive to stable operation, in polymerization system, by generating a large amount of oligopolymer, the molecular weight distribution of polymkeric substance is broadened, cause corresponding mechanical property, optical property to decline.On the other hand, along with the rising working pressure of temperature is also wanted corresponding increase, the manufacturing cost of reactor increases, and for the Financial cost of producing, is disadvantageous.
Control the final polymer content of polymerization system in 55～80% scopes.When polymer concentration is lower than 55% time, will increase the load that reclaims volatile matter operation.When polymer content surpasses 80%, polymerization system viscosity is too high, for stable control reaction brings difficulty.In addition, polymer content is too high, and system cannot evenly be mixed, and causes molecular weight distribution to broaden, thereby affects polymer performance.So will carry out polymerization within the scope of applicable polymer content.
In the present invention, in order to reach the polymkeric substance of higher polymerisation conversion and applicable molecular weight, the mean residence time in circulating tube type reactor remained within the scope of 1～4 hour, preferably 1.5～2 hours.Polymerization time is too short, reacts insufficient, can not get the polymkeric substance of enough molecular weight, is difficult to meet the mechanical property requirements of product.Polymerization time is long, not only causes production efficiency to decline, and by generating too much dipolymer, especially for high temperature polymerization, reacts.In preheater, polymerization time was controlled within the scope of 10～40 minutes, was more preferably 15～25 minutes.
In the present invention, adopt devolatilization forcing machine to carry out continuous devolatilization processing to reacting complete polymeric blends.From the angle of volatilization effect and operating cost, consider, the forcing machine device with 2-4 outlet orifice is suitable.The devolatilization forcing machine using in the present invention is minute some sections of different temperature provinces between each outlet orifice, and whole devolatilization temperature is controlled within the scope of 200～220 ℃.Under comparatively high temps, carrying out polymerisate devolatilization process will complete in setting-up time, to prevent polymerisate generation thermal destruction or to form more oligopolymer.Enter after forcing machine through every section of regional temperature raise gradually, and each outlet orifice is controlled at respectively under different vacuum degree condition.Devolatilization forcing machine is at least provided with four venting ports, and one of them is in the rear end of polymkeric substance inlet, and can carry out nitrogen purging.Its excess-three is located between inlet and extruder die head successively, and each venting port arranges different pressures.The absolute pressure of rear end venting port is 100～150KPa, and the absolute pressure of second row gas port is 40～100KPa, and the absolute pressure of the 3rd venting port is 10～30KPa, and the absolute pressure of the 4th venting port is 0.5～20KPa.In polymeric blends, most of volatile substances is removed by rear exhaust port, along with the step increase of vacuum tightness, further removes the volatile matter such as residual unreacted monomer and solvent.
The present invention proposes a kind of optical-grade polymethylmethacrylacontinuous method of continuous production.The continuous production that is particularly useful for optical-grade polymethylmethacrylacontinuous moulding compound.By thering is the circulating tube type reactor of good mass-transfer heat-transfer capability, realize the steady running of introducing a small amount of solvent or not introducing the mass polymerization of solvent, and reached higher polymerisation conversion.Reasonable control by devolatilization forcing machine obtains high-purity polymer.According to the inventive method, can stably prepare the pure polymethyl methacrylate as molding material product of high printing opacity.
Embodiment
Embodiment 1
In methyl methacrylate and methyl acrylate mixture, add initiator tert-butyl peroxide and the tertiary lauryl mercaptan of chain-transfer agent, above raw material is mixed in proportion.Mixture feed composition: the monomer mixture of take is benchmark as 100 parts (quality), 97 parts of methyl methacrylates, 3 parts of methyl acrylates, 0.005 part of tert-butyl peroxide and 0.2 part of tertiary lauryl mercaptan.In monomer mixture, be filled with nitrogen, remove the oxygen of sneaking into, control oxygen level is wherein at 2ppm.With pump, in the circulating tube type reactor through nitrogen replacement, add above raw material mixing solutions continuously.Material circulates in reactor by recycle pump, and Matter Transfer speed is controlled as 80:1 with the ratio of feeding rate.In circulating tube type reactor, temperature remains on 150 ℃.Reach 59.5% to polymerisation conversion, by entirely following the toothed gear pump of tubular reactor bottom, polyblend is delivered in preheater, the polymerization temperature in preheater is 160 ℃.When polymerisation conversion reaches 78.7%, polymeric blends is sent in twin screw devolatilization forcing machine and carried out devolatilization separation, last extruding pelletization.Mean residence time is 1.5h.In forcing machine, minute differing temps regional control temperature is within the scope of 200-230 ℃.From inlet to die head direction, the absolute pressure of four venting ports is controlled successively as 120KPa, 60KPa, 20KPa and 6KPa.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 obtaining is sent into recycle in material-compound tank.Polymkeric substance test result is listed in table 1.
Embodiment 2
Use the method identical with embodiment 1.Except the composition of mixing solutions is: 95 parts of methyl methacrylates, 5 parts of methyl acrylates, Matter Transfer speed is 90:1 with the ratio of feeding rate, the absolute pressure of four venting ports is controlled successively as 120KPa, 50KPa, 15KPa and 4KPa, and other condition is identical with embodiment 1.Question response is complete, and polymeric blends is sent into and in vented extruder, carried out devolatilization separation.Polymkeric substance test result is listed in table 1.
Embodiment 3
Use the method identical with embodiment 1.Except the composition of mixing solutions is: 97 parts of methyl methacrylates, 3 parts of ethyl propenoates, circulating tube type temperature of reactor is 145 ℃, Matter Transfer speed is 50:1 with the ratio of feeding rate, the absolute pressure of four venting ports is controlled successively as 130KPa, 60KPa, 10KPa and 5KPa, and other condition is identical with embodiment 1.Question response is complete, and polymeric blends is sent into and in vented extruder, carried out devolatilization separation.Polymkeric substance test result is listed in table 1.
Embodiment 4
Use the method identical with embodiment 1.Except the composition of mixing solutions is: 95 parts of methyl methacrylates, 5 parts of ethyl propenoates and 3 parts of toluene are as solvent, circulating tube type temperature of reactor is 140 ℃, Matter Transfer speed is 60:1 with the ratio of feeding rate, the absolute pressure of four venting ports is controlled successively as 110KPa, 50KPa, 15KPa and 4KPa, and other condition is identical with embodiment 1.Question response is complete, and polymeric blends is sent into and in vented extruder, carried out devolatilization separation.Polymkeric substance test result is listed in table 1.
Comparative example 1
Use the method identical with embodiment 1.Except the composition of mixing solutions is: 95 parts of methyl methacrylates, 5 parts of methyl acrylates, Matter Transfer speed is 30:1 with the ratio of feeding rate.The absolute pressure of four venting ports is controlled successively as 110KPa, 50KPa, 15KPa and 4KPa, and other condition is identical with embodiment 1.Question response is complete, and polymeric blends is sent into and in vented extruder, carried out devolatilization separation.Polymkeric substance test result is listed in table 1.
Comparative example 2
Use the method identical with embodiment 1.Except the composition of mixing solutions is: 95 parts of methyl methacrylates, 5 parts of methyl acrylates, the amount of initiator tert-butyl peroxide is increased to 0.02 part, Matter Transfer speed is 50:1 with the ratio of feeding rate, the absolute pressure of four venting ports is controlled successively as 120KPa, 60KPa, 20KPa and 5KPa, and other condition is identical with embodiment 1.Question response is complete, and polymeric blends is sent into and in vented extruder, carried out devolatilization separation.Polymkeric substance test result is listed in table 1.
Comparative example 3
Use the method identical with embodiment 1.Except the composition of mixing solutions is: 95 parts of methyl methacrylates, 5 parts of methyl acrylates and 2 parts of toluene are as solvent, Matter Transfer speed is 80:1 with the ratio of feeding rate, the absolute pressure of four venting ports is controlled successively as 120KPa, 60KPa, 40KPa and 30KPa, and other condition is identical with embodiment 1.Question response is complete, and polymeric blends is sent into and in vented extruder, carried out devolatilization separation.Polymkeric substance test result is listed in table 1.
Comparative example 4
Adopt two tank reactors of mixing completely with chuck and stirring of connecting to carry out mass polymerization.Mixing solutions consist of 95 parts of methyl methacrylates, 5 parts of methyl acrylates, 5 parts of toluene as solvent, 0.01 part of tert-butyl peroxide and 0.2 part of tertiary lauryl mercaptan.After nitrogen is removed the dissolved oxygen in monomer, to send into first and mix completely in tank reactor, polymerization temperature is respectively 150 ℃.When polymerisation conversion reaches 43%, the polyblend in the first reactor is delivered in the second reactor of series connection with it, polymerization temperature is 155 ℃, and wherein polymerisation conversion reaches 68.5%, and polymerization process mean residence time is 2h.Question response is complete, and polymeric blends is sent into and in devolatilization forcing machine, carried out devolatilization separation.The absolute pressure of four venting ports is controlled successively as 110KPa, 50KPa, 15KPa and 3Kpa.Volatiles is through Separation and Recovery, by the unreacted monomer recycle obtaining.Polymkeric substance test result is listed in table 1.Mixing completely in tank reactor, because heat and mass is unfavorable, causing polymerization-filling inhomogeneous, light transmission decreases.
Table 1
Note: in comparative example 4, be with * data for mixing data in tank reactor completely.
Claims (5)
1. the method that continuous production is optical-grade polymethylmethacrylacontinuous, it is characterized in that: in circulating tube type reactor, supply with (methyl) acrylic ester monomer or add the solution polymerization that is less than or equal to 5% inert solvent continuously, polymerization temperature is controlled within the scope of 130～160 ℃, and polymer content is controlled at 40～65%; Reaction mass is sent into further polymerization in well heater continuously, and by its Temperature Setting, within the scope of 140～170 ℃, polymer content is brought up to 55-80%; The reaction mixture obtaining is delivered in devolatilization forcing machine, this continuously separation remove volatile matter;
In described circulating tube type reactor, control the ratio of Matter Transfer speed and feeding rate in the scope of 40:1-120:1.
2. according to the optical-grade polymethylmethacrylacontinuous method of continuous production described in claim l, it is characterized in that: described well heater is in series by 3 sections of tubular unit with chuck built-in detachable static mixer.
3. according to the optical-grade polymethylmethacrylacontinuous method of continuous production described in claim l, it is characterized in that: described devolatilization forcing machine is at least provided with four venting ports, one of them venting port is in the rear end of polymkeric substance inlet, and can carry out nitrogen purging, its excess-three is located between inlet and extruder die head successively, from inlet rear end to die head direction, the absolute pressure of four venting ports is controlled within the scope of 100-150KPa, 40-100KPa, 10-30KPa and 0.5-20KPa successively.
4. according to the optical-grade polymethylmethacrylacontinuous method of continuous production described in claim l, it is characterized in that: in the preparation method of described polymkeric substance, residual monomer content is lower than 1000-3000ppm.
5. according to the optical-grade polymethylmethacrylacontinuous method of continuous production described in claim l, it is characterized in that: the weight-average molecular weight of resulting polymkeric substance is controlled at 50,000-15, in 0000 scope.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031202A (en) * | 2014-06-17 | 2014-09-10 | 中国科学院化学研究所 | Polyacrylic acid printing ink resin and preparation method thereof |
| CN107428860A (en) * | 2015-02-27 | 2017-12-01 | 株式会社可乐丽 | The manufacture method of (methyl) acrylic resin composition |
| CN111303338A (en) * | 2020-04-10 | 2020-06-19 | 成都优威易比应用技术有限公司 | Method for preparing vinyl polymer by bulk polymerization |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031202A (en) * | 2014-06-17 | 2014-09-10 | 中国科学院化学研究所 | Polyacrylic acid printing ink resin and preparation method thereof |
| CN107428860A (en) * | 2015-02-27 | 2017-12-01 | 株式会社可乐丽 | The manufacture method of (methyl) acrylic resin composition |
| CN107428860B (en) * | 2015-02-27 | 2020-09-01 | 株式会社可乐丽 | Method for producing (meth) acrylic resin composition |
| CN111303338A (en) * | 2020-04-10 | 2020-06-19 | 成都优威易比应用技术有限公司 | Method for preparing vinyl polymer by bulk polymerization |
| CN111303338B (en) * | 2020-04-10 | 2021-09-03 | 成都优威易比应用技术有限公司 | Method for preparing vinyl polymer by bulk polymerization |
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Application publication date: 20140129 |