CN1605593A - Production method of (methyl) acrylic acid polymer - Google Patents
Production method of (methyl) acrylic acid polymer Download PDFInfo
- Publication number
- CN1605593A CN1605593A CN 200410074605 CN200410074605A CN1605593A CN 1605593 A CN1605593 A CN 1605593A CN 200410074605 CN200410074605 CN 200410074605 CN 200410074605 A CN200410074605 A CN 200410074605A CN 1605593 A CN1605593 A CN 1605593A
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- Prior art keywords
- methyl
- mentioned
- composition
- acid polymer
- acrylic acid
- Prior art date
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- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims description 131
- 229920002125 Sokalan® Polymers 0.000 title claims description 70
- 239000000203 mixture Substances 0.000 claims abstract description 121
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000178 monomer Substances 0.000 claims abstract description 63
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 38
- 238000011084 recovery Methods 0.000 claims abstract description 22
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 20
- 239000011541 reaction mixture Substances 0.000 claims abstract description 14
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 66
- 238000004821 distillation Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 33
- -1 mercaptan compound Chemical class 0.000 claims description 23
- 238000007872 degassing Methods 0.000 claims description 21
- 238000012545 processing Methods 0.000 claims description 9
- 241000282326 Felis catus Species 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 abstract 3
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 54
- 239000007789 gas Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 11
- 239000012442 inert solvent Substances 0.000 description 9
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 125000005250 alkyl acrylate group Chemical group 0.000 description 6
- 238000012662 bulk polymerization Methods 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 229920000642 polymer Polymers 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
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- BDFAOUQQXJIZDG-UHFFFAOYSA-N 2-methylpropane-1-thiol Chemical compound CC(C)CS BDFAOUQQXJIZDG-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012467 final product 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
- 238000005286 illumination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 238000005502 peroxidation Methods 0.000 description 2
- 239000013308 plastic optical fiber Substances 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical group CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 2
- 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
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-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
- XMWKORAMQLARNP-UHFFFAOYSA-N C(CCCCCCCCCCC)(=O)O.C(C)(C)(C)OO Chemical compound C(CCCCCCCCCCC)(=O)O.C(C)(C)(C)OO XMWKORAMQLARNP-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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- XYVQFUJDGOBPQI-UHFFFAOYSA-N Methyl-2-hydoxyisobutyric acid Chemical class COC(=O)C(C)(C)O XYVQFUJDGOBPQI-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- LOCHFZBWPCLPAN-UHFFFAOYSA-N butane-2-thiol Chemical compound CCC(C)S LOCHFZBWPCLPAN-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 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
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation 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
- 230000003292 diminished effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 239000004519 grease 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
- 239000012535 impurity 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
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-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
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940074869 marquis Drugs 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VBUNOIXRZNJNAD-UHFFFAOYSA-N ponazuril Chemical compound CC1=CC(N2C(N(C)C(=O)NC2=O)=O)=CC=C1OC1=CC=C(S(=O)(=O)C(F)(F)F)C=C1 VBUNOIXRZNJNAD-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-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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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a method for producing a (meth)acrylic polymer in which unreacted (meth)acrylic monomer can be recovered/reutilized in a state in which self-polymerization is not carried out. The method for producing the (meth)acrylic polymer comprises steps for continuously feeding a raw material composition containing a (meth)acrylic monomer containing >=50 mass% methyl methacrylate, a radical polymerization initiator and a chain-transfer agent to a polymerization vessel, continuously extracting a reaction mixture containing a (meth)acrylic polymer obtained by polymerizing at least a part of the (meth)acrylic monomer from the polymerization vessel, carrying out devolatilization treatment for separating and removing a volatile component containing a methyl methacrylate dimer and unreacted (meth)acrylic monomer, introducing the separated and removed volatile component into a distilling column and recovering a recovery component containing the methyl methacrylate dimer and the unreacted (meth)acrylic monomer so that the content of the methyl methacrylate dimer becomes 0.1-1.0 mass%.
Description
Technical field
The invention relates to manufacture method with successive polymerization manufactured (methyl) acrylic acid polymer.
Background technology
Polymerization is that (methyl) acrylic monomer of principal constituent is made (methyl) acrylic acid polymer and had characteristics such as the transparency, gasproof marquis property and good appearance with the methyl methacrylate, can be applicable to various fields such as illumination, billboard class, vehicle.Also be widely used in optical lens, optical applications such as disk basal disc, plastic optical fiber.
As the manufacture method of (methyl) acrylic acid polymer, generally use suspension polymerization more.But owing to used auxiliary agents such as suspension dispersive agent are sneaked into and its transparency are descended be not suitable for optical applications.In addition, owing to miscellaneous operations such as manufacturing processed needs to filter, washs, drying reduce productivity.
As the manufacture method of (methyl) acrylic acid polymer, except that above-mentioned suspension polymerization, also have known mass polymerization, solution polymerization process.Can make (methyl) acrylic acid polymer that the transparency does not reduce, has good characteristic with these methods.And recently noticeable be that the solution polymerization process that adopts mass polymerization or contain a small amount of solvent is made the continuous polymerization of boosting productivity continuously.But when making (methyl) acrylic acid polymer with these methods, in case uprising, the containing ratio of this polymkeric substance will produce what is called " gel effect ", and cause the phenomenon that polymerization rate sharply increases, promptly under the higher state of polymer content, be difficult to control stable polyreaction takes place.
Therefore, for realizing stable polyreaction, the degassing treatment process that the low stage of polymkeric substance containing ratio of being everlasting enters next step.Promptly under the low state of percent polymerization, stop polyreaction, thereby in the volatilization composition, have a large amount of unreacted (methyl) acrylic monomers, the discarded like this problem that can cause raw materials cost to increase.
So, just relevant for utilizing distillation tower etc. from this volatilization composition, to reclaim unreacted (methyl) acrylic monomer, the discussion of the gimmick that this unreacted (methyl) acrylic monomer is utilized again.But (methyl) acrylic monomer that reclaims also contains more other compositions, as utilizing these (methyl) acrylic monomers again, the problem that (methyl) acrylic acid polymer transparency reduces, thermotolerance descends of manufacturing is arranged.In addition, because conditions such as environment or management, (methyl) acrylic monomer generation auto-polymerization forms polymkeric substance and securely attached in the pipe arrangement before and after the distillation tower or in the accumulator tank, makes the manufacturing of (methyl) acrylic acid polymer be difficult to stable carrying out.
For example, the spy opens in the flat 10-87705 communique and disclosed the acidic substance that produce by removing in system, even utilize (methyl) acrylic monomer that reclaims also can obtain the method for high (methyl) acrylic acid polymer of the transparency again.Thereby need special equipment to produce the problem that manufacturing cost raises but remove acidic substance.In addition, can not prevent the problem of the auto-polymerization that when reclaiming (methyl) acrylic monomer, produces.Still exist the manufacturing that makes (methyl) acrylic acid polymer to be difficult to stable problem of carrying out.
Summary of the invention
In view of the foregoing, the purpose of this invention is to provide at unreacted (methyl) acrylic monomer and do not take place under the situation of auto-polymerization, the manufacture method of (methyl) acrylic acid polymer that can reclaim, utilize again.
The present invention is the manufacture method of (methyl) acrylic acid polymer, and it has
(A) the feedstock composition of (methyl) acrylic monomer, free radical polymerization initiator and the chain-transfer agent of the methyl methacrylate that contains at least 50 quality % supply with continuously polymeric kettle operation and
(B) in this polymeric kettle, make at least a portion polymerization of above-mentioned (methyl) acrylic monomer and obtain to contain above-mentioned (methyl) acrylic monomer partially polymerized at least (methyl) acrylic acid polymer the reaction mixture operation and
(C) this reaction mixture is extracted out continuously, is separated and remove the degassing processing that contains methyl methacrylate dipolymer and unreacted (methyl) acrylic monomer volatilization composition from above-mentioned polymeric kettle, obtain the operation of above-mentioned (methyl) acrylic acid polymer,
It is characterized in that it further has
(D) the above-mentioned volatilization composition of removing through separation being imported distillation tower, is the operation that reclaims under the condition of 0.1～1.0 quality % to the recovery composition above-mentioned methyl methacrylate dimer content in this recovery composition of control that has comprised at least a portion that is contained in the above-mentioned methyl methacrylate dipolymer in the above-mentioned volatilization composition and be contained in above-mentioned unreacted (methyl) acrylic monomer at least a portion in the above-mentioned volatilization composition.Manufacture method with this (methyl) acrylic acid polymer reclaims unreacted (methyl) acrylic monomer under the state that auto-polymerization does not take place, utilization becomes possibility again.
In above-mentioned operation (D), preferably keep the pressure in certain above-mentioned distillation tower, the reflux ratio by adjusting distillation tower and/or the thermophore temperature of the liquid phase portion in the above-mentioned distillation tower are Yi Bian the gas temperature of under reduced pressure controlling cat head is in 48～60 ℃ of scopes, Yi Bian distill.In addition, at least a portion of above-mentioned recovery composition is mixed into above-mentioned (methyl) acrylic monomer contained in the above-mentioned raw materials composition as being provided with (E) again, then better as the operation that at least a portion of feedstock composition is utilized again.
The manufacture method of above-mentioned (methyl) acrylic acid polymer is suitable during for mercaptan compound at above-mentioned chain-transfer agent.
Adopting the manufacture method of (methyl) of the present invention acrylic acid polymer to make to carry out recycling under the state of auto-polymerization does not take place unreacted (methyl) acrylic monomer becomes possibility.
Embodiment
The manufacture method of (methyl) of the present invention acrylic acid polymer is highly suitable for the mass polymerization or the solution polymerization of (methyl) acrylic monomer.At least to contain the methyl methacrylate of 50 quality % as (methyl) acrylic monomer, individually methyl methacrylate also can, the mixture of (methyl) alkyl acrylate beyond (methyl) methyl acrylate and the methyl methacrylate also can.(methyl) alkyl acrylate beyond the methyl methacrylate is not particularly limited, can uses (methyl) alkyl acrylate beyond the methyl methacrylate in (methyl) alkyl acrylate of the alkyl that for example has carbonatoms 1～18 to use.Concrete can enumerate methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) n-butyl acrylate, (methyl) vinylformic acid 2-ethylhexanoate, (methyl) dodecyl acrylate, (methyl) octadecyl acrylate etc.These can be separately with also but two or more is also used.In addition, said here " (methyl) vinylformic acid " is meant methacrylic acid or vinylformic acid (down together).
The present invention is applicable to make and contains methyl methacrylate units 80 quality % or more than it, also contain methyl methacrylate units (methyl) alkyl acrylate unitary (methyl) acrylic acid polymer in addition.At this moment, because methymethacrylate is generally all different with the polymerization activity of methyl methacrylate (methyl) alkyl acrylate in addition, so make under the situation of above-mentioned (methyl) acrylic acid polymer, suitably select the composition of (methyl) acrylic monomer according to its polymerization activity.For example, make that to contain methyl methacrylate units be that 80 quality % and methyl acrylate unit or ethyl propenoate unit are when being (methyl) acrylic acid polymer of 20 quality %, (methyl) though the composition of acrylic monomer with the difference of conditions such as the kind of free radical polymerization initiator, polymerization temperature and different, but still wish that methyl methacrylate is about 75 quality %, methyl acrylate or ethyl propenoate are for well about 25 quality %.
Free radical polymerization initiator of the present invention limits especially, known free radical polymerization initiators such as known organo-peroxide or azo-compounds independent or two or more be used in combination and get final product.Preferably using transformation period under the polymerization temperature of polymeric kettle is 10 seconds～1 hour free radical polymerization initiator.Too short free-radical initiator of transformation period can make the reaction homogeneity descend, and long free-radical initiator easily produced polymer blocks, was difficult to steady running in polymeric kettle the transformation period.It is best that to be to use transformation period under the polymerization temperature of polymeric kettle be 120 seconds～30 minutes free radical polymerization initiator.In addition, the value of " transformation period " of above-mentioned free radical polymerization initiator for be recorded in Japanese grease (strain) or and known products catalogue such as light pharmacy (strain) in numerical value.Have as such free-radical initiator: as tert-butyl hydroperoxide-3,5,5-tri-methyl hexanoic acid ester, the tert-butyl hydroperoxide laurate, tert-butyl hydroperoxide sec.-propyl one carbonic ether, uncle's hexyl peroxidation sec.-propyl one carbonic ether, tert-butyl hydroperoxide acetic ester, 1, two (tert-butyl hydroperoxides) 3 of 1-, 5,5-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 two (tert-butyl hydroperoxide) hexanes of 5-; 2-(formamyl 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).
The usage quantity of free radical polymerization initiator can be carried out appropriate selection according to the needs of polymerization temperature, productivity, and for example, (methyl) acrylic monomer with respect to 1 mole can use 5.0 * 10
-6～5.0 * 10
-5Amount about mole.
Chain-transfer agent of the present invention does not limit especially, as chlorine-containing compound, benzene compound, known chain-transfer agent such as mercaptan compound separately or two or more be used in combination and all can, but from chain-transfer agent efficient highland, angle that the heat-resisting decomposability of manufacturing (methyl) acrylic acid polymer is good considers that mercaptan compound is better.
Have as mercaptan compound: n-butyl mercaptan, isobutyl mercaptan, octyl mercaptan, positive Dodecyl Mercaptan, sec-butyl thioalcohol, secondary Dodecyl Mercaptan, tert.-butyl mercaptan etc. have alkyl or substituted alkyl primary, secondary, uncle's mercaptan compound; Thiophenol, thiocresol, aromatic series thiol compounds such as the 4-tertiary butyl-o-toluene thiophenol, Thiovanic acid and its ester, the mercaptan compound of carbonatomss such as hydroxyethyl mercaptan 3～18 etc.In these mercaptan compounds, with tert.-butyl mercaptan, n-butyl mercaptan, octyl mercaptan, particularly suitables such as positive Dodecyl Mercaptan.
Can be considered as about the usage quantity of chain-transfer agent purpose (methyl) acrylic acid polymer rerum natura and select suitable amount.For example, it is more suitable to make the weight-average molecular weight (polystyrene standard scaled value) of (methyl) acrylic acid polymer reach the usage quantity of 70000～150000 scopes.Specifically, to 100 moles of (methyl) acrylic monomers, the usage quantity of chain-transfer agent is 0.01～1.0 mole, and the best is 0.05～0.5 mole.Use the problem that the polymerization degree that (methyl) acrylic acid polymer too much can occur is low, product strength descends.Consumption is very few, the problem of the pyrolytic decline of (methyl) acrylic acid polymer can occur.
Both be applicable to as the form of at least a portion of polymerization of the present invention (methyl) Acrylic Acid Monomer and mass polymerization without inert solvent be applicable to the solution polymerization of using inert solvent again.Particularly preferably be mass polymerization.As use solution polymerization, preferably the amount of the inert solvent of Shi Yonging is less than 5 all quality % of reaction mixture, the same with mass polymerization like this, use small-amount free base polymerization starter just can improve percent polymerization effectively, make good (methyl) acrylic acid polymer of heat decomposition resistance more efficiently.As using the inert solvent amount to use at 5 quality % or the solution polymerization system more than it, unreacted (methyl) propylene of recovery is to have a large amount of inert solvents to exist in the monomer, thereby will establish separation circuit in addition sometimes.Can use methyl alcohol, ethanol as inert solvent, toluene, dimethylbenzene, acetone, hexone, ethylbenzene, ethyl methyl ketone, known organic solvent such as butylacetate.Particularly preferably be methyl alcohol, toluene, ethylbenzene, ethyl acetate.Inert solvent can be added in the feedstock composition of (methyl) acrylic monomer of above-mentioned containing, free radical polymerization initiator and chain-transfer agent and use.
Polymeric kettle of the present invention can use the slot type reaction unit that is provided with feedstock composition inlet, reaction mixture extraction opening and whipping appts.Whipping appts preferably has the polymeric kettle of making integral body can both keep the blended performance.In addition, as required, preferably be provided with the mechanism that energy heat extraction or control are heated to the polymerization temperature of setting.Temperature is controlled available known method and is carried out.As can adopting chuck to carry out temperature control, carry out temperature control by the thermophore circulation of the thrust-augmenting nozzle that in polymeric kettle, is provided with or coil pipe etc., also can implement temperature control by the temperature of regulating feedstock composition.By the polymerization temperature that temperature control sets, can be according to the kind of raw material, mixture is selected the temperature that suits than waiting.
The present invention has the reaction mixture that the auto-polymerization still is derived (methyl) acrylic acid polymer contained to the polymerization of small part (methyl) acrylic monomer, remove with unreacted (methyl) acrylic monomer to be the processing that outgases of the volatilization composition of major ingredient, to obtain the operation of (methyl) acrylic acid polymer in order to separate.The average retention time of reaction mixture in polymeric kettle is controlled to be implemented better in the scope in 1～6 hour.Controlled polymerization and can make good (methyl) acrylic acid polymer of molding processability stably in this scope.The too short usage quantity that then needs to increase free-radical initiator of residence time because of the increase of free-radical initiator makes polyreaction restive and the terminal double link content of (methyl) acrylic acid polymer is increased, and is difficult to make the good polymkeric substance of heat-resisting decomposability.Therefore the residence time preferably was at least 2 hours.Then reduce productivity and the dipolymer of (methyl) acrylic monomer is increased but above-mentioned average retention time is long, golden hour is controlled at and is at most 5 hours.
In addition, the polymkeric substance containing ratio from the reaction mixture that polymeric kettle is derived is controlled in 35～65 quality % scopes better.Too high can the generation of polymkeric substance containing ratio mixed and the heat transfer efficiency reduction problem of poor stability.The polymkeric substance containing ratio crosses that low can to make separation be that the cost of the volatile matter of major ingredient increases and industrialness is worth and reduces with unreacted (methyl) acrylic monomer.
The enforcement that the degassing is handled is under reduced pressure (when for example handling on being provided with the degassing extruding device of two outlets, the upside top hole pressure is adjusted at-0.01～-0.04Mpa about (gauge pressure), the downside top hole pressure is adjusted at-0.09～-0.1Mpa (gauge pressure) about), the reaction mixture of sending here continuously is heated to 200～290 ℃, separates continuously and remove the major part volatilization composition that unreacted to contain (methyl) acrylic monomer is a major ingredient.For example, outlet extruding machine (ベ Application ト エ ス Network ト Le one ダ) the type degassing extruding devices such as TEX (trade(brand)name) that can adopt JSW to make are handled in this degassing.The outlet number is not particularly limited, but it is better to consider to be provided with the degassing extruding devices of 2～4 outlets from degassing efficiency and operating cost.Remain in the preferred 1000 quality ppm of methymethacrylate dipolymer in gained (methyl) acrylic acid polymer or below it, and (methyl) acrylic monomer is at 3000 quality ppm or below it.Like this, can form (methyl) acrylic acid polymer with high heat-drawn wire and good plastic-molded workability.In addition, remaining chain-transfer agent is preferably at 50 quality ppm or below it.In the time of can suppressing molding processing (methyl) acrylic acid polymer like this because heating and painted problem.Above-mentioned these can be realized by the pressure of suitable setting degassing processing, the condition of temperature.
Can as required toward (methyl) acrylic acid polymer in add lubricant, UV light absorber, thermo-stabilizer, tinting material and antistatic agents etc. such as higher alcohols, high-grade aliphatic ester class when the above-mentioned degassing is handled or thereafter.
Separate the volatilization composition importing distillation tower of removing above-mentioned through degassing processing.Distillation tower is not had special restriction, use known getting final product.For example: about internal diameter 700mm * high 3600mm (recoverer 1800mm, the cold doubtful 1800mm of portion), stage number is about 6～20 sections, and reflux ratio is that about 0.4～2.0 multi-stage type distillation tower is better.
Separate unreacted (methyl) acrylic monomer that contains in the volatilization composition of removing as principal constituent through above-mentioned degassing processing, also contain the methyl methacrylate dipolymer shown in the following formula (1) (the following MMA dipolymer that also claims) usually
In addition, also may contain chain-transfer agent, the impurity that contains in inert solvent or the raw material, other reactant methanols, methyl propionate, methyl isobutyrate, various compositions such as vinylformic acid formicester, Alpha-hydroxy isobutyric acid methyl esters.
Generally speaking, because the boiling point of unreacted (methyl) acrylic monomer is lower than the boiling point of MMA dipolymer, the present invention is reclaimed as reclaiming composition through condensation from the gas that the distillation tower cat head obtains.Reclaim in the composition and contain MMA dipolymer and unreacted (methyl) acrylic monomer (also containing chain-transfer agent, inert solvent and above-mentioned various compositions etc. sometimes).But the present invention distills under the condition of 0.1～1.0 quality % with the content that the MMA dipolymer in the composition is reclaimed in control distillation back, reclaims composition and be maximum feature.Reclaim with this condition, both made and do not added stopper in addition to reclaiming in the composition, monomer polymerization such as methyl methacrylate can not take place yet and polymkeric substance securely attached to the pipe arrangement before and after the distillation tower, the phenomenon in the withdrawing can, the manufacturing of (methyl) acrylic acid polymer can be carried out continuously and stably.When MMA dipolymer amount less than 0.1 quality % the time, polymkeric substance can be securely attached in the pipe arrangement before and after the distillation tower, in the withdrawing can, the manufacturing of (methyl) acrylic acid polymer can not stably be carried out, and at the bottom of distilling Tata, derive the amount increase of discarded liquid and lose economy.When for a long time, utilize back (methyl) acrylic acid polymer to have degradation problem under painted, the thermotolerance again than 1.0 quality %.Preferably be controlled in 0.2～0.5 quality % scope.Polymerization the polymkeric substance machine matter that can not adhere to securely that becomes also at length do not get across, but generally infer it is the cause that the MMA dipolymer has been controlled the auto-polymerization of (methyl) acrylic monomer.MMA dimer shown in the above-mentioned formula (1) is the compound of 236 ℃ of boiling points, viscosity 4.1MPaS (25 ℃).For example, can record it with gas-chromatography and reclaim content in composition.
The adjustment of contained MMA dimer content in the above-mentioned recovery composition can realize by the gas temperature of control distillation tower cat head usually.Can reduce the content that reclaims MMA dipolymer in the composition by reducing distillation tower overhead gas temperature, improve the overhead gas temperature and increase and reclaim the dimeric content of MMA in the composition.Though will reclaim composition that the content of the MMA dipolymer in the composition is controlled to be 0.1～1.0 quality % and (methyl) acrylic monomer, create conditions etc. different and different, can be by for example under reduced pressure realizing by the distillation tower overhead gas is controlled between 48～60 ℃.The control of the gas temperature of cat head can make in the distillation tower and the pressure of front and back gas pipe arrangement etc. keeps certain state by vacuum pump etc., and the thermophore temperature of adjusting liquid phase portion in reflux ratio, the distillation tower realizes.
As mentioned above, the present invention is the manufacture method of (methyl) acrylic acid polymer, and it has
(A) contain methyl methacrylate 50 quality % or (methyl) acrylic monomer more than it, free radical polymerization initiator and chain-transfer agent feedstock composition successive supply with the polymeric kettle operation and
(B) in this polymeric kettle, make at least a portion polymerization of above-mentioned (methyl) acrylic monomer and obtain containing partially polymerized at least (methyl) acrylic acid polymer of above-mentioned (methyl) acrylic monomer the reaction mixture operation and
(C) this reaction mixture is extracted out continuously, handled to separate through the degassing and remove the volatilization composition that contains methyl methacrylate dipolymer and unreacted (methyl) acrylic monomer and the operation that obtains above-mentioned (methyl) acrylic acid polymer in above-mentioned polymeric kettle
It is characterized in that it further has
(D) the above-mentioned volatilization composition of removing through separation is imported distillation tower, to having comprised at least a portion that is contained in the above-mentioned methyl methacrylate dipolymer in the above-mentioned volatilization composition and be contained in the operation that reclaims under the recovering condition of above-mentioned methyl methacrylate dimer content to 0.1～1.0 quality % that the recovery composition of above-mentioned (methyl) acrylic monomer at least a portion in the above-mentioned volatilization composition contains in this recovery composition of control.Make with the manufacture method of this (methyl) acrylic acid polymer and under the state of auto-polymerization does not take place unreacted (methyl) acrylic monomer, not reclaim, to utilize again and become possibility.
Can partly or entirely discard though reclaim composition, one of them part can be reused in the manufacturing of (methyl) acrylic acid polymer.That is, the manufacture method as above-mentioned (methyl) of the present invention acrylic acid polymer preferably also is provided with
(E) at least a portion of above-mentioned recovery composition is mixed into above-mentioned (methyl) acrylic monomer that is contained in the above-mentioned raw materials composition, the operation of utilizing again as at least a portion of feedstock composition.Particularly be controlled at 10～50 quality % that (methyl) acrylic acid polymer makes used metha crylic monomer full dose for well reclaiming composition.Reclaim too much then (methyl) acrylic acid polymer of manufacturing of composition painted possibility is arranged.Reclaim the very few meeting of composition and cause the maintaining period that reclaims composition long and can not use, increase the discarded amount that reclaims composition and raw materials cost is increased.
Moreover in the manufacture method of (methyl) of the present invention acrylic acid polymer, in feedstock composition, having the chain-transfer agent of considerable influence to be divided into two compositions to the rerum natura of (methyl) acrylic acid polymer especially, to add polymeric kettles also be preferred embodiment.Promptly be divided into the adjustment composition of at least a portion that contains chain-transfer agent and at least two compositions of the main raw material composition beyond the adjustment composition and supply with polymeric kettles.When in polymeric kettle, mixing, as feedstock composition should by fixed proportioning supply with.At this moment, be transferred to than main raw material and become in one's duty chain transfer agent concentration height, can use as so-called masterbatch adjusting composition being adjusted in one's duty chain transfer agent concentration.By this quadrat method, adjust as required to the feed rate of the polymeric kettle of adjusting composition and the chain-transfer agent in the feedstock composition is finely tuned, thereby reach the rerum natura of adjusting (methyl) acrylic acid polymer of making to reach.
In addition, the one or more rerum natura (as melt flow rate, molecular weight etc.) of at least a portion of (methyl) acrylic acid polymer of making is carried out continuous or discontinuous mensuration.Have according to the operation of the rerum natura adjustment that records, (methyl) acrylic acid polymer rerum natura deviation that makes is diminished to the feed rate of the polymeric kettle of adjusting composition.
Have the superior transparency and weathering resistance with manufacture method of the present invention prepared (methyl) acrylic acid polymer and be widely used in various fields such as illumination, billboard class, vehicle.Also be applicable to simultaneously optical applications such as optical lens, disk basal disc, plastic optical fiber.In addition, also be applicable to when extrusion molding long large-scale moulded work and the high thin-walled moldings of setting resin temperature of the residence time in tube.
[embodiment]
Below, describe the present invention in detail with embodiment
(Production Example I)
In being provided with the slot type reaction unit of whipping appts, make dissolved oxygen be lower than 1ppm with nitrogen replacement after, drop into by following proportioning raw materials mixed composition 1, set 135 ℃ of polymerization temperatures, average retention time 3 hours carries out polyreaction.
＜feedstock composition 1 〉
Methyl methacrylate (MMA) 98.0 mass parts
Vinylformic acid formicester (MA) 2.0 mass parts
Octyl mercaptan 0.25 mass parts
Tert-butyl hydroperoxide-3,5,5 Trimethylhexanoic acid ester (MMA and MA add up to total amount relatively)
70 quality ppm
2), processings that outgas (250 ℃, upside top hole pressure-0.02MPa (gauge pressure), downside top hole pressure-0.097MPa (gauge pressure)) manufacturing (methyl) acrylic acid polymer the reaction mixture of extracting out from the slot type reaction unit is imported outlet extrude type degassing extruding device (the system TEX65 (trade(brand)name) of JSW, outlet number:.Gained (methyl) acrylic acid polymer is that transparent, HDT is that 100 ℃, residual (methyl) acrylic monomer are that 2400 quality ppm, residual MMA dipolymer are 500 quality ppm.HDT is with JIS K7191-1, and 2 estimate, and the content of residual composition is with the gas-chromatography evaluation.
(embodiment 1)
Internal diameter * highly (recoverer 1800mm is in the multi-stage type distillation tower of condensation part (1800mm), 8 sections of stage number, tower top pressure-0.084MPa (gauge pressure) for 700mm * 3600mm handling the volatilization composition importing of being removed through the degassing in the Production Example 1.This moment, the reflux ratio through adjusting distillation tower was that 0.55 to make the distillation tower tower top temperature be 52 ℃.With this understanding, the gas that comes from cat head of condensation, reclaim the fraction that obtains as following recovery composition 1.
＜recovery composition 1 〉
Methyl methacrylate (MMA) 97.5 mass parts
Propylene ester methyl ester (MA) 2.5 mass parts
Octyl mercaptan 0.11 mass parts
Secondly, with remembering that down feedstock composition 2 carries out and polyreaction, the degassing processing in the same manner of above-mentioned condition, make (methyl) acrylic acid polymer continuously.In addition, mix with other raw material compositions and obtain feedstock composition 2 reclaiming composition, after making dissolved oxygen content be lower than 1ppm with nitrogen replacement, use feedstock composition 2.
＜feedstock composition 2 〉
Methyl methacrylate (MMA) 68.75 mass parts
Methyl acrylate (MA) 1.25 mass parts
Reclaim composition 1 30.0 mass parts
Octyl mercaptan 0.217 mass parts
Tert-butyl hydroperoxide-3,5,5 Trimethylhexanoic acid ester (also comprise the MMA and the MA that reclaim composition relatively and add up to total amount) 70 quality ppm
Use feedstock composition 2 to implement running, handle the volatilization composition removed under these conditions through the degassing, the fraction of distilling, obtaining after the condensation replaces reclaiming composition 1, uses repeatedly, makes (methyl) acrylic acid polymer in 10 days continuously.Manufacturing can be stablized at 10 days and successive carries out.From making the percent polymerization of beginning after 10 days is 51 quality %, confirms that through gas-chromatography the amount of contained MMA dipolymer in the recovery composition is 0.2 quality %.It is transparent making (methyl) acrylic acid polymer, the weight-average molecular weight that converts with polystyrene standard is 98000, the mass ratio of each monomeric unit in the polymkeric substance is MMA/MA=98.5/1.5, HDT is that 100 ℃, residual (methyl) acrylic monomer are 2400 quality ppm, and residual MMA dipolymer is 700 quality ppm.
(embodiment 2)
Making the overhead gas temperature by the reflux ratio of adjusting distillation tower is 55 ℃, and identical with embodiment 1 in addition method reclaims following recovery composition 2 as fraction.
＜recovery composition 2 〉
Methyl methacrylate (MMA) 97.6 mass parts
Methyl acrylate (MA) 2.4 mass parts
Octyl mercaptan 0.12 mass parts
Secondly, use note feedstock composition 3 down to handle under the volatilization composition of removing is controlled at 55 ℃ in distillation tower overhead gas temperature the condition to distill through the degassing, condensation obtains fraction, except that replace reclaiming with it composition 2 uses repeatedly, with the same continuous manufacturing of carrying out metha crylic polymer on the 10th of method of embodiment 1.
＜feedstock composition 3 〉
Methyl methacrylate (MMA) 68.72 mass parts
Methyl acrylate (MA) 1.28 mass parts
Reclaim composition 2 30.0 mass parts
Octyl mercaptan 0.214 mass parts
Tert-butyl hydroperoxide-3,5,5 Trimethylhexanoic acid ester (also comprise the MMA and the MA that reclaim composition relatively and add up to total amount) 70 quality ppm
Manufacturing can be stablized at 10 days and successive carries out.The percent polymerization that begins after 10 days from manufacturing is 51 quality %, reclaims the content of contained MMA dipolymer in the composition and confirms as 0.4 quality % through gas-chromatography.Gained (methyl) acrylic acid polymer is transparent, the weight average molecular weight that polystyrene standard converts is 98000, the mass ratio of each monomeric unit in the polymkeric substance is MMA/MA=98.5/1.5, HDT is that 100 ℃ of residual (methyl) acrylic monomers are 2500 quality ppm, and residual MMA polymers is 800 quality ppm.
(comparative example 1]
Distilling the cat head gas temperature by the control of reflux ratio of adjusting distillation tower is outside 45 ℃, and reclaiming down with embodiment 1 with quadrat method, note reclaims composition 3 as fraction.
＜recovery composition 3 〉
Methyl methacrylate (MMA) 97.3 mass parts
Methyl acrylate (MA) 2.7 mass parts
Octyl mercaptan 0.09 mass parts
Secondly, use note feedstock composition 4 down, handle under the volatilization composition remove is controlled at 45 ℃ in distillation tower overhead gas temperature the condition through the degassing distill, condensation obtains fraction, except that replace reclaiming with it composition 3 uses repeatedly, with same method manufacturing (methyl) acrylic acid polymer of embodiment 2.
＜feedstock composition 4 〉
Methyl methacrylate (MMA) 68.81 mass parts
Methyl acrylate (MA) 1.19 mass parts
Reclaim composition 3 30.0 mass parts
Octyl mercaptan 0.223 mass parts
Tert-butyl hydroperoxide-3,5,5 Trimethylhexanoic acid ester (relatively also comprise and reclaim composition MMA and MA total total amount) 70 quality ppm
Make beginning after back 6 days, polymer attached and stopped up pipe arrangement securely all in the gas pipe arrangement from the distillation tower top of tower to total condenser can not be proceeded manufacturing.The content of the contained MMA dipolymer of recovery composition before pipe arrangement is about to obturation is confirmed as 0.05 quality % through gas-chromatography.
(comparative example 2)
Be controlled to be 64 ℃ except that the reflux ratio of adjusting distillation tower makes distillation cat head gas temperature, reclaim following recovery composition 4 as fraction with Production Example 1 same method.
＜recovery composition 4 〉
Methyl methacrylate (MMA) 97.8 mass parts
Methyl acrylate (MA) 2.2 mass parts
Octyl mercaptan 0.13 mass parts
Secondly, use note feedstock composition 5 down, to handle the volatilization composition remove through the degassing distills, replaces recovery composition 4 and outside using repeatedly, make (methyl) acrylic acid polymer with embodiment 1 continuously with quadrat method with condensation gained fraction under the overhead gas temperature of distillation tower is 64 ℃ condition.
＜feedstock composition 5 〉
Methyl methacrylate (MMA) 68.66 mass parts
Methyl acrylate (MA) 1.34 mass parts
Reclaim composition 4 30.0 mass parts
Octyl mercaptan 0.211 mass parts tert-butyl hydroperoxide-3,5,5 Trimethylhexanoic acid ester (relatively also containing the MMA that reclaims composition and the total total amount of MA) 70 quality ppm
Manufacturing can be stablized at 10 days and successive carries out.From making the percent polymerization of beginning after 10 days is 50 quality %, reclaims the amount of the MMA polymkeric substance that contains in the composition, confirms as 1.5 weight % through gas-chromatography.Gained (methyl) acrylic acid polymer is slightly yellow, with polystyrene standard converted weight molecular-weight average is 97000, the mass ratio of each monomeric unit: MMA/MA=98.5/1.5 in the polymkeric substance, HDT is 98 ℃, residual (methyl) acrylic monomer is 2800 quality ppm, and residual MMA dipolymer is 2400 quality ppm.
From above result, the amount of contained methyl methacrylate dipolymer is in 0.1～1.0 quality % scope in reclaiming composition, unreacted (methyl) acrylic monomer can reclaim under the state that auto-polymerization does not take place, and good (methyl) acrylic acid polymer of quality bills of materials stably.
Claims (4)
1. the manufacture method of (methyl) acrylic acid polymer, it has
(A) the feedstock composition of (methyl) acrylic monomer, free radical polymerization initiator and the chain-transfer agent of the methyl methacrylate that contains at least 50 quality % supply with continuously polymeric kettle operation and
(B) in this polymeric kettle, make at least a portion polymerization of above-mentioned (methyl) acrylic monomer and obtain to contain above-mentioned (methyl) acrylic monomer partially polymerized at least (methyl) acrylic acid polymer the reaction mixture operation and
(C) this reaction mixture is extracted out continuously, is separated and remove the degassing processing that contains methyl methacrylate dipolymer and unreacted (methyl) acrylic monomer volatilization composition from above-mentioned polymeric kettle, obtain the operation of above-mentioned (methyl) acrylic acid polymer,
It is characterized in that it further has
(D) the above-mentioned volatilization composition of removing through separation being imported distillation tower, is the operation that reclaims under the condition of 0.1～1.0 quality % to the recovery composition above-mentioned methyl methacrylate dimer content in this recovery composition of control that has comprised at least a portion that is contained in the above-mentioned methyl methacrylate dipolymer in the above-mentioned volatilization composition and be contained in above-mentioned unreacted (methyl) acrylic monomer at least a portion in the above-mentioned volatilization composition.
2. the manufacture method of (methyl) as claimed in claim 1 acrylic acid polymer, in above-mentioned operation (D), make in the above-mentioned distillation tower and keep certain pressure, by the reflux ratio of adjustment distillation tower and/or the thermophore temperature of the liquid phase portion in the above-mentioned distillation tower, the gas temperature of under reduced pressure controlling cat head is at 48～60 ℃, Yi Bian distill on one side.
3. the manufacture method of (methyl) as claimed in claim 1 or 2 acrylic acid polymer, it comprises that also (E) is mixed at least a portion of above-mentioned recovery composition in above-mentioned (methyl) acrylic monomer contained in the above-mentioned raw materials composition, the operation of utilizing again as at least a portion of feedstock composition.
4. as the manufacture method of any one described (methyl) acrylic acid polymer in the claim 1～3, described chain-transfer agent is a mercaptan compound.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003315502A JP4676687B2 (en) | 2003-09-08 | 2003-09-08 | Method for producing (meth) acrylic polymer |
| JP2003315502 | 2003-09-08 |
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| CN1605593A true CN1605593A (en) | 2005-04-13 |
| CN100410282C CN100410282C (en) | 2008-08-13 |
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| CN104203990A (en) * | 2012-03-22 | 2014-12-10 | 株式会社可乐丽 | Polymer compound, method for producing same, and molded article of same |
| CN104395360A (en) * | 2012-06-29 | 2015-03-04 | 株式会社可乐丽 | Methacrylic resin composition, molded product of same, and method for producing same |
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| JP5247314B2 (en) * | 2008-09-03 | 2013-07-24 | 三菱レイヨン株式会社 | Methacrylic resin composition |
| JP5621836B2 (en) * | 2012-12-13 | 2014-11-12 | 三菱レイヨン株式会社 | Methacrylic resin composition |
| JP5672321B2 (en) * | 2013-03-07 | 2015-02-18 | 三菱レイヨン株式会社 | Methacrylic resin composition |
| JP6575126B2 (en) * | 2014-05-08 | 2019-09-18 | 三菱ケミカル株式会社 | Method for producing furfural and method for producing furan |
| WO2016104701A1 (en) | 2014-12-26 | 2016-06-30 | 株式会社クラレ | Process for producing (meth)acrylic resin composition |
| EP3263610B1 (en) | 2015-02-27 | 2020-02-12 | Kuraray Co., Ltd. | Process for producing (meth)acrylic resin composition |
| DE102023107156A1 (en) | 2023-03-22 | 2024-09-26 | Röhm Gmbh | Process for improved processing of monomer-containing exhaust gases |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3277583B2 (en) * | 1993-02-02 | 2002-04-22 | 住友化学工業株式会社 | Method for producing methyl methacrylate polymer |
| JPH101511A (en) * | 1996-06-18 | 1998-01-06 | Mitsubishi Gas Chem Co Inc | Production of polymer |
| JP3636554B2 (en) * | 1996-09-20 | 2005-04-06 | 旭化成ケミカルズ株式会社 | Method for removing impurities in continuous solution polymerization |
| JP3289627B2 (en) * | 1996-12-26 | 2002-06-10 | 住友化学工業株式会社 | Method for producing methyl methacrylate polymer |
| US5980790A (en) * | 1997-03-04 | 1999-11-09 | Mitsubishi Gas Chemical Company, Inc. | Process for producing a copolymer |
| JP3628518B2 (en) * | 1998-07-14 | 2005-03-16 | 三菱レイヨン株式会社 | Methacrylic polymer and process for producing the same |
| JP3905781B2 (en) * | 2002-03-20 | 2007-04-18 | 株式会社日本触媒 | Method for producing polyacrylic acid |
| JP2004123896A (en) * | 2002-10-02 | 2004-04-22 | Mitsubishi Rayon Co Ltd | Method for manufacturing methacrylic polymer |
-
2003
- 2003-09-08 JP JP2003315502A patent/JP4676687B2/en not_active Expired - Lifetime
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104203990A (en) * | 2012-03-22 | 2014-12-10 | 株式会社可乐丽 | Polymer compound, method for producing same, and molded article of same |
| CN104203990B (en) * | 2012-03-22 | 2016-03-16 | 株式会社可乐丽 | Macromolecular compound and manufacture method thereof and molding |
| CN104395360A (en) * | 2012-06-29 | 2015-03-04 | 株式会社可乐丽 | Methacrylic resin composition, molded product of same, and method for producing same |
| CN104395360B (en) * | 2012-06-29 | 2016-12-07 | 株式会社可乐丽 | Methacrylic resin composition and its formed products and manufacture method |
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| CN100410282C (en) | 2008-08-13 |
| JP2005082687A (en) | 2005-03-31 |
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