CN100366645C - Process for producing methacrylate polymer - Google Patents
Process for producing methacrylate polymer Download PDFInfo
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- CN100366645C CN100366645C CNB2004100691720A CN200410069172A CN100366645C CN 100366645 C CN100366645 C CN 100366645C CN B2004100691720 A CNB2004100691720 A CN B2004100691720A CN 200410069172 A CN200410069172 A CN 200410069172A CN 100366645 C CN100366645 C CN 100366645C
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- type reactor
- tube
- liquid composition
- radical polymerization
- polymerization initiator
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- 229920000642 polymer Polymers 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 15
- 230000008569 process Effects 0.000 title description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 59
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 41
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 39
- 239000000126 substance Substances 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 24
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000005395 methacrylic acid group Chemical group 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 36
- 238000002347 injection Methods 0.000 claims description 25
- 239000007924 injection Substances 0.000 claims description 25
- 230000004044 response Effects 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- -1 alkyl methacrylate Chemical compound 0.000 description 17
- 125000005250 alkyl acrylate group Chemical group 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 9
- 239000003999 initiator Substances 0.000 description 8
- 239000012442 inert solvent Substances 0.000 description 7
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 230000009466 transformation Effects 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
- 238000012662 bulk polymerization Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 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
- 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
- 239000000463 material 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
- 239000003795 chemical substances by application 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
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000284 extract Substances 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
- 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
- ODNRTOSCFYDTKF-UHFFFAOYSA-N 1,3,5-Trimethyl-cyclohexan Natural products CC1CC(C)CC(C)C1 ODNRTOSCFYDTKF-UHFFFAOYSA-N 0.000 description 1
- LQWSBXWILISUST-UHFFFAOYSA-N 1,3,5-trimethylcyclohexane Chemical compound CC1[CH]C(C)CC(C)C1 LQWSBXWILISUST-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
- 241000446313 Lamella Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- 206010044565 Tremor Diseases 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
- 230000008859 change Effects 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
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 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
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 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
- 239000011259 mixed solution 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
- 238000012797 qualification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect 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
- 238000000926 separation method Methods 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
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
Landscapes
- Polymerisation Methods In General (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 adding a radical polymerization initiator and a chain transfer agent to a monomer composition comprising methyl methacrylate to obtain the reaction solution composition, continuously supplying the reaction solution composition into a perfect mixing type reactor to polymerize the reaction solution composition, supplying the polymerization product composition into a pipe type reactor to further polymerize the polymerization product composition, and then removing the volatile substances, is characterized in that the inner diameter D [m] of the pipe in the pipe type reactor and the linear speed u[m/sec] of the reaction solution composition in the pipe type reactor are in the range of expression (1).
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 agents such as dispersion agent, therefore the polymkeric substance transparency that obtains is very excellent, and because the radical polymerization initiator in supply response district is with considerably less amount cause such as just can deal with problems, so study very early.
And known, for example the spy opens the 2000-26507 communique, in order to improve productivity, the manufacture method of complete hybrid reactor of configured in series and tube-type reactor.
Summary of the invention
Though opening the manufacture method of putting down in writing in the 2000-26507 communique the spy is the high manufacture method of productivity, still requires productivity further to improve.The objective of the invention is to,, further improve productivity by the bore in the qualification tube-type reactor and the linear velocity of the reactive composition in the tube-type reactor.
Main points of the present invention are, the manufacture method of metha crylic polymer, in the monomer composition that contains methyl methacrylate, adding radical polymerization initiator and chain-transfer agent as reacting liquid composition, this reacting liquid composition supplied to continuously carry out polymerization in the complete hybrid reactor, then supply to and carry out further polymerization in the tube-type reactor, remove volatile matter then and obtain the manufacture method of the metha crylic polymer of polymkeric substance, it is characterized in that the bore D[m in the tube-type reactor] and tube-type reactor in the linear velocity u[m/s of reacting liquid composition] in the scope of following (1) formula.
0.07≤8×u/D≤0.7 …(1)
Preferably to tube-type reactor supply response fluid composition the time, the relative response fluid composition appends the injection radical polymerization initiator continuously in the velocity range of following (2) formula, then carries out polymerization in tube-type reactor.
Ua≤Ub …(2)
Ua: the linear velocity [m/s] of the reacting liquid composition of radical polymerization initiator injection portion
Ub: the injection linear velocity [m/s] of radical polymerization initiator
The present invention can provide a kind of productivity good, stably makes the manufacture method of the metha crylic polymer of high quality polymer.
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 are the independent polymerization by methyl methacrylate respectively, perhaps contains the monomer mixture copolymerization of methyl methacrylate and (methyl) alkyl acrylate (except the methyl methacrylate) and obtains.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 more than 2 kinds or 2 kinds.Moreover, also can and use alkyl acrylate more than a kind or a kind and the alkyl methacrylate more than a kind or a kind except that 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, the perhaps wantonly multipolymer more than a kind or a kind in methyl methacrylate and methyl acrylate, ethyl propenoate or the butyl acrylate.About multipolymer as previously mentioned, the multipolymer that more preferably contains 80 quality % or more methyl methacrylate units.
The present invention makes as above-mentioned monomer by mass polymerization or solution polymerization and carries 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 more than 2 kinds or 2 kinds.
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 starting monomer, import rare gas elementes such as nitrogen,, make dissolved oxygen preferably reach 2 quality ppm or below it, more preferably reach 1 quality ppm or below it perhaps by starting monomer under reduced pressure being kept certain hour.Under the situation of the solution polymerization of using inert solvent, also carry out same operation for the mixed solution of starting monomer and 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.
From monomer composition, remove dissolved oxygen by this way, add radical polymerization initiator and chain-transfer agent.
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, the disadvantageous tendency that becomes is economically arranged.
In addition, the radical polymerization initiator of Tian Jiaing herein is because the generation of the polymer blocks in can the inhibited reaction device, runs steadily, and even under situation about shutting down suddenly because of having a power failure etc., 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, as the chain-transfer agent that uses in the present invention, can enumerate mercaptan compound or β-terpinene, γ-terpinene, terpinolene etc.As mercaptan compound, preferably can enumerate alkyl with normal-butyl, isobutyl-, n-octyl, dodecyl, sec-butyl, secondary dodecyl, tert-butyl mercaptan etc. or 1 grade, 2 grades or 3 grades of mercaptan of substituted alkyl; Aromatic mercaptans such as thiophenol, 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 be preferably 0.01mol% or more than, be preferably especially 0.05mol% or more than, and, be preferably 1mol% or below it, be preferably 0.5mol% especially or below it.
Then, the reacting liquid composition that will contain chain-transfer agents such as monomer, radical polymerization initiator and mercaptan compound such as this methyl methacrylate is supplied with a complete hybrid reactor continuously, carries out polymerization.
In operation of the present invention, in complete hybrid reactor, preferably in the polymerization temperature of reacting liquid composition is 110～170 ℃ scope, reacting liquid composition is carried out mixing in fact equably.
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.
If polymerization temperature is low excessively, 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.Preferable polymerization temperature be 120 ℃ or more than.
On the other hand, if polymerization temperature is too high, 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 the mean residence time of the reacting liquid composition in hybrid reactor fully or more than, preferred especially 2 hours or more than.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 65 quality % or below it more preferably, more preferably 40 quality % or more than.
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, extracts reacting liquid composition from complete hybrid reactor continuously out, preferably appends the injection radical polymerization initiator in this reacting liquid composition, carries out further polyreaction in tube-type reactor.As tube-type reactor, can enumerate possess with thermal medium or warm water or steam etc. can heat, the cylindrical vessel of refrigerative strap clamp cover etc.Material is SUS304, SUS316 etc. preferably, but is not limited only to these.
In addition, as tube-type reactor, the tube-type reactor of static(al) mixing tank is housed in preferred.As the static(al) mixing tank, can enumerate the static(al) mixing tank of ノ リ ケ カ Application パ ニ one Co., Ltd.'s system or the ス Le one ザ mixing tank of Sumitomo heavy-duty machine tool Co., Ltd. system etc.
As radical polymerization initiator, can enumerate previous illustrative radical polymerization initiator.
Radical polymerization initiator append injection rate, relatively the polymkeric substance in the reacting liquid composition is converted into 1 mole of the aggregate value of monomeric amount and unreacted monomer amount, preferably 5.0 * 10
-6～5.0 * 10
-5In the scope of mole.
In the present invention, the bore D[m in the tube-type reactor] and tube-type reactor in the linear velocity u[m/s of reacting liquid composition] relation that satisfies (1) formula is important.In addition, the tube-type reactor among the present invention is meant to have the caliber that satisfies (1) formula with respect to linear velocity, and is meant the part of the cast that carries out polyreaction.
0.07≤8×u/D≤0.7 … (1)
Less than 0.07 o'clock, the polymkeric substance transformation efficiency did not uprise, and is not preferred in the value of 8 * u/D.Think that this is because the undercompounding of the radial direction in tube-type reactor.In addition, greater than 0.7 o'clock, for the mean residence time that makes the reacting liquid composition in the tube-type reactor reaches the suitable time, the total length of tube-type reactor is elongated, industrial be disadvantageous.Preferred 0.1≤8 * u/D≤0.5.
The ratio of the length L of tube-type reactor and inside diameter D, L/D is preferably 10～200.In order not form short path, L/D more preferably 20 or more than.In addition, consider that L/D more preferably 150 or below it from making cheap this reason of cost of equipment.
Polymerization temperature in the tube-type reactor is preferably in 130～200 ℃ scope.
Have again, the present invention is to tube-type reactor supply response fluid composition the time, in the velocity range of (2) formula, reacting liquid composition is appended the injection radical polymerization initiator continuously, then in tube-type reactor, carry out polymerization, make methyl methacrylate polymer or multipolymer, the polymkeric substance transformation efficiency is risen, and is preferred therefore.
Ua≤Ub … (2)
Ua: the linear velocity [m/s] of the reacting liquid composition of radical polymerization initiator injection portion
Ub: the injection linear velocity [m/s] of radical polymerization initiator
Moreover, so-called radical polymerization initiator injection portion is the part at the 2 plumes interflow of reacting liquid composition and radical polymerization initiator, can be arranged in the tube-type reactor, tube-type reactor is near the ingress of upper reaches portion, upper reaches portion etc. before tube-type reactor.
Linear velocity Ub when injecting radical polymerization initiator is during less than the linear velocity Ua of the reacting liquid composition of radical polymerization initiator injection portion, think injection part at radical polymerization initiator, because containing the injection liquid of radical polymerization initiator becomes intermittently, therefore produce patch in the radical polymerization initiator concentration of in reacting liquid composition, appending, thereby the polymkeric substance transformation efficiency can not uprise.Be added the radical polymerization initiator of injection, can inject separately, also can inject as initiator solution with dilutions such as methyl methacrylates.
In addition, the present invention is so that append the radical polymerization initiator of injection and the good mixing of reacting liquid composition is a purpose, preferably between the injection portion of radical polymerization initiator and tube-type reactor online mixing tank is set.As the on-line mixing device, for example can enumerate the rotatable lamella/stator type on-line mixing device of シ Le バ-ソ Application corporate system or tremble the ス Le-ザ mixing tank etc. of Sumitomo Heavy Industries, Ltd's system of KRC ニ-ダ, static(al) mixing tank of this ironworker Co., Ltd. system with compulsory mixing function.
The present invention after such polymerization process, is conveyed into volatile matter with the reacting liquid composition of extracting out and removes operation, and it is the volatile matter of principal constituent that separation is removed with the unreacted monomer, 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 according to embodiment, but these embodiment do not limit the present invention.
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 %) and as 1 of radical polymerization initiator, two (tert-butyl hydroperoxides) 3 of 1-, 3,5-trimethyl-cyclohexane 1.0 * 10
-5Mol/ monomer 1mol (0.003 quality %) mixes.
Then, this reacting liquid composition is supplied with the complete hybrid reactor that 135 ℃ of polymerization temperatures mix continuously, implement to make the mean residence time of reaction zone reach 3.0 hours polymerization.
Then, from reaction zone, extract reacting liquid composition continuously out with the speed of 20L/h on one side, on one side before the interior pipe arrangement portion that 10 the system SMX ス of unit Sumitomo Heavy Industries, Ltd Le-ザ mixing tanks are housed, be infused in the methyl methacrylate monomer concentration dissolving 1 with 0.04L/h with 1.0 quality %, two (tert-butyl hydroperoxides) 3 of 1-, 3, the initiator solution behind the 5-trimethicone.Mixed radical polymerization initiator concentration relatively is converted into the polymkeric substance in the reacting liquid composition 1 mole of the aggregate value of monomeric amount and unreacted monomer amount, is 6.6 * 10
-6Mol (0.002 quality %).The bore of the body of initiator solution injection portion, the bore of the SMX ス Le that is attached thereto in addition-ザ mixing tank portion all is 0.0272m, the linear velocity Ua of the reacting liquid composition of injection portion is 0.00956m/s.In addition, the injection tube internal diameter of initiator solution is 0.001m.Therefore the injection linear velocity Ub of initiator solution is 0.0141m/s.
After SMX ス Le-ザ mixing tank, the bore that the static(al) mixing tank of ノ リ ケ Co., Ltd. system is housed in the configuration is that 0.0659m, pipe range are the tube-type reactor of 3.0m (L/D=45.5), carry out polyreaction, export continuously to devolatilization forcing machine supply response fluid composition from tube-type reactor then, separate and remove, obtain polymkeric substance with the volatile matter of unreacted monomer as principal constituent.Tube-type reactor possesses chuck in flank portion, is set in 150 ℃ by the temperature of regulating thermal medium.The linear velocity of the reacting liquid composition in the tube-type reactor is 0.00163m/s, 8 * U/D=0.198[l/s].And mean residence time is 30.7 minutes.At this moment, the polymkeric substance containing ratio of hybrid reactor outlet is 47 quality % fully, and the polymkeric substance containing ratio of tube-type reactor outlet is 61 quality %.
Embodiment 2
Except in embodiment 1, the injection tube internal diameter of initiator solution is reached beyond the 0.002m, with obtaining polymkeric substance with embodiment 1 identical method.The injection speed Ub of initiator solution is 0.0035m/s.At this moment, the polymkeric substance containing ratio of hybrid reactor outlet is identical with embodiment 1 fully, is 47 quality %, but the polymkeric substance containing ratio of tube-type reactor outlet is 59.5 quality %.
Comparative example 1
The injection tube internal diameter of the initiator solution among the embodiment 1 reaches 0.002m, and be that 0.1023m, pipe range are the tube-type reactor of 1.3m (L/D=12.7) as the bore that the static(al) mixing tank of ノ リ ケ Co., Ltd. system is housed in the tube-type reactor configuration, carry out polyreaction.At this moment, Ua is 0.00956m/s, and Ub is 0.0035m/s.In addition, the linear velocity u of the reacting liquid composition in the tube-type reactor is 0.00068m/s, and 8 * U/D becomes 0.053[l/s].At this moment, identical at the polymkeric substance containing ratio of hybrid reactor outlet fully with embodiment 1, be 47 quality %, but the polymkeric substance containing ratio that exports at tube-type reactor is 58.0 quality %.
Claims (2)
1. the manufacture method of metha crylic polymer, in containing the monomer composition of methyl methacrylate, add radical polymerization initiator and chain-transfer agent and form reacting liquid composition, this reacting liquid composition supplied with in complete hybrid reactor continuously carry out polymerization, then supply with tube-type reactor and carry out further polymerization, remove the method that volatile matter obtains the metha crylic polymer of polymkeric substance then, it is characterized in that, the polymkeric substance containing ratio of the reacting liquid composition that above-mentioned complete hybrid reactor carries out is the scope of 35-70 quality %, the bore D[m of tube-type reactor] and tube-type reactor in the linear velocity u[m/s of reacting liquid composition] be in the scope of following (1) formula:
0.07≤8×u/D≤0.7…(1)。
2. the manufacture method of metha crylic polymer according to claim 1, wherein, when supply response fluid composition in tube-type reactor, the relative response fluid composition, append the injection radical polymerization initiator continuously in the velocity range of following (2) formula:
Ua≤Ub …(2)
Ua: the linear velocity [m/s] of the reacting liquid composition of radical polymerization initiator injection portion
Ub: the injection linear velocity [m/s] of radical polymerization initiator.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003195867 | 2003-07-11 | ||
| JP2003195867A JP2005029677A (en) | 2003-07-11 | 2003-07-11 | Method for producing methacrylic polymer |
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| Publication Number | Publication Date |
|---|---|
| CN1576286A CN1576286A (en) | 2005-02-09 |
| CN100366645C true CN100366645C (en) | 2008-02-06 |
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|---|---|---|---|
| CNB2004100691720A Expired - Lifetime CN100366645C (en) | 2003-07-11 | 2004-07-05 | Process for producing methacrylate polymer |
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Citations (7)
| 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 |
| JPH08253507A (en) * | 1995-03-16 | 1996-10-01 | Mitsubishi Gas Chem Co Inc | Production of methacrylic resin |
| 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 |
| CN1259975A (en) * | 1997-05-14 | 2000-07-12 | 三菱丽阳株式会社 | (Meth) acrylic resin composition for thermoset injection molding, process for preparing same, and process for producing moldings of same |
| 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 |
| JP2003082004A (en) * | 2001-06-29 | 2003-03-19 | Mitsubishi Rayon Co Ltd | Method for producing vinylic polymer |
-
2003
- 2003-07-11 JP JP2003195867A patent/JP2005029677A/en active Pending
-
2004
- 2004-07-05 CN CNB2004100691720A patent/CN100366645C/en not_active Expired - Lifetime
Patent Citations (7)
| 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 |
| JPH08253507A (en) * | 1995-03-16 | 1996-10-01 | Mitsubishi Gas Chem Co Inc | Production of methacrylic resin |
| 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 |
| CN1259975A (en) * | 1997-05-14 | 2000-07-12 | 三菱丽阳株式会社 | (Meth) acrylic resin composition for thermoset injection molding, process for preparing same, and process for producing moldings of same |
| 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 |
| JP2003082004A (en) * | 2001-06-29 | 2003-03-19 | Mitsubishi Rayon Co Ltd | Method for producing vinylic polymer |
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|---|---|
| JP2005029677A (en) | 2005-02-03 |
| CN1576286A (en) | 2005-02-09 |
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