CN100369943C - Process for producing methacrylate polymer - Google Patents
Process for producing methacrylate polymer Download PDFInfo
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- CN100369943C CN100369943C CNB2004100691716A CN200410069171A CN100369943C CN 100369943 C CN100369943 C CN 100369943C CN B2004100691716 A CNB2004100691716 A CN B2004100691716A CN 200410069171 A CN200410069171 A CN 200410069171A CN 100369943 C CN100369943 C CN 100369943C
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- polymerization initiator
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- 229920000642 polymer Polymers 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 title abstract 2
- 230000008569 process Effects 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims abstract description 50
- 239000000178 monomer Substances 0.000 claims abstract description 44
- 239000000126 substance Substances 0.000 claims abstract description 27
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 26
- 125000005395 methacrylic acid group Chemical group 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 95
- 239000007858 starting material Substances 0.000 claims description 23
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 description 26
- -1 alkyl methacrylate Chemical compound 0.000 description 17
- 125000005250 alkyl acrylate group Chemical group 0.000 description 12
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 11
- 238000012662 bulk polymerization Methods 0.000 description 7
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 7
- 239000012442 inert solvent Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- 238000005502 peroxidation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical group CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 2
- YKFLAYDHMOASIY-UHFFFAOYSA-N γ-terpinene Chemical compound CC(C)C1=CCC(C)=CC1 YKFLAYDHMOASIY-UHFFFAOYSA-N 0.000 description 2
- PYOLJOJPIPCRDP-UHFFFAOYSA-N 1,1,3-trimethylcyclohexane Chemical compound CC1CCCC(C)(C)C1 PYOLJOJPIPCRDP-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- LXUNZSDDXMPKLP-UHFFFAOYSA-N 2-Methylbenzenethiol Chemical compound CC1=CC=CC=C1S LXUNZSDDXMPKLP-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 description 1
- DUZJXKYBSMFDIU-UHFFFAOYSA-N 4-tert-butyl-2-methylbenzenethiol Chemical compound CC1=CC(C(C)(C)C)=CC=C1S DUZJXKYBSMFDIU-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MUPIEMDDBGZNRU-UHFFFAOYSA-N C(C)(C)C(=O)O.C(C)(C)(C)OO Chemical compound C(C)(C)C(=O)O.C(C)(C)(C)OO MUPIEMDDBGZNRU-UHFFFAOYSA-N 0.000 description 1
- FVLVWBKHSDWKMM-UHFFFAOYSA-N CC(C)(C)OO.CCCCC(CC)C(O)=O Chemical compound CC(C)(C)OO.CCCCC(CC)C(O)=O FVLVWBKHSDWKMM-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 206010062717 Increased upper airway secretion Diseases 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229930006974 beta-terpinene Natural products 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical class CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 208000026435 phlegm Diseases 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- WJXKWIFHRZWPET-UHFFFAOYSA-N tert-butyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC(C)(C)C WJXKWIFHRZWPET-UHFFFAOYSA-N 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- SCWPFSIZUZUCCE-UHFFFAOYSA-N β-terpinene Chemical compound CC(C)C1=CCC(=C)CC1 SCWPFSIZUZUCCE-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
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- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a method for producing a methacrylic polymer, by which the polymer having a high quality can stably be produced in good productivity. This method for producing the methacrylic polymer, comprising continuously feeding a methacrylate-containing monomer composition and a radical polymerization initiator into a perfect mixing type reactor, respectively, is characterized by adjusting the feeding amount of the radical polymerization initiator to polymerize the monomer composition at a constant temperature of 110 to 170[deg.]C and then continuously removing volatile substances. For the production method, it is preferable to adjust the temperature of the monomer composition continuously fed into the perfect mixing reactor to polymerize the monomer composition at a constant temperature within a range of 110 to 170[deg.]C.
Description
Technical field
The present invention relates to the manufacture method of metha crylic polymer.
Background technology
By the continuous bulk polymerization of polymethylmethacrylate (PMMA) or the polymerization process of continuous solution polymerization, compare with step suspension polymerization, the productivity excellence, owing to do not need auxiliary agent such as dispersion agent, thereby the polymkeric substance transparency that obtains is very excellent.And, because the radical polymerization initiator in supply response district be with just the dealing with problems of considerably less amount, thereby the unusual cause of excellence etc. of the heat-resisting decomposability of the polymkeric substance that obtains, so study very early.
In order to obtain the polymkeric substance of excellent quality, the mass polymerization of carrying out certain polymerization temperature is necessary.Generally be in the complete hybrid reactor that in continuous bulk polymerization or continuous solution polymerization, uses, around liquid phase portion or gas phase portion, chuck be set and heat-the refrigerative method.Wherein known, for example the spy opens flat 3-111408 communique, on the complete top of hybrid reactor multi tube heat exchanger is set further, and the method for cooling off this gas phase portion also yes.
Summary of the invention
But this method exists the precise dose that makes in the polyreaction to control problems such as the difficulty that becomes.The objective of the invention is to address these problems.
Main points of the present invention, be in complete hybrid reactor, to supply with continuously respectively to contain the monomer composition of methyl methacrylate and the method that radical polymerization initiator is made metha crylic polymer, feed rate by the increase and decrease radical polymerization initiator, carry out polymerization under the certain temperature in 110～170 ℃ of scopes, constantly remove volatile matter then and obtain the manufacture method of the metha crylic polymer of polymkeric substance.
Preferably when polymerization temperature increases 0.2 ℃, the addition that makes polymerization starter 5 quality % with interior scope in decrement, when polymerization temperature reduces by 0.2 ℃, the addition that makes polymerization starter 5 quality % with interior scope in increment.
And, preferably undertaken by regulating the temperature of the monomer composition of in complete hybrid reactor, supplying with continuously, make under the certain temperature that is aggregated in 110～170 ℃ of scopes.
Can provide the manufacture method that productivity is good, can stably make the metha crylic polymer of high-quality polymkeric substance by the present invention.
Embodiment
Below, explain the present invention.
The present invention is applicable to metha crylic polymer, i.e. the manufacturing of Polymerization of Methyl thing or multipolymer.Especially preferably be applicable to the independent polymkeric substance of methyl methacrylate, perhaps contain the manufacturing of 80 quality % or more methyl methacrylate units and 20 quality % or the unitary multipolymer of (methyl) alkyl acrylate (except the methyl methacrylate) still less.These metha crylic polymers, the independent polymerization by methyl methacrylate respectively, perhaps contain methyl methacrylate and (methyl) alkyl acrylate (except the methyl methacrylate) monomer mixture copolymerization and obtain.Here said (methyl) alkyl acrylate is meant alkyl acrylate or alkyl methacrylate.
When carrying out copolymerization, the alkyl acrylate that uses together as monomer and methyl methacrylate, preferably has carbonatoms and is the alkyl acrylate of 1～18 alkyl, for example can enumerate, have the alkyl acrylate of alkyl such as methyl, ethyl, n-propyl, normal-butyl, 2-ethylhexyl, dodecyl, octadecyl.
In addition, the alkyl methacrylate that uses together as monomer and methyl methacrylate, preferably has carbonatoms and is the alkyl methacrylate of 2～18 alkyl, for example can enumerate, have the alkyl methacrylate of alkyl such as ethyl, n-propyl, normal-butyl, 2-ethylhexyl, dodecyl, octadecyl.
(methyl) alkyl acrylate (except the methyl methacrylate) can use a kind, also can be also with 2 kinds or more than it.Moreover, also can and with the above alkyl acrylate of a kind or its and a kind or alkyl methacrylate more than it except the methyl methacrylate.
As the metha crylic polymer that obtains according to the present invention, the independent polymkeric substance of special preferable methyl methyl acrylate, be polymethylmethacrylate, perhaps above multipolymer of wantonly a kind or its in methyl methacrylate and methyl acrylate, ethyl propenoate or the butyl acrylate.About multipolymer as previously mentioned, the multipolymer that preferably contains 80 quality % or more methyl methacrylate units.
In the present invention, make as above-mentioned monomer by mass polymerization or solution polymerization and carry out polymerization.Because can obtain the polymkeric substance of heat-resisting decomposability excellence, so preferably carry out mass polymerization.
Carrying out as inert solvent, can using known solvents such as methyl alcohol, ethanol, toluene, dimethylbenzene, acetone, hexone, ethylbenzene, ethyl methyl ketone, butylacetate when of the present invention with solution polymerization.Inert solvent can use a kind, also can be also with 2 kinds or more than it.
When carrying out solution polymerization, the usage quantity of inert solvent, in reacting liquid composition preferably less than 5 quality %.More preferably do not use the mass polymerization of inert solvent, if but the usage quantity of inert solvent in reacting liquid composition less than 5 quality %, just infringement is the heat-resisting decomposability of solution polymerization shortcoming in the past hardly, in addition, with mass polymerization similarly, by utilizing gel effect,, just can improve percent polymerization effectively by using a spot of radical polymerization initiator.
In the present invention, at first, in containing the monomer composition of methyl methacrylate, import rare gas elementes such as nitrogen, perhaps by monomer composition under reduced pressure being kept certain hour, make dissolved oxygen preferably reach 2 quality ppm or below it, more preferably reach 1 quality ppm or below it.Under the situation of the solution polymerization of using inert solvent, also carry out same operation for the monomer composition that contains inert solvent, make dissolved oxygen preferably reach 2 quality ppm or below it, more preferably reach 1 quality ppm or below it.If make dissolved oxygen reach 2 quality ppm or below it, polyreaction is just stably carried out, and, even polymerization process keeps long-time, high temperature, also produce coloring components hardly, obtain high-quality polymkeric substance.In addition, in the present invention,, also be called monomer composition for convenience even only constitute by methyl methacrylate.
In complete hybrid reactor, supply with monomer composition and the radical polymerization initiator of having removed dissolved oxygen by this way respectively continuously.Radical polymerization initiator can be supplied with separately, also can be added in a part of monomer composition and other monomer composition is supplied with respectively.
The radical polymerization initiator of Tian Jiaing herein, decomposed hardly before in radical polymerization initiator is evenly dispersed in reactor, obtain the utilising efficiency of very high radical polymerization initiator, therefore under the polymerization temperature in complete hybrid reactor, preferably 10 seconds or more than it transformation period, especially preferably 120 seconds or more than it.Even the transformation period of radical polymerization initiator is short, strengthen stirring intensity, radical polymerization initiator is disperseed before decomposition, but need very large stirring power for this reason, there is the disadvantageous tendency that becomes economically.
In addition, the generation of the polymer blocks in the radical polymerization initiator of Tian Jiaing herein, inhibited reaction device can runs steadily.And, even waiting under the situation about suddenly shutting down because of having a power failure, the polymerization of reaction solution also can be carried out, not too can become high viscosity, restart easily, therefore, under the polymerization temperature in complete hybrid reactor, transformation period is preferably 1 hour or below it, is preferably 30 minutes especially or below it.Consider polymerization temperature, for example can from following compound, select: tert-butyl hydroperoxide-3,5,5-tri-methyl hexanoic acid ester, the peroxide lauric acid tert-butyl ester, tert-butyl hydroperoxide sec.-propyl one carbonic ether, uncle's hexyl peroxidation sec.-propyl one carbonic ether, tert-butyl peroxy acetate, 1, two (tert-butyl hydroperoxides) 3 of 1-, 3, the 5-trimethyl-cyclohexane, 1, two (tert-butyl hydroperoxide) hexanaphthenes of 1-, the tert-butyl hydroperoxide 2-ethylhexanoate, the tert-butyl hydroperoxide isobutyrate, uncle's hexyl peroxidation 2-ethylhexanoate, ditertiary butyl peroxide, 2,5-dimethyl-2, organo-peroxides such as 5-two (tert-butyl hydroperoxide) hexane, perhaps, 2-(carbamyl azo)-isopropyl cyanide, 1,1 '-azo two (1-cyclohexanenitrile), 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2-methylbutyronitrile), 2,2 '-azo-bis-iso-dimethyl, 2,2 '-azo two (2,4, the 4-trimethylpentane), 2,2 '-azo two azo-compounds such as (2-methylpropanes) etc.
The usage quantity of the radical polymerization initiator of Tian Jiaing herein, can be according to the polymerization temperature in the complete hybrid reactor, mean residence time, determine aptly as the percent polymerization of target, but polymkeric substance for the few heat-resisting decomposability excellence of the terminal double link amount that obtains polymkeric substance, relative 1 mole of monomer, the usage quantity of radical polymerization initiator is preferably 5.0 * 10
-5Mole or below it, in addition, if consider the productivity of industry, relative 1 mole of monomer is preferably 5.0 * 10
-6The mole or more than it.
In addition, the present invention can use chain-transfer agent.As chain-transfer agent, can enumerate mercaptan compound or β-terpinene, γ-terpinene, terpinolene etc.As mercaptan compound, preferably can enumerate 1 grade, 2 grades or 3 grades of mercaptan of alkyl such as having normal-butyl, isobutyl-, n-octyl, dodecyl, sec-butyl, secondary dodecyl, tert-butyl mercaptan or substituted alkyl; Aromatic mercaptans such as phenyl mercaptan, thiocresol, 4-tert-butyl o thiocresol; Thiovanic acid and ester thereof; Carbonatomss such as hydroxyethyl mercaptan are 3～18 mercaptan.These can use separately, and can be used in combination more than 2 kinds or 2 kinds.Especially, preferably use tert-butyl mercaptan, normal-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan.
Be shaped the possible suitable polymerization degree of processing (generally as the scope of shaped material in industrial use while keeping product strength to obtain, the weight-average molecular weight of finally removing the polymkeric substance behind the volatile component is 70,000～150,000) time, can make the polymkeric substance of heat-resisting decomposability excellence, therefore, relative monomer, the usage quantity of chain-transfer agent is preferably 0.01mol% or more than it, be preferably 0.05mol% especially or more than it, and, be preferably 1mol% or below it, be preferably 0.5mol% especially or below it.Chain-transfer agent can be added in the monomer composition in advance, also can additionally supply with continuously.
Then, in complete hybrid reactor, supply with this monomer composition and radical polymerization initiator respectively continuously, carry out polymerization.Below, the liquid in the complete hybrid reactor is called reacting liquid composition.
In operation of the present invention, in complete hybrid reactor, the polymerization temperature of reacting liquid composition carries out reacting liquid composition to mix in fact equably in 110～170 ℃ scope.At this moment, polymerization temperature remains on certain temperature.The said certain temperature of the present invention is meant in the scope of desired relatively temperature ± 0.4 ℃.In order to remain in this scope, the preferential selection when polymerization temperature uprises, reduced the feed rate of polymerization starter, when the polymerization temperature step-down, increases the feed rate of polymerization starter.More preferably, when polymerization temperature increases 0.2 ℃, the feed rate that makes polymerization starter 5 quality % with interior scope in decrement, when polymerization temperature reduces by 0.2 ℃, the feed rate that makes polymerization starter 5 quality % with interior scope in increment.When desired relatively temperature 0.3 ℃ of change takes place or 0.1 ℃ of change takes place, also can increase and decrease the feed rate of radical initiator.
Chuck further is set around complete hybrid reactor, conducts heat and reduce phlegm and internal heat or the share of methods such as the cooling supply of heating, monomer mixture (reacting liquid composition), reflux cooling, can be controlled at certain polymerization temperature by leading to thermal medium circulations such as the vent-pipe that is provided with in the reaction zone or spiral tube.
Preferred and usefulness in these methods when the refrigerative monomer composition is supplied with, is regulated the method that cooling temperature is controlled at certain polymerization temperature according to the change of this polymerization temperature in complete hybrid reactor.As the adjustment criteria of cooling temperature, preferably, when polymerization temperature increased 0.2 ℃, the supplying temperature that makes monomer composition reduced in interior scope at 5 ℃, reduced by 0.2 o'clock at polymerization temperature, rose in interior scope at 5 ℃.When desired relatively temperature 0.3 ℃ change takes place or 0.1 ℃ change takes place, also can regulate the supplying temperature of monomer composition.
If polymerization temperature is lower than 110 ℃, the polymerization velocity hastening phenomenon that is caused by gel effect becomes big, and therefore under the low condition of percent polymerization, it is difficult carrying out runs steadily, is disadvantageous economically.Polymerization temperature is preferably 120 ℃ or more than it.
On the other hand, if polymerization temperature is higher than 170 ℃, polyreaction can stably be carried out, and therefore can improve percent polymerization, but because the generation of dipolymer becomes many, has the polymkeric substance transparency after volatile component is removed, the tendency that physical strength reduces.In addition, on the stereospecific of polymkeric substance, syndyotactic ratio reduces, and therefore has the tendency of the heat-drawn wire reduction of polymkeric substance.Known in addition, the content of the alkyl acrylate of copolymer composition is many more, and the heat-drawn wire of polymkeric substance descends, but heat-resisting decomposability improves.On the other hand, when the identical polymkeric substance of the ratio of making methyl methacrylate and alkyl acrylate, the side that polymerization temperature is low, syndyotactic ratio uprises, and the heat-drawn wire of polymkeric substance uprises.Therefore, if reduce polymerization temperature, compare with the situation that polymerization temperature is high, though make the content of alkyl acrylate improve heat-resisting decomposability more, but the reduction of heat-drawn wire is little, and as the polymkeric substance that has high heat distortion temperature and heat-resisting decomposability concurrently, the dominance of industry is very big.Polymerization temperature is preferably 140 ℃ or below it.
Because can control the usage quantity of radical polymerization initiator, so the control of polyreaction is easy, the terminal double link quantitative change of polymkeric substance gets very few, can obtain the polymkeric substance of heat-resisting decomposability excellence, therefore preferred 1 hour of mean residence time in hybrid reactor fully or more than it, preferred especially 2 hours or more than it.In addition, in order to obtain high productivity, it is very few that the generation of dipolymer becomes, therefore fully preferred 6 hours of mean residence time in the hybrid reactor or below it, preferred especially 5 hours or below it.By making mean residence time in the complete hybrid reactor in above-mentioned scope, can when making the polymerization control stabilization, can make the polymkeric substance of shaping excellent in workability.
And then, in process of the present invention, in complete hybrid reactor, preferably accomplish to make the polymkeric substance containing ratio of reacting liquid composition to maintain certain certain value in 35～70 quality % scopes in fact.The polymkeric substance containing ratio is preferably 65 quality % or below it, is preferably 40 quality % or more than it.
Complete hybrid reactor as using in the present invention can use the grooved reaction unit that possesses supplying opening, conveying end and whipping appts, and it is necessary that whipping appts has the mixed performance that spreads all over the entire reaction district.
The present invention uses commercially available pumps such as toothed gear pump, extract reacting liquid composition continuously out from complete hybrid reactor, in this reacting liquid composition, add radical polymerization initiator, in the tube-type reactor of the interior strap clamp cover that the static(al) mixing tank is housed etc., also can carry out polyreaction further.
The present invention sends the reacting liquid composition of extracting out continuously into volatile matter and removes operation behind such polymerization process, and separating removal is the volatile matter of principal constituent with unreacted monomer, just can make metha crylic polymer.
When the metha crylic polymer of making by this way uses as shaped material, can add lubricants such as higher alcohols, high-grade aliphatic ester class.In addition, as required, can add UV light absorber, thermo-stabilizer, tinting material, anti-static electrification agent etc.
Below, illustrate in greater detail the present invention by embodiment, but these embodiment limit the present invention anything but.
Embodiment 1
In the monomer mixture that the methyl acrylate by refined methyl methacrylate of 98 quality % and 2 quality % constitutes, import nitrogen, after dissolved oxygen reaches 0.5 quality ppm, relative monomer mixture, add the octyl mercaptan of 0.171mol% (0.25 quality %), mix, obtain monomer composition A.In addition, the monomer mixture that is deployed into relatively equally adds 1.0 * 10 as radical polymerization initiator
-31,1 of mol '-two (tert-butyl hydroperoxide) 3,3,5-trimethyl-cyclohexane/1mol (0.3 quality %) monomer mixture mixes.With it as polymerization starter liquid A.
Then, relative this monomer composition of 100 mass parts A, with the ratio of 1 mass parts polymerization starter liquid A, in the complete hybrid reactor that 135 ℃ of polymerization temperatures are mixing, supply with continuously respectively, implementing to make mean residence time in the reaction zone is 3.0 hours polymerization.The temperature of the monomer composition A that supplied with is set at necessarily, is 15 ℃.The liquid phase portion of hybrid reactor heats down at 120 ℃ by thermal medium fully, and gas phase portion is cooled to 60 ℃ by cold medium.Transformation period in the polymerization temperature (135 ℃) of employed radical polymerization initiator is 230 seconds.
In the way, when polymerization temperature reached 135.2 ℃, the feed rate decrement 2 quality % with polymerization starter liquid A promptly, reached 0.98 mass parts.Get back to moment of 135.0 ℃ at polymerization temperature, the feed rate of polymerization starter liquid A is also returned to 1 mass parts.In addition, when polymerization temperature was reduced to 134.8 ℃, the feed rate increment 2 quality % with polymerization starter liquid A promptly, reached 1.02 mass parts.Get back to moment of 135.0 ℃ at polymerization temperature, the feed rate of polymerization starter liquid A is also returned to 1 mass parts.Moreover, extract reacting liquid composition continuously out, removing with unreacted methyl methacrylate with the devolatilization forcing machine is the volatile matter of principal constituent, obtains metha crylic polymer.Feed rate by inching polymerization starter liquid A like this, between on-stream period, do not finely tune the temperature of the monomer composition A of the jacket temperature of complete hybrid reactor and supply, Yi Bian polymerization temperature is maintained in 135 ℃ ± 0.4 ℃ the scope, Yi Bian carry out 5 days continuous operation.
Embodiment 2
Except radical polymerization initiator is altered to 3.0 * 10
-3The tert-butyl hydroperoxide of mol-3,5,5 Trimethylhexanoic acid ester/1mol (0.7 quality %) monomer mixture is as beyond the polymerization starter liquid B, carries out the operation same with embodiment 1, carries out polyreaction.The transformation period of the polymerization temperature (135 ℃) of the polymerization starter that uses is 810 seconds.
In the way, when polymerization temperature reached 135.2 ℃, the feed rate decrement 3 quality % with polymerization starter liquid B promptly, reached 0.97 mass parts, got back to moment of 135.0 ℃ at polymerization temperature, and the feed rate of polymerization starter liquid B is returned to 1 mass parts.In addition, when polymerization temperature was reduced to 134.8 ℃, the feed rate increment 3 quality % with polymerization starter liquid B promptly, reached 1.03 mass parts, got back to moment of 135.0 ℃ at polymerization temperature, and polymerization starter liquid B feed rate is returned to 1 mass parts.Feed rate by inching polymerization starter liquid B like this, in between on-stream period, do not finely tune the temperature of the monomer composition A of the jacket temperature of complete hybrid reactor and supply, Yi Bian polymerization temperature is maintained in 135 ℃ ± 0.4 ℃ the scope, Yi Bian carry out 5 days continuous operation.
Embodiment 3
When polymerization temperature reaches 135.2 ℃, the temperature of the monomer composition A that supplied with is altered to 13 ℃, when turning back to 135.0 ℃ the moment, polymerization temperature make the temperature of the monomer composition A that is supplied with reach 15 ℃.In addition, when polymerization temperature is reduced to 134.8 ℃, the temperature of monomer composition A is altered to 17 ℃, gets back to moment of 135.0 ℃, make the temperature of monomer composition A reach 15 ℃ at polymerization temperature, and with these two kinds of methods of operation, in addition, carry out 1 identical operations, do not finely tune the jacket temperature of complete hybrid reactor with embodiment, polymerization temperature is maintained in 135 ℃ ± 0.3 ℃ the scope, Yi Bian carry out 5 days continuous operation.
Comparative example 1
Relative 100 mass parts monomer composition A, ratio with 1 mass parts polymerization starter liquid B makes the feed rate of radical polymerization initiator certain, the cold medium cooling of the thermal medium heating of the liquid phase portion by complete hybrid reactor, gas phase portion makes polymerization temperature keep certain, in addition, carry out 1 identical operations, carried out 3 days continuous operation with embodiment.In between on-stream period, when polymerization temperature rose to 135.2 ℃, though make the heat medium temperature setting of liquid phase portion and the cold medium temperature setting of gas phase portion reduce by 3 ℃, heat medium temperature and cold medium temperature can not reduce at once, and polymerization temperature rises to 136.4 ℃.In addition, when polymerization temperature is reduced to 134.8 ℃, risen 3 ℃ though heat medium temperature setting and cold medium temperature are set, heat medium temperature and cold medium temperature can not rise at once, and polymerization temperature is reduced to 134.0 ℃.In addition, the polymerization temperature (135.0 ℃) that can control to once more as target needs 40 minutes, will follow wave phenomenon if shorten this activity duration, and running is carried out continuously.
Claims (3)
1. the manufacture method of metha crylic polymer, in complete hybrid reactor, supply with the method that the monomer composition contain methyl methacrylate and radical polymerization initiator are made metha crylic polymer respectively continuously, it is characterized in that, by when polymerization temperature increases with the feed rate decrement of radical polymerization initiator, when polymerization temperature reduces with the feed rate increment of radical polymerization initiator, carry out polymerization under the certain temperature in 110～170 ℃ of scopes, continuously remove volatile matter then, obtain polymkeric substance.
2. the manufacture method of metha crylic polymer according to claim 1, wherein, when polymerization temperature increases 0.2 ℃, with the addition of polymerization starter 5 quality % with interior scope in decrement, when polymerization temperature reduces by 0.2 ℃, with the addition of polymerization starter 5 quality % with interior scope in increment.
3. the manufacture method of metha crylic polymer according to claim 1 and 2 wherein, also by regulate the temperature of the monomer composition of supplying with continuously in complete hybrid reactor, is carried out polymerization under the certain temperature in 110～170 ℃ of scopes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003193643 | 2003-07-08 | ||
| JP2003193643A JP2005029613A (en) | 2003-07-08 | 2003-07-08 | Method for producing methacrylic polymer |
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| CN1576285A CN1576285A (en) | 2005-02-09 |
| CN100369943C true CN100369943C (en) | 2008-02-20 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022090526A1 (en) | 2020-11-02 | 2022-05-05 | Röhm Gmbh | Device for degassing of a two-component multiphase polymer-monomer material and use thereof in a degassing extruder |
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| JP4323406B2 (en) | 2004-10-04 | 2009-09-02 | 住友化学株式会社 | Continuous polymerization apparatus and continuous polymerization method using the same |
| 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 |
| CN111378066B (en) * | 2018-12-30 | 2022-05-06 | 中国石油天然气股份有限公司 | Method for preparing methyl methacrylate polymer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58132002A (en) * | 1982-01-29 | 1983-08-06 | Asahi Chem Ind Co Ltd | Continuous production of methacrylate copolymer |
| CN1238785A (en) * | 1996-07-25 | 1999-12-15 | 三菱丽阳株式会社 | Process for the prepration of poly(meth) acrylic acid ester |
| CN1303397A (en) * | 1998-07-14 | 2001-07-11 | 三菱丽阳株式会社 | Process for producing metha crylic polymer |
| JP2003002912A (en) * | 2001-06-21 | 2003-01-08 | Mitsubishi Rayon Co Ltd | Method for producing methacrylate polymer |
-
2003
- 2003-07-08 JP JP2003193643A patent/JP2005029613A/en active Pending
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2004
- 2004-07-05 CN CNB2004100691716A patent/CN100369943C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58132002A (en) * | 1982-01-29 | 1983-08-06 | Asahi Chem Ind Co Ltd | Continuous production of methacrylate copolymer |
| CN1238785A (en) * | 1996-07-25 | 1999-12-15 | 三菱丽阳株式会社 | Process for the prepration of poly(meth) acrylic acid ester |
| CN1303397A (en) * | 1998-07-14 | 2001-07-11 | 三菱丽阳株式会社 | Process for producing metha crylic polymer |
| JP2003002912A (en) * | 2001-06-21 | 2003-01-08 | Mitsubishi Rayon Co Ltd | Method for producing methacrylate polymer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022090526A1 (en) | 2020-11-02 | 2022-05-05 | Röhm Gmbh | Device for degassing of a two-component multiphase polymer-monomer material and use thereof in a degassing extruder |
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| CN1576285A (en) | 2005-02-09 |
| JP2005029613A (en) | 2005-02-03 |
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