CN1067085C - Process for preparing methyl methacrylate polymer - Google Patents
Process for preparing methyl methacrylate polymer Download PDFInfo
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- CN1067085C CN1067085C CN94101745A CN94101745A CN1067085C CN 1067085 C CN1067085 C CN 1067085C CN 94101745 A CN94101745 A CN 94101745A CN 94101745 A CN94101745 A CN 94101745A CN 1067085 C CN1067085 C CN 1067085C
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- monomer
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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
- C08F20/00—Homopolymers and 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
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/04—Acids, Metal salts or ammonium salts thereof
- C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/001—Removal of residual monomers by physical means
-
- 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
-
- 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
- C08F2/04—Polymerisation in solution
-
- 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
- C08F20/00—Homopolymers and 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
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A process for producing a methacrylic polymer comprises bulk or solution polymerization of a methacrylic monomer (a), e.g. methyl methacrylate, to obtain a liquid polymer composition (b) containing an unreacted methacrylic monomer and separating a volatile component (c) containing said unreacted monomers to obtain said polymer (d) wherein said volatile component (c) containing said unreacted monomer is treated with a compound having a sulphonic acid group and then with an amine, and is recycled to the polymerizing step.
Description
The present invention relates to the preparation method of methacrylate polymer.Specifically, relate to the mass polymerization or the solution polymerization process that prepare methacrylate polymer, can be used as raw material comprising unreacted methacrylic acid monomer and recycle.
For the polymerization process of methacrylic acid monomer, adopt water medium, intermittent type suspension polymerization usually, recently, adopt increasing of mass polymerization or solution polymerization, because the waste water handling problem that this does not have water medium to bring, and help improving productive rate, cut down the consumption of energy.
For the mass polymerization of methacrylic acid monomer, multiple scheme has been proposed, for example, GB1423288-A, GB2005282-A, the open communique 111408/1991 of Japanese patent gazette 49295/1989,26642/1990 and Japanese Patent.The open communique 132002/1983 and 57613/1988 of Japanese patent gazette 7845/1980 and Japanese Patent discloses the monomeric solution polymerization process of methacrylic.
In above-mentioned mass polymerization or solution polymerization process, general, liquid polymeric compositions contains polymkeric substance and the unreacted methacrylic acid monomer of 30-80% (weight).Unreacted monomer is removed unreacted monomer by reclaiming in the reaction system by evaporation, obtains methacrylate polymer.For this method of evaporating, be known that and adopt the permeability type forcing machine to carry out, for example see the open communique 89710/1987 and 49925/1991 of GB1467045-A and Japanese patent gazette 29914/1976,17555/1977,53682/1989 and Japanese Patent.
By evaporation, from liquid polymeric compositions, separate and volatile matter in, compare with the amount of polymkeric substance, unreacted monomeric amount accounts for the overwhelming majority, thereby in industry produced, unreacted monomer should re-use as raw material.But when monomer was used continuously, the character of the methacrylate polymer of production can degenerate, polymer belt look for example, and the weathering resistance of polymkeric substance reduces, or the like.
The purpose of this invention is to provide a kind of method of producing methacrylate polymer, even polymerization process carry out this method for a long time also can be stably with high quality, the described polymkeric substance of high efficiency production, unreacted monomer re-uses continuously simultaneously.
This purpose and other purpose will become clearly in following narration of the present invention.
The invention provides the method for preparing methacrylate polymer, described method comprises:
Make methacrylic acid monomer (a) carry out mass polymerization or solution polymerization, with the liquid polymeric compositions (b) that obtains containing unreacted methacrylic acid monomer;
The volatile constituent (c) that will contain described unreacted monomer is separated, to obtain described polymkeric substance (d); Wherein,, be with sulfonic compound treatment, handle with amine compound then with a kind of to the volatile constituent (c) that contains described unreacted monomer; And, be circulated to and carry out the polymeric operation.
Fig. 1 is the schema of the specific embodiments of polymerization process of the present invention, is to implement side to adopt;
Fig. 2 is the schema of other embodiment of polymerization process of the present invention.
Methacrylic acid monomer refers to methyl methacrylate or methyl methacrylate and at least one Plant the with it mixture of the alkenyl monomer of copolymerization.
Methyl methacrylate can be used conventional method preparation example such as acetone cyanohydrin method, a kind of bag Draw together catalytic oxidation isobutene or the tert-butyl alcohol and obtain methacrylic acid, then with the method for methanol esterification etc.
The example of other alkenyl monomer have methyl acrylic ester (for example EMA, Propyl methacrylate, butyl methacrylate, benzyl methacrylate etc.), acrylate Class (for example methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, propylene Acid 2-ethylhexyl ester etc.), unsaturated carboxylic acid (for example acrylic acid, methacrylic acid, Malaysia Acid, itaconic acid etc.), acid anhydrides (such as maleic anhydride, itaconic anhydride etc.), with hydroxyl Monomer (for example acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxy propyl ester, acrylic acid one glycol Ester, 2-hydroxyethyl methacrylate, hydroxy propyl methacrylate, methacrylic acid one are sweet Alcohol ester etc.), nitrogen containing monomer (for example acrylamide, Methacrylamide, acrylonitrile, methyl Acrylonitrile, DAAM, dimethylaminoethyl methacrylate etc.), contain epoxy The monomer of base (for example allyl glycidyl ether, acrylic acid glyceride, metering system acid glycerol Ester etc.), styrene monomer (such as styrene, AMS etc.) etc.
Polymerisation in bulk itself is known in the art, GB1423288-A for example, GB2005282-A Japanese patent gazette 32665/1977,21325/1984,21326/1984,49295/ 1989,26642/1990 and the open communique 111408/1991 of Japan Patent.
That is to say and to use any polymerization, as long as it is to make the methacrylic acid monomer polymerization And the liquid polymeric compositions that will contain unreacted monomer reclaims.
Solution polymerization itself also is known in the art, for example the open communique 132002/1983 and 57613/1988 of Japanese patent gazette 7845/1980 and Japanese Patent.
That is to say and to use any polymerization process,, make the methacrylic acid monomer polymerization, and will contain the liquid polymeric compositions recovery of solvent and unreacted monomer as long as in the presence of inert solvent.
In the present invention, " volatile constituent " is meant material that contains the unreacted methacrylic acid monomer in bulk polymerisation process and the material that contains unreacted methacrylic acid monomer and inert solvent in solution polymerization process (volatile constituent hereinafter referred to as).
Can adopt known arbitrary method that volatile constituent in the liquid polymeric compositions and polymkeric substance are separated, for example, the open communique 89170/1987 of GB1467045-A, Japanese patent gazette 53682/1989 and Japanese Patent and 49925/1991 disclosed those methods.
That is to say, liquid polymeric compositions is heated, evaporate volatile constituent, thereby volatile constituent is separated with polymkeric substance with disc type or the ventilative forcing machine of screw.
Volatile constituent after the separation is handled by contact with amine compound then with containing sulfonic compound treatment.
Above-mentioned contact is handled and is carried out better carrying out also passable under the gaseous state under liquid state after the described volatile constituent condensation.
Part or whole volatile constituents continuously or off and on containing sulfonic compound treatment, handle with amine compound then.Whether be part or whole volatile constituents contact processing, or be not to contact processing continuously or off and on, this depend on the character of prepared polymkeric substance, particularly polymkeric substance colourity, be coloring degree.In order to be easy to handle, to make a part of volatile constituent carry out above-mentioned contact and handle, and regulate the percentage ratio of processed volatile constituent by the colourity of observing polymkeric substance.
Owing to may contain the mercaptan that uses in dipolymer or oligopolymer and/or chain-transfer agent such as the polymerization in the volatile constituent, before or after volatile constituent is carried out above-mentioned contact processing, preferably they be removed as " high boiling point last running " by distillation.
When in the process water being arranged, can utilize the proportion difference, adopt the method that is separated that itself and volatile constituent are separated.
When the row distillation was advanced in the contact processing, the gasiform volatile constituent can directly add in the distillation plant.
The polymerization of unreacted monomer might take place in the volatile constituent of liquefaction, thereby it is better to add stopper in the step that is fit in volatile constituent.
As for stopper, any methacrylate monomer stopper commonly used all can use.The example of stopper has quinhydrones, quinhydrones-methyl ether, thiodiphenylamine, benzo thiodiphenylamine etc.The consumption of stopper is generally about 10-100ppm (weight) of unreacted monomer.
The sulfonic compound that contains that the present invention uses can be solid-state or liquid.The example of this compounds has sulfuric acid, Phenylsulfonic acid, tosic acid, dioctyl sulfo-Succinic Acid, strongly acidic cation-exchange as containing the styrene diethylene benzene copoly mer of sulfonate functional groups.
The consumption that contains sulfonic compound is generally the every mole of about 0.0001-0.01 equivalent of last reaction monomers sulfonic group.
Treatment time is generally 10-120 minute.
Treatment temp is generally 0-60 ℃.When temperature was too low, processing efficiency reduced, and temperature is when too high, the easy hydrolysis of monomer.
Treatment condition depend on the concentration of impurity, after the several times test, are easy to make decision.
Can in suitable still such as stirring tank, its mixing be carried out with containing sulfonic compound treatment volatile constituent.Then by liquid-liquid separating method commonly used as be separated, distill, method such as evaporation isolates volatile constituent from mixture.
Perhaps, be solid chemical compound and when being insoluble to volatile constituent when containing sulfonic compound, for example be ion exchange resin, it is poured in the pillar, volatile constituent is passed through pillar then.This method is preferred, because its method is simple, equipment is not corroded, the seldom hydrolysis of unreacted monomer.
When volatile constituent was handled with the pillar of filling, it was generally about 0.1-10 hour by the space velocity of pillar
-1
After containing sulfonic compound treatment, volatile constituent is handled with the amine compound contact again.
In the present invention, amine compound comprises amine and hydrazine.
The amine compound that boiling point is higher than methyl methacrylate is preferred.More preferably, its boiling point is at least 150 ℃ under the normal pressure.
As amine compound, primary amine or secondary amine or hydrazine compound are use.The example of amine compound has aliphatic amine (for example thanomin, hexanediamine, octylame, triethylene five amine, tetren etc.), aromatic amine (for example aniline, phenylenediamine etc.) etc.
The example of hydrazine compound has hydrazine, phenylhydrazine etc.
When handling volatile constituent with amine compound or hydrazine compound, any liquid-liquid mixing method all can use, as long as they can fully contact.
For example, in having the still of agitator, they are mixed, perhaps with them by porous plate being housed or being filled with the pillar of filler.
Usually, treatment temp is extremely about 80 ℃ of room temperatures, and the treatment time is 5-120 minute.
The consumption of amine compound or hydrazine compound is generally every mole of non-reaction monomers 0.0001-0.01 equivalent.
Treated volatile constituent can be undertaken by the method for any liquid-liquid separation with separating of amine or hydrazine class compound.Usually, by porous plate bolt or filling bolt fractionation by distillation.
This distillation can only be used for component and the amine compound that separating volatile is handled, and it also can be used for removing in the lump dipolymer or oligopolymer and mercaptan simultaneously, and untreated volatile constituent can be distilled with the volatile constituent of handling.
The volatile constituent of handling that contains unreacted monomer is mixed with new monomer, is used for polymerization procedure.
According to the present invention, can prepare the good methacrylate polymer of high quality, particularly colourity, even in the continuous bulk or solution polymerization process of described polymkeric substance, unreacted monomer is re-used for a long time continuously also can be like this.
Following embodiment will be used for illustrating the present invention, but they are not limitation of the scope of the invention.
The used method of embodiment is seen Fig. 1, wherein 1 represent the raw material methacrylic acid monomer, 2 represent the raw material vinyl monomer, 3 represent chain-transfer agent, 4 represent polymerization starter, 5 representation polymers, and on behalf of waste liquid, 7,6 represent amine compound, compound " a " to represent liquid polymeric compositions, " b " represents volatile constituent, the recovery monomer that " c " representative recycles.
Being described as follows of major equipment among the figure:
Monomer preparation still:
20 liters, SUS 304 stainless steels are equipped with paddle agitator, have chuck.
The catalyst dissolution still:
10 liters, SUS 304 stainless steels are equipped with paddle agitator, have chuck.
Polymerization reactor:
10 liters, SUS 304 stainless steels are equipped with helical ribbon agitator, have chuck.Well heater:
Internal diameter is that 16.7mm, length are 3m, has chuck.The permeability type forcing machine:
Twin screw extruder (TEX-30 Nippon Steel Work Co., Ltd makes), incorgruous rotation, screw diameter 30mm, tube length 1200mm has 1 metapore and 3 preceding holes.Volatile constituent reclaims post
Internal diameter 100mm, long 3m, SUS 304 stainless steels,, being filled with 3/8 inch Raschig ring of SUS 304 stainless steels, the inspissation partial-length is 0.7m, recovery part length is 0.3m.Ion exchange resin column:
3 liters, SUS 304 stainless steels are filled with 2 liters and contain sulfonic strong acid ion exchange resin (Ltd makes for Duolite C-26c, Sumitomo Chemical Co.).Amine compound is handled still:
1 liter, SUS 304 stainless steels are equipped with paddle agitator, have chuck.
The character of all polymkeric substance is estimated with following method.
(1) melt flow rate (MFR)
With fusion index instrument (Ltd makes for Takara Industries, Co.), under load 3.8Kg, 230 ℃, press JIS K-7210 method measurement melt flow rate.
(2) colourity
With the 40mm forcing machine with T die head (Tanabe Plastics Co., Ltd make), 250 ℃ down with polymer-extruded, is maintained at about 100 ℃ and passes through 3 polishing rolls down, obtains the sheet material that thickness is 3mm.
From the sheet material of extruding, (5cm * 5cm), press the method for JISK-7103 measures its jaundice index (YI) with beam split dyeing instrument SZ-∑ 80 (Ni ppon DenshokuInductries Co., Ltd makes) to take off a square sheet material sample.
(3) weathering resistance
With the sheet material sample of measuring colourity, under 63 ℃, with illumination weather instrument (Ltd makes for WE-SUN-HCA-1 type, Suga Testing Machines Co.) irradiation 2000 hours.Measure jaundice index (Y1) then, these data are as the index of weathering resistance.Embodiment 1
Starting monomer adopts methyl methacrylate (hereinafter being called " MMA ") (Ni pponMethacryl Monomer co., Ltd makes) and methyl acrylate (hereinafter being called " MA ") (Toa Synthesis Co., Ltd makes).Polymerization starter is with Diisopropyl azodicarboxylate (hereinafter being called " AI BN "), and chain-transfer agent is with octyl mercaptan (hereinafter being called " OM ").
In the catalyst dissolution still, add MMA and be the MA of 6.2 weight % and be the AIBN of 0.12 weight % with respect to MMA with respect to MMA, stir, be dissolved in fully in the monomer until AIBN, obtain catalyst solution.
By the circulation of refrigerant in the chuck, the internal temperature of catalyst dissolution still is remained on 5 ℃.
The catalyst solution for preparing is continuously pumped in the polymerization reactor with 1.47 kilograms/hour speed.
In monomer preparation still, the amount by controlling new MMA, MA and OM and the composition and the quantity of round-robin unreacted monomer make and consist of 93.65% (weight) MMA, 6.2% (weight) MA, the monomer mixture of 0.15% (weight) OM.
By the circulation of chuck internal cooling agent, the temperature that monomer is prepared in the still remains on 5 ℃.
The monomer mixture that prepared the speed with 13.279 kilograms/hour is pumped in the polymerization reactor.
Above-mentioned catalyst solution and monomer mixture infeed from the bottom of reactor, and the residence time is 39 minutes, 150 ± 2 ℃ of temperature, and polymerization reaches 45% (weight) until mean polymerisation degree.The liquid polymeric compositions that obtains is removed from the top of polymerization reactor, supplied with well heater.
In well heater,, liquid polymer composition is heated to 200 ℃, pressure 20kg/cm by the circulation of heating medium in the chuck
2G supplies with the permeability type forcing machine then.
Liquid polymeric compositions keeps each breather hole at decompression state by forcing machine simultaneously, and the tube temperature is about 250 ℃, reclaims volatile constituent from breather hole, and it is supplied with volatile constituent reclaim post.
Be strip behind molten state polymer-extruded.After water cooling, the polymkeric substance of strip is cut into granular, average yield is 6.65 kilograms/hour.
The gaseous state volatile constituent that will reclaim from the back breather hole of forcing machine is supplied with the recovery part that volatile constituent reclaims post, the volatile constituent cooling that place, the preceding hole of forcing machine is reclaimed simultaneously becomes liquid, supply with the bottom that volatile constituent reclaims post then, consecutive evaporation goes out volatile constituent, and reflux ratio is 1.
The effluent that reclaims the recovered overhead of post from volatile constituent is circulated to monomer preparation still with average 7.98 kilograms/hour speed, and distilled liquid is supplied with ion exchange resin column with 1 kilogram/hour speed.
The waste liquid of amine-containing compound (the amine compound treatment step is employed), the reaction product of amine compound and impurity are discharged from the end that volatile constituent reclaims post with the speed of average 147 Grams Per Hours.
Reclaim the top of post from volatile constituent and add quinhydrones (stopper) continuously with the speed of about 0.5 Grams Per Hour.
The effluent that volatile constituent reclaims post passes through ion exchange resin column continuously with average 1 kilogram/hour speed.In this step, space velocity is about 0.5 hour.
In the effluent of ion exchange resin column, add tetren continuously with the speed of 2 Grams Per Hours, make this mixture flow into amine compound then and handle in still.In still, monomer and amine compound thorough mixing, mean residence time are about 1 hour, and keeping temperature in the kettle by the chuck heating simultaneously is 50 ℃.
Amine compound is handled the effusive liquid of still supply with the bottom that volatile constituent reclaims post.
Above-mentioned operate continuously was carried out 30 days continuously, and the polymer samples when getting 10 days, 20 days and 30 days is respectively estimated its character.
The melt flow rate of every kind of polymkeric substance is 1.5, and Y1 is 0.4, and according to the YI index, weathering resistance is 0.7.Embodiment 2
Method by embodiment 1 prepares polymkeric substance, and difference is to replace tetren to supply with amine with octylame to handle still.
The melt flow index of every kind of polymkeric substance is 1.5, and Y1 is 0.4, and according to the YI index, weathering resistance is 0.7.Embodiment 3
Method by embodiment 1 prepares polymkeric substance, difference is: the concentration of MA is adjusted to 10.5% (weight) in the catalyst dissolution still, and the concentration of MMA, MA and OM is adjusted to 8.9.03% (weight), 10.51% (weight) and 0.46% (weight) respectively at the bottom of the monomer preparation still.
The melt flow rate of every kind of polymkeric substance is 20, and YI is 0.4, and according to the YI index, weathering resistance is 0.7.Comparative Examples 1
Method by embodiment 1 prepares polymkeric substance, and difference is: the effusive whole effluents in top of volatile constituent recovery post needn't further be handled and direct cycle in the monomer preparation still.
The characteristic of polymkeric substance sees the following form.Comparative Examples 2
Method by embodiment 1 prepares polymkeric substance, and difference is: do not add amine compound in the effluent of ion exchange resin column, promptly do not carry out amine and handle.
The character of polymkeric substance sees the following form.Comparative Examples 3
Method by embodiment 1 prepares polymkeric substance, and difference is: the effluent that reclaims post by the property sent out component is directly supplied with amine processing still, promptly skips ion exchange resin treatment ground step.
The character of polymkeric substance sees the following form.Table
Comparative Examples MFR Y1 weathering resistance
After 10 days after 1.5 3 71 20 days 1.5 7＞15
After 30 days 1.5 10＞15
After 10 days after 1.5 1.5 32 20 days 1.5 37
After 30 days 1.5 6＞15
After 10 days after 1.5 2 53 20 days 1.5 12
After 30 days 1.5 7 15
Claims (5)
1. method for preparing methacrylate polymer, it comprises:
Make methacrylic acid monomer (a) carry out mass polymerization or solution polymerization, with the liquid polymeric compositions (b) that obtains containing unreacted methacrylic acid monomer;
The volatile constituent (c) that will contain described unreacted monomer is separated, to obtain described polymkeric substance (d); Wherein,
To the volatile constituent (c) that contains described unreacted monomer, contain sulfonic compound treatment with a kind of, handle with amine compound then; And, be circulated to polymerization process.
2. method according to claim 1 wherein, was distilling the volatile constituent (c) that contains described unreacted monomer earlier before containing sulfonic compound treatment.
3. method according to claim 1 wherein, is distilled after handling with described amine compound the described volatile constituent (c) that contains unreacted monomer.
4. method according to claim 1, wherein, described to contain sulfonic compound be to contain sulfonic Zeo-karb.
5. method according to claim 1, wherein, described amine compound is that boiling point is at least 150 ℃ primary amine or secondary amine under barometric point.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP015362/93 | 1993-02-02 | ||
| JP01536293A JP3277583B2 (en) | 1993-02-02 | 1993-02-02 | Method for producing methyl methacrylate polymer |
| JP015362/1993 | 1993-02-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1091749A CN1091749A (en) | 1994-09-07 |
| CN1067085C true CN1067085C (en) | 2001-06-13 |
Family
ID=11886691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94101745A Expired - Fee Related CN1067085C (en) | 1993-02-02 | 1994-02-02 | Process for preparing methyl methacrylate polymer |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP3277583B2 (en) |
| KR (1) | KR100272063B1 (en) |
| CN (1) | CN1067085C (en) |
| GB (1) | GB2274845B (en) |
| SG (1) | SG48717A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4676687B2 (en) * | 2003-09-08 | 2011-04-27 | 三菱レイヨン株式会社 | Method for producing (meth) acrylic polymer |
| JP2006335804A (en) * | 2005-05-31 | 2006-12-14 | Kaneka Corp | Imide resin, and optical film using the same |
| DE102005039156B4 (en) * | 2005-08-17 | 2014-12-24 | Evonik Degussa Gmbh | Process for the preparation of (meth) acrylic acid with heavy-boiling work-up by crystallization |
| SG11201408751QA (en) | 2012-06-29 | 2015-01-29 | Kuraray Co | Method for producing (meth)acrylic resin composition |
| SG11201605240WA (en) * | 2013-12-27 | 2016-08-30 | Kuraray Co | Method for manufacturing (meth)acrylic resin composition |
| JP6248742B2 (en) * | 2014-02-21 | 2017-12-20 | 三菱ケミカル株式会社 | Method for purifying (meth) acrylic acid ester and method for producing (meth) acrylic acid ester polymer |
| WO2016104701A1 (en) * | 2014-12-26 | 2016-06-30 | 株式会社クラレ | Process for producing (meth)acrylic resin composition |
| JP6640828B2 (en) | 2015-02-27 | 2020-02-05 | 株式会社クラレ | Method for producing (meth) acrylic resin composition |
| TWI796324B (en) * | 2017-03-09 | 2023-03-21 | 日商東亞合成股份有限公司 | Method for producing (meth)acrylate |
| CN113461854A (en) * | 2020-03-30 | 2021-10-01 | 中石油吉林化工工程有限公司 | PMMA continuous bulk polymerization process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041163A (en) * | 1988-09-12 | 1990-04-11 | 珊瑚化工厂 | The novel method of solution-polymerizing polymethylacrylate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5442035B2 (en) * | 1974-02-04 | 1979-12-12 |
-
1993
- 1993-02-02 JP JP01536293A patent/JP3277583B2/en not_active Expired - Lifetime
-
1994
- 1994-02-02 CN CN94101745A patent/CN1067085C/en not_active Expired - Fee Related
- 1994-02-02 KR KR1019940001901A patent/KR100272063B1/en not_active IP Right Cessation
- 1994-02-02 SG SG1996000422A patent/SG48717A1/en unknown
- 1994-02-02 GB GB9401978A patent/GB2274845B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041163A (en) * | 1988-09-12 | 1990-04-11 | 珊瑚化工厂 | The novel method of solution-polymerizing polymethylacrylate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1091749A (en) | 1994-09-07 |
| KR940019740A (en) | 1994-09-14 |
| SG48717A1 (en) | 1998-05-18 |
| JP3277583B2 (en) | 2002-04-22 |
| GB2274845B (en) | 1996-09-25 |
| GB9401978D0 (en) | 1994-03-30 |
| KR100272063B1 (en) | 2000-11-15 |
| GB2274845A (en) | 1994-08-10 |
| JPH06228203A (en) | 1994-08-16 |
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