CN100339401C - Manufacturing method of methacrylate ester size and resin plate - Google Patents
Manufacturing method of methacrylate ester size and resin plate Download PDFInfo
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- CN100339401C CN100339401C CNB2004100004545A CN200410000454A CN100339401C CN 100339401 C CN100339401 C CN 100339401C CN B2004100004545 A CNB2004100004545 A CN B2004100004545A CN 200410000454 A CN200410000454 A CN 200410000454A CN 100339401 C CN100339401 C CN 100339401C
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- acrylic ester
- nitrogen
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- -1 methacrylate ester Chemical class 0.000 title claims abstract description 55
- 239000011347 resin Substances 0.000 title claims abstract description 23
- 229920005989 resin Polymers 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 145
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 122
- 239000001301 oxygen Substances 0.000 claims abstract description 122
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 122
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 73
- 239000002994 raw material Substances 0.000 claims abstract description 69
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 238000004220 aggregation Methods 0.000 claims description 81
- 230000002776 aggregation Effects 0.000 claims description 81
- 239000002002 slurry Substances 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 38
- 238000005266 casting Methods 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 22
- 238000004090 dissolution Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 238000005187 foaming Methods 0.000 abstract description 15
- 230000000379 polymerizing effect Effects 0.000 abstract description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract 4
- 239000006188 syrup Substances 0.000 abstract 2
- 235000020357 syrup Nutrition 0.000 abstract 2
- 230000007547 defect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000113 methacrylic resin Substances 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 238000005502 peroxidation Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 230000006837 decompression Effects 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000005341 toughened glass Substances 0.000 description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- VXHFNALHLRWIIU-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)OC(=O)C(C)(C)C VXHFNALHLRWIIU-UHFFFAOYSA-N 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-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
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 238000007582 slurry-cast process Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical group CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-OUBTZVSYSA-N Ammonia-15N Chemical compound [15NH3] QGZKDVFQNNGYKY-OUBTZVSYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- BIVQBWSIGJFXLF-UHFFFAOYSA-N PPM-18 Chemical compound C=1C(=O)C2=CC=CC=C2C(=O)C=1NC(=O)C1=CC=CC=C1 BIVQBWSIGJFXLF-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- LOCHFZBWPCLPAN-UHFFFAOYSA-N butane-2-thiol Chemical compound CCC(C)S LOCHFZBWPCLPAN-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 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
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- IZYBEMGNIUSSAX-UHFFFAOYSA-N methyl benzenecarboperoxoate Chemical group COOC(=O)C1=CC=CC=C1 IZYBEMGNIUSSAX-UHFFFAOYSA-N 0.000 description 1
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 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
- 239000000049 pigment Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical group CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
To produce a methacrylate resin sheet substantially free from appearance defects such as polymerization foaming and voids with good productivity by effectively reducing the concentration of dissolved oxygen in monomers. A method for producing a methacrylate resin sheet comprises the steps of supplying a raw material comprising solely methyl methacrylate or a monomer mixture of 60 mass% or more of methyl methacrylate and 40 mass% or less of an acrylic ester into a polymerization vessel in which oxygen concentration is reduced to 3 mass% or less by supplying gaseous nitrogen beforehand, obtaining a methacrylate syrup by polymerizing part of the raw material with a dissolved oxygen concentration of 0.5 ppm or less in the polymerization vessel in the presence of a radical initiator such that the content of the polymer is from 10 mass% to 35 mass%, and polymerizing the methacrylate syrup obtained in the polymerization vessel by pouring the same into a mold.
Description
Technical field
The present invention relates to the dissolved oxygen concentration in independent methyl methacrylate or the monomer whose mixture is effectively reduced, make its partially polymerized method of making the methyl acrylic ester slurry, also relate to by making its polymerization make the manufacture method of methyl acrylic ester resin board on this slurry injection casting mold.
Background technology
As the method for making the methyl acrylic ester resin board, for example have methyl methacrylate or monomer whose mixture, perhaps the slurry that a part of polymerization of methyl methacrylate or monomer whose mixture is obtained injects between various models or two sheet glass or two metal sheets, makes its polymeric method in the presence of polymerization starter.
In addition, with methyl methacrylate the method that the dissolved oxygen concentration in the raw material of main component reduces, feed the method (with reference to patent documentation 1, special fair 7-94506 communique) of nitrogen in for example oriented stock liquid.Specifically, raw material injected casting mold after, for suppressing the generation of transparent inhibition Pyruvic Acid Methyl ester, use sebific duct etc. in stock liquid, to blast nitrogen, go out dissolved oxygen with nitrogen replacement.The raw material that has reduced dissolved oxygen concentration like this makes its polymerization in casting mold, just can obtain the superior methacrylic resin plate of the transparency.
According to the method for patent documentation 1 record, can improve the quality of methacrylic resin plate.But owing to directly blast nitrogen in the raw material in casting mold, the nitrogen that needs to carry out retaining in the casting mold before heated polymerizable is discharged to the operation outside the casting mold.In addition, the occasion that nitrogen is not exclusively discharged, remaining nitrogen foams when heated polymerizable in the casting mold, will form the vestige of recess on the resin board surface.And use sebific duct etc. feeds the complicated operation of nitrogen, imperfection aspect operability in casting mold.
Summary of the invention
The present invention is in order to solve above-mentioned prior art problems, promptly the purpose of this invention is to provide productivity and make the dissolved oxygen concentration that effectively reduces in the raw material well, be suitable for method, the manufacture method of methyl acrylic ester resin board also is provided as the slurry of the methyl acrylic ester resin board raw material of having eliminated macroscopic irregularitys such as polymerization foaming and space in essence.
The inventor for achieving the above object, research found that with keen determination, can reduce independent methyl methacrylate easily or be dissolved oxygen concentration in the monomer mixture of main component with the methyl methacrylate by specific method, so that finish the present invention.
Be that the present invention is the manufacture method of methyl acrylic ester slurry, this method comprises: oxygen concn is not higher than in the aggregation container of 3 quality % after feeding nitrogen in advance, add methyl methacrylate or add the operation of the raw material that forms by 60 quality % or the methyl methacrylate more than the 60 quality % and 40 quality % or the acrylate monomer blend below the 40 quality % and the dissolved oxygen concentration in the aggregation container smaller or equal to the raw material of 0.5ppm, exist the lower section that polymerization takes place at radical initiator, the polymer content that makes its formation is 10 quality %～35 quality %, thereby obtains the operation of methyl acrylic ester slurry.
The suitable manufacture method of above-mentioned methyl acrylic ester slurry comprises: with methyl methacrylate or the raw material that formed by 60 quality % or the methyl methacrylate more than the 60 quality % and 40 quality % or the acrylate monomer blend below the 40 quality %, oxygen concn was not higher than in the container (1) of 3 quality % after adding fed nitrogen in advance, up to the supply operation that is 25～67 volume % of container (1) cubic capacity; Carry out nitrogen replacement by the gas phase partial pressure that feeds nitrogen in the raw material in being added on container (1) or reduce in the container (1), the dissolved oxygen concentration that makes the interior raw material of container (1) is greater than the operation of 0.5ppm smaller or equal to 3ppm; The dissolved oxygen concentration that container (1) is interior is the raw material smaller or equal to 3ppm, oxygen concn was in the aggregation container (2) smaller or equal to 3 quality % after adding fed nitrogen in advance, and control adds the operation of the dissolved oxygen concentration of the raw material behind the aggregation container (2) smaller or equal to 0.5ppm.
Other suitable manufacture method of above-mentioned methyl acrylic ester slurry comprise: oxygen concn is not higher than in the aggregation container of 3 quality % after feeding nitrogen in advance, add methyl methacrylate or add the operation of the raw material that forms by 60 quality % or the methyl methacrylate more than the 60 quality % and 40 quality % or the acrylate monomer blend below the 40 quality % and carry out nitrogen replacement, make the operation of the interior material dissolution oxygen concn of aggregation container smaller or equal to 0.5ppm by the gas phase portion pressure that feeds nitrogen in the raw material in adding aggregation container or reduce in the aggregation container.
In addition, the present invention is the manufacture method of methyl acrylic ester resin board, and this method comprises that the methyl acrylic ester slurry that above-mentioned manufacture method is obtained injects casting mold, makes its polymeric operation.
The DO/O that uses central science society (セ Application ト ラ Le science society) to make in the present invention
2(model: the UC-12-SOL type) numerical value of Ce Dinging is obtained oxygen concn and dissolved oxygen concentration to instrument.Oxygen concn value in the container is used DO/O
2The mensuration unit of display " quality % " of instrument, the amount of material dissolution oxygen is with DO/O
2The mensuration unit of display " mg/L " of instrument is converted into concentration unit ppm (quality part per million).
Embodiment
Dissolved oxygen concentration in preferred in the present invention independent methyl methacrylate or the raw material that formed by 60 quality % or the methyl methacrylate more than the 60 quality % and 40 quality % or the acrylate monomer blend below the 40 quality % is reduced to 0.5ppm or below the 0.5ppm by ad hoc approach.For example can enumerate methyl acrylate, ethyl propenoate, butyl acrylate, cyclohexyl acrylate, 2-EHA, benzyl acrylate etc. as acrylate herein.
And preferred in aggregation container dissolved oxygen concentration exist at radical initiator smaller or equal to the raw material of 0.5ppm and issue the first portion polymerization, the polymer content of formation is 10 quality %～35 quality %, thereby forms the methyl acrylic ester slurry.Its polymerization process is not particularly limited, and can adopt known in the past the whole bag of tricks.
Radical polymerization initiator for example can be enumerated di-isopropyl peroxydicarbonate, new peroxide tert-butyl caprate, cross organo-peroxides such as trimethylacetic acid tertiary butyl ester, lauric acid superoxide, benzoyl peroxide, peroxy isopropyl carbonic acid tertiary butyl ester, peroxidized t-butyl perbenzoate, dicumyl peroxide, ditertiary butyl peroxide; 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-Diisopropyl azodicarboxylate, 1, and 1 '-azo two (cyclohexanenitrile) (1,1 '-Azobis (cyclohexane-1-carbonitrile), 2,2 '-azo two azo-compounds such as (2,4, the 4-trimethylpentane).With respect to 100 mass parts of monomer total amount, the addition of preferred radical polymerization initiator is 0.01～0.5 mass parts.
In addition, can also use molecular weight regulator as required.This molecular weight regulator for example can use have alkyl or substituted alkyl primary, second month in a season, uncle's mercaptan etc.Specifically, can enumerate for example n-butyl mercaptan, isobutyl mercaptan, octyl mercaptan, n-dodecane mercaptan, sec-butyl thioalcohol, secondary dodecyl mercaptans, tert.-butyl mercaptan etc.With respect to 100 mass parts of monomer total amount, the addition of preferred molecular weight conditioning agent is 0～0.5 mass parts.
As described above, more satisfactory in the present invention is in aggregation container by dissolved oxygen concentration obtain the methyl acrylic ester slurry smaller or equal to the raw material of 0.5ppm after, this methyl acrylic ester slurry is injected casting mold, make it that polymerization take place and make the methyl acrylic ester resin board.
Polymerization in the casting mold for example, at first makes the polymerization in 70～90 ℃ of temperature ranges of methyl acrylic ester slurry, reaches 80～95 quality % up to percent polymerization, makes its polymerizing curable form plate object again in 91～140 ℃ of temperature ranges.Polymerization time under preferred 70～90 ℃ is about 5 minutes～1 hour.Polymerization time under preferred 91～140 ℃ is about 3 minutes～2 hours.In addition, for the polymerization under 91～140 ℃, the preferred polymeric rate is more than or equal to 96 quality %, and more preferably percent polymerization is more than or equal to 99 quality %.
Heating means during polymerization can adopt known in the past the whole bag of tricks, for example, and heating in water bath, warm water spraying heating, steam heating, hot blast heating, electric heating heating, infrared heating, ultraviolet ray heating, electromagnetic induction heating etc.
Casting mold for example can list the casting mold that the pad by plate objects such as toughened glass, chrome plating, stainless plate and flexible vinyl chloride system etc. constitutes, perhaps by a pair of annular belt that moves with same speed along same direction relative to and and the casting mold that constitutes at the pad that its both sides of the edge and annular belt move with same speed etc.
The peroxide initiator of preferred 10 hours half life temperatures of the employed polymerization starter of polymerization in 50～58 ℃ of scopes in the casting mold.The object lesson of peroxide initiator for example can be enumerated; peroxyesters such as the own ester of peroxidation trimethylacetic acid uncle, the peroxidation trimethylacetic acid tert-butyl ester, the new hecanoic acid t-butyl ester of peroxidation; diacyl classes such as 2,4 dichloro benzene formyl radical superoxide, adjacent methyl benzoyl peroxide.Wherein, 10 hours half life temperatures of preferred polymeric initiator are more than or equal to 52 ℃ material, are more preferably less than to equal 56 ℃ material.In addition, have color when it is dyeed, consider, preferred peroxyesters, the preferred especially own ester of peroxidation trimethylacetic acid uncle, the peroxidation trimethylacetic acid tert-butyl ester from good color developing aspect for making the methyl acrylic ester resin board.
Peroxide initiator except that peroxyesters; for example diacyl class or two carbonates; equally can boost productivity with peroxyesters, but the tone first mate degree ground of specific colorants such as green colouring material is gone down, so must take into full account.In addition, use the polymerization starter of azo class such as azo two methyl pentane nitriles in a large number, can accelerate polymerization velocity, but the methacrylic resin plate that obtains can produce a large amount of bubbles, easily causes problems such as foaming during hot briquetting methacrylic resin plate.
The preferred per 1 gram methyl acrylic ester slurry of the addition of polymerization starter is 0.2 * 10
-6～20.0 * 10
-6In the mol scope, preferably its lower value is more than or equal to 0.4 * 10
-6Mol, preferred especially its lower value is more than or equal to 1.0 * 10
-6Mol.Addition can suitably determine by resin board thickness as requested.
In addition, in the methyl acrylic ester slurry, can also add various additives as required, for example antioxidant, softening agent, dyestuff, pigment, stripper etc.
Like this with the plate object that obtains after the slurry polymerisation, operation such as peel off through the casting mold of associating, just obtain the methyl acrylic ester resin board.The temperature of the preferred mo(U)ld face of temperature when peeling off is in 70～110 ℃ of scopes.The thickness of the methyl acrylic ester resin board that obtains in addition, is preferably 1～10mm.
Below the method that reduces independent methyl methacrylate in advance or reduce dissolved oxygen concentration in the raw material (being designated hereinafter simply as raw material) that is formed by 60 quality % or the methyl methacrylate more than the 60 quality % and 40 quality % or the acrylate monomer blend below the 40 quality % is in advance described.Reduce the operation of material dissolution oxygen concn among the present invention, used to have fed in advance that oxygen concn specifically, has following two suitable method (a) and (b) smaller or equal to the aggregation container of 3 quality % behind the nitrogen.
(a) after feeding nitrogen in advance in the container (1) of oxygen concn smaller or equal to 3 quality %, add 25～67 volume %s of raw material to container (1) cubic capacity, carry out nitrogen replacement by the gas phase portion pressure that feeds nitrogen in the raw material in being added on container (1) or reduce in the container (1) then, make in the raw material in the container (1) dissolved oxygen concentration smaller or equal to 3ppm, then with the raw material of the dissolved oxygen concentration in the container (1) smaller or equal to 3ppm, add and to feed in advance behind the nitrogen in the aggregation container (2) of oxygen concn smaller or equal to 3 quality %, make the dissolved oxygen concentration that adds the raw material in the aggregation container (2) smaller or equal to 0.5ppm.
(b) after feeding nitrogen in advance in the aggregation container of oxygen concn smaller or equal to 3 quality %, add raw material, carry out nitrogen replacement by the gas phase portion pressure that feeds nitrogen in the raw material in adding aggregation container or reduce in the aggregation container then, make the interior material dissolution oxygen concn of aggregation container smaller or equal to 0.5ppm.
At first method (a) is described.
In method (a), the material quantity that adds in the container (1) is 25～67 volume % of container (1) cubic capacity.Promptly add in the container (1) behind the raw material, gas phase portion accounts for 33～75 volume % of container (1) cubic capacity.If the add-on of raw material is smaller or equal to 67 volume % of container (1) cubic capacity, particularly, can suppresses raw material and be discharged to the outer amount of container when container bottom blasts nitrogen or when reducing gas phase portion pressure in the aggregation container and carrying out nitrogen replacement.In addition, if the add-on of raw material more than or equal to 25 volume % of container (1) cubic capacity, promptly the gas phase portion in the container (1) is smaller or equal to 75 volume %, is more satisfactory from the angle of costs of equipment such as container (1) miniaturization.
In method (a), before the adding raw material, feed nitrogen (promptly using air in the nitrogen replacement container) in advance and make the interior oxygen concn of container (1) smaller or equal to 3 quality %.People know, and the saturation capacity of monomer dissolved oxygen content is generally about tens ppm, make oxygen concn smaller or equal to 3 quality % by feed nitrogen in advance in container (1), can be reduced in the material dissolution oxygen concn that adds in the container (1).Herein, when the oxygen concn in the container (1) surpassed 3 quality %, the dissolved oxygen concentration of the raw material of adding can not reduce too much, in order to make final dissolved oxygen concentration smaller or equal to 0.5ppm, operating frequency or required time will increase, and see it is unfavorable from the angle of producing.
Then carry out nitrogen replacement by the gas phase portion pressure that feeds nitrogen in the raw material to being added on container (1) in or reduce in the container (1), the dissolved oxygen concentration that makes the interior raw material of container (1) greater than 0.5ppm smaller or equal to 3ppm.For example, can adopt from container (1) bottom directly feeds the mode (promptly blasting the nitrogen mode) and the gas phase portion pressure in the reduction reactor of nitrogen to raw material after, feed the mode known substitute modes such as (promptly reduce pressure nitrogen replacement mode) of nitrogen to barometric point.In addition, in order to finish nitrogen replacement rapidly, can increase operation with the interior raw material of agitator stirred vessel (1).
And then pass through the material dissolution oxygen concn in the container (1) greater than the raw material of 0.5ppm smaller or equal to 3ppm, add and to feed in advance behind the nitrogen in the aggregation container (2) of oxygen concn smaller or equal to 3 quality %, make the material dissolution oxygen concn that adds behind the aggregation container (2) smaller or equal to 0.5ppm.Promptly, only just can reduce dissolved oxygen concentration in the aggregation container (2), need in aggregation container (2), not reduce the operation of dissolved oxygen concentration to wherein adding raw material by making the interior oxygen concn of aggregation container (2) in advance smaller or equal to 3 quality %.In addition, even add material dissolution oxygen concn in the aggregation container (2) when surpassing 0.5ppm, by stirring in smaller or equal to the aggregation container (2) of 3 quality % at oxygen concn, just being easy to make the dissolved oxygen concentration of raw material is smaller or equal to 0.5ppm.
When the oxygen concn in the aggregation container (2) surpasses 3 quality % herein, the material dissolution oxygen concn that adds can not reduce too much, make final dissolved oxygen concentration must carry out other operations smaller or equal to 0.5ppm, and operating frequency increases, required time is elongated, sees it is unfavorable from the angle of producing.
Material quantity in the adding aggregation container (2) preferably accounts for 20～40 volume % of aggregation container (2) cubic capacity.Promptly add gas phase quality award from the ministry choosing in the aggregation container (2) behind the raw material and account for 60～80 volume % of container (2) cubic capacity.The add-on of raw material is smaller or equal to 40 volume %, the methyl acrylic ester slurry is made the back for suppressing, the aspect of the slurry foaming that causes during by the cooling of the decompression type of cooling, promptly suppress to cause by foaming raw material be leaked to outside the aggregation container (2) aspect more satisfactory.In addition, when the add-on of raw material more than or equal to 20 volume %, when promptly the interior gas phase of aggregation container (2) portion is smaller or equal to 80 volume %, more satisfactory from the angle of costs of equipment such as aggregation container (2) miniaturization.
Below method (b) is described.
In method (b), before the adding raw material, feed nitrogen in advance and make the interior oxygen concn of aggregation container smaller or equal to 3 quality %.People know, and the saturation capacity of monomer dissolved oxygen content is generally about tens ppm, but make oxygen concn in the aggregation container smaller or equal to 3 quality % by feeding nitrogen in advance, can reduce the material dissolution oxygen concn that joining in the aggregation container.If the oxygen concn in the aggregation container surpasses 3 quality % herein, the material dissolution oxygen concn that adds just can not reduce too many, make final dissolved oxygen concentration smaller or equal to 0.5ppm, and operating frequency will increase, required time will be elongated, see it is unfavorable from the angle of producing.
Gas phase portion pressure carries out nitrogen replacement in nitrogen or the reduction aggregation container by feeding in the raw material in adding aggregation container then, makes the interior material dissolution oxygen concn of aggregation container smaller or equal to 0.5ppm.Its concrete grammar or raw material add-on are identical with aforesaid method (a).
Aforesaid method (a) (b), promptly feed behind the nitrogen oxygen concn in advance smaller or equal to container and/or the aggregation container of 3 quality % by using, reduce the operation of material dissolution oxygen concn, describe in detail as the front then, by partially polymerized formation methyl acrylic ester slurry in aggregation container, with making its polymerization in this slurry injection casting mold, can make the methyl acrylic ester resin board again.
Same method (b) is compared, method (a) is required expense height on device, but during owing to manufacturing methyl acrylic ester slurry in aggregation container (2), the raw material that can in container (1), add the methyl acrylic ester slurry of making next time, reduce the dissolved oxygen concentration of this raw material, therefore improved the productivity of slurry.
Embodiment
The present invention will be described in more detail below by embodiment.Following " part " expression mass parts.And measure and estimate by following method.
1) the polymer content measuring method of slurry:
The slurry that obtains is added in a large amount of normal hexanes, filter the throw out that generates, the filter residue that obtains is carried out drying under reduced pressure, its quality of weighing calculates the ratio with former slurry, the percent polymerization of this ratio as the polymkeric substance of slurry.
2) measuring method of oxygen concn:
DO/O with central science society (セ Application ト ラ Le science society) manufacturing
2(model: the UC-12-SOL type) measure, the oxygen concentration of air value is directly used DO/O to instrument in the container
2The eudiometry unit of display " quality % " of instrument, the material dissolution oxygen concn is with DO/O
2The liquid assay unit of display " mg/L " of instrument is converted into concentration unit ppm (quality part per million).
3) ocular estimate of resin board:
By visual resin board surface imperfection and the inner foaming of observing manufacturing.
Embodiment 1
In the internal capacity that has prolong, stirring rake, outside chuck is 5 liters aggregation container, fed nitrogen 20 minutes with the speed of 0.3 liter of per minute, replace with nitrogen, make the oxygen concn in the aggregation container reach 1.5 quality %.Then, the inlet adding 1500g dissolved oxygen concentration from aggregation container top is the methyl methacrylate (hereinafter to be referred as MMA) of 8.5ppm.The MMA dissolved oxygen concentration is 2.0ppm behind the adding aggregation container.Then, stir with the rotating speed of 150rpm with stirring rake, simultaneously from upper end of condenser with vacuum pump with-90kPa pressure to the gas phase portion decompression of reactor 10 minutes, feed nitrogen subsequently to barometric point.Decompression nitrogen replacement required time is 12 minutes.The dissolved oxygen concentration of MMA is reduced to 0.5ppm like this.
With respect to 100 parts of MMA, add 0.05 part 2,2 '-azo two (2 then, the 4-methyl pentane nitrile) polymerization starter, heating kept after internal temperature reaches 80 ℃ 10 minutes, subsequently aggregation container inside was cooled to temperature in obtaining and is 30 ℃ methyl acrylic ester slurry.The polymer content of this methyl acrylic ester slurry is 25 quality %.
Then, adds 0.2 part of own ester of peroxidation trimethylacetic acid uncle, stir, outgased 5 minutes with-90kPa pressure decompression simultaneously, inject casting mold then with respect to 100 parts of methyl acrylic ester slurries.Casting mold adopts is that the flexible vinyl chloride gasket is arranged is a pair of stainless plate of 3mm between the thickness of wherein 300mm * 300mm, carries out lamination with the interval of about 8mm, usefulness clip fixed casting mold.Casting mold behind the injection slurry kept 30 minutes under 76 ℃ warm water atomize, make its polymerizing curable, thermal treatment 40 minutes in 130 ℃ air superheater then is cooled to about 90 ℃, cured article in the casting mold is peeled off from casting mold, obtained the methacrylic resin plate of the about 6mm of thickness of slab.Evaluation result is as shown in table 1.
Embodiment 2
In the internal capacity that has prolong, stirring rake, outside chuck is 20 liters aggregation container, fed nitrogen 10 minutes with the speed of 1.5 liters of per minutes, replace with nitrogen, make the oxygen concn in the aggregation container reach 3.0 quality %.Then the top inlet adding 9500g dissolved oxygen concentration from aggregation container is the MMA of 8.2ppm.MMA dissolved oxygen concentration behind the adding aggregation container is 2.5ppm.Insert the pipe arrangement of internal diameter 2.0mm then among the MMA in aggregation container, blasted nitrogen 25 minutes, carry out nitrogen replacement from the bottom with the speed of 1.5 liters of per minutes.Make the dissolved oxygen concentration of MMA be reduced to 0.3ppm like this.Subsequently with embodiment 1 same operation make the methyl acrylic ester slurry.The polymer content of this methyl acrylic ester slurry is 30 quality %.
Then the methyl acrylic ester slurry with respect to 100 parts adds 0.2 part of 2,4 dichloro benzene formyl radical superoxide, stirs, and reduces pressure and outgases 10 minutes with-120kPa pressure simultaneously, injects casting mold then.Casting mold adopts is that the flexible vinyl chloride gasket is arranged is a pair of stainless plate of 1.5mm between wherein 500mm * 500mm thickness, carries out lamination with the interval of about 10mm, usefulness clip fixed casting mold.Kept 40 minutes injecting the warm water tank that casting mold behind the slurry is dipped in 70 ℃, make its polymerizing curable, thermal treatment 1 hour in 120 ℃ infrared heating oven then is cooled to about 80 ℃, cured article in the casting mold is peeled off from casting mold, obtained the methacrylic resin plate of the about 8mm of thickness of slab.Evaluation result is as shown in table 1.
Embodiment 3
Speed with 1.0 liters of per minutes in internal capacity is 10 liters container (1) fed nitrogen 10 minutes, replaced with nitrogen, made oxygen concn reach 2.0 quality %.Then the top inlet from container (1) adds 4000gMMA and 2200g butyl acrylate (hereinafter to be referred as BA) (dissolved oxygen concentration of monomer mixture is 9.0ppm).Monomer dissolved mixture oxygen concn behind the adding container (1) is 6.5ppm.Insert the pipe arrangement of internal diameter 2.0mm then in the monomer mixture in container (1), the speed from the bottom with 0.7 liter of per minute fed nitrogen 15 minutes, carried out nitrogen replacement.The dissolved oxygen concentration of monomer mixture is reduced to 2.0ppm like this.
Secondly the top inlet of the monomer mixture in the container (1) from aggregation container (2) added the aggregation container (2), this aggregation container (2) feeds 20 minutes nitrogen with the speed of 1.5 liters of per minutes in advance, carry out nitrogen replacement, making oxygen concn is 0.5 quality %, and the internal capacity that has prolong, stirring rake, an outside chuck is 20 liters.Monomer dissolved mixture oxygen concn behind the adding aggregation container (2) is reduced to 0.9ppm.Then the rotating speed with 150rpm stirs in aggregation container (2), make the hot water circulation that adds in the chuck simultaneously, when internal temperature reaches 50 ℃, monomer mixture with respect to 100 parts adds 0.08 part 2 as polymerization starter, 2 '-Diisopropyl azodicarboxylate is heated to internal temperature 100 ℃ again and kept 8 minutes.Herein, to reach 50 ℃ of required times be 10 minutes to internal temperature, measures the interior monomer dissolved mixture oxygen concn of aggregation container (2) when internal temperature reaches 50 ℃, this concentration is reduced to 0.1ppm.
Kept 8 minutes at 100 ℃ once more, make internal temperature be cooled to 40 ℃ by the decompression cooling then, add 0.0005 part 2,6-two-tertiary butyl-4-methylphenol polymerization retarder obtains the methyl acrylic ester slurry.The polymer content of this methyl acrylic ester slurry is 31 quality %.
Then the methyl acrylic ester slurry with respect to 100 parts adds 0.2 part of own ester of peroxidation trimethylacetic acid uncle, stirs, and outgases 10 minutes with-90kPa pressure decompression simultaneously, injects casting mold then.Casting mold adopts is that the flexible vinyl chloride gasket is arranged is a pair of armourplate glass of 6mm between wherein 300mm * 300mm thickness, carries out lamination with the interval of about 8mm, usefulness clip fixed casting mold.Kept 30 minutes injecting the warm water that casting mold behind the slurry is dipped in 80 ℃, make its polymerizing curable, thermal treatment 1 hour in 130 ℃ hot-blast heater then is cooled to about 70 ℃, cured article in the casting mold is peeled off from casting mold, obtained the methacrylic resin plate of the about 5mm of thickness of slab.Evaluation result is as shown in table 2.
Comparative Examples 1
After in aggregation container, feeding nitrogen in advance and adding MMA, do not carry out the nitrogen replacement operation, with embodiment 1 identical operations, obtain the methacrylic resin plate of the about 6mm of thickness of slab.The variation and the evaluation result of the oxygen concn in the aggregation container, the dissolved oxygen concentration of MMA are as shown in table 1.
Comparative Examples 2
Except that in aggregation container, feeding in advance the nitrogen, with embodiment 1 identical operations, obtain the methacrylic resin plate of the about 6mm of thickness of slab.Oxygen concn in the aggregation container, the variation of the dissolved oxygen concentration of MMA and evaluation result are as shown in table 1.
Comparative Examples 3
Except that the operation that blasts nitrogen, with embodiment 2 identical operations, obtain the methacrylic resin plate of the about 8mm of thickness of slab.Oxygen concn in the aggregation container, the variation of the dissolved oxygen concentration of MMA and evaluation result are as shown in table 1.
Comparative Examples 4
In aggregation container, do not feed nitrogen in advance, in oxygen concn is the aggregation container of state of saturation, add among MMA, the MMA in this aggregation container and insert the metal tube of internal diameter 2.0mm, blast nitrogen from the bottom with the speed of 1.5 liters of per minutes and made that dissolved oxygen concentration is 2.0ppm the MMA in 25 minutes, in addition with embodiment 2 identical operations, obtain the methacrylic resin plate of the about 8mm of thickness of slab.Oxygen concn in the aggregation container, the variation of the dissolved oxygen concentration of MMA and evaluation result are as shown in table 1.
Comparative Examples 5
In comparative example 4, the operating time that blasts nitrogen becomes 50 minutes, makes that dissolved oxygen concentration is 0.3ppm among the MMA.In addition with Comparative Examples 4 identical operations, obtain the methacrylic resin plate of the about 8mm of thickness of slab.Oxygen concn in the aggregation container, the variation of the dissolved oxygen concentration of MMA and evaluation result are as shown in table 1.In this Comparative Examples, though ocular estimate is good, owing to reduce the dissolved oxygen concentration of MMA, the operation required time is elongated, and productivity significantly descends.
Comparative Examples 6
Except that in aggregation container (2), not feeding in advance the operation of nitrogen, with embodiment 3 identical operations, obtain the methacrylic resin plate of the about 5mm of thickness of slab.Oxygen concn in each container, the variation of the dissolved oxygen concentration of monomer mixture and evaluation result are as shown in table 2.
Comparative Examples 7
In the monomer mixture that does not carry out in being added on container (1), blast the operation of nitrogen, with embodiment 3 identical operations, obtain the methacrylic resin plate of the about 5mm of thickness of slab.Oxygen concn in each container, the variation of the dissolved oxygen concentration of monomer mixture and evaluation result are as shown in table 2.
Comparative Examples 8
Remove and in container (1), not feed nitrogen in advance, adding monomer mixture, operating time of blasting nitrogen become 60 minutes in oxygen concn is the container (1) of state of saturation, the dissolved oxygen concentration that makes monomer mixture is beyond the 2.0ppm, with with embodiment 3 identical operations, obtain the methacrylic resin plate of the about 5mm of thickness of slab.Oxygen concn in each container, the variation of the dissolved oxygen concentration of monomer mixture and evaluation result are as shown in table 2.In this Comparative Examples, though ocular estimate is good, owing to reduce the dissolved oxygen concentration of monomer mixture, the operation required time is elongated, and productivity significantly descends.
As shown in table 1, for embodiment 1～3, the dissolved oxygen concentration by reducing raw material can obtain not having polymerization foaming, the good goods of outward appearance in end article methyl acrylic ester resin board to make the methyl acrylic ester slurry smaller or equal to 1ppm.The opposing party and, Comparative Examples 1～4 and Comparative Examples 6～7 because the dissolved oxygen concentration of raw material reduces insufficiently when making the operation of methyl acrylic ester slurry, so cured article produces small foaming, visual appearance is relatively poor.In addition, Comparative Examples 5 and 8, though the outward appearance of methacrylic resin plate is good, in order to reduce dissolved oxygen concentration, the operation required time was elongated before raw material was partially polymerized, productivity significantly descends.
As mentioned above, the present invention effectively reduces the dissolved oxygen concentration of raw material (monomer or monomer mixture), has eliminated the methyl acrylic ester slurry that raw material was suitable for and the methyl acrylic ester resin board of the methyl acrylic ester resin board of macroscopic irregularitys such as polymerization foaming and space in essence, they can by high productivity of the present invention create.
Table 1
| Monomeric species | Oxygen concentration | Reduce the dissolved oxygen concentration required time | The polymer content of slurry | Casting mold | Cured thickness (mm) | Outward appearance | ||||
| Raw material before adding | Air in the aggregation container | Raw material in the aggregation container | Raw material before partially polymerized | |||||||
| Embodiment 1 | MMA | 8.5 ppm | 1.5 quality % | 2.0 ppm | 0.5 ppm | 32 minutes | 25 quality % | Stainless steel | 6 | Well |
| Embodiment 2 | MMA | 8.2 ppm | 3 quality % | 2.5 ppm | 0.3 ppm | 35 minutes | 30 quality % | Stainless steel | 8 | Well |
| Comparative Examples 1 | MMA | 8.5 ppm | 21 quality % | 8.5 ppm | 8.5 ppm | - | 18 quality % | Stainless steel | 6 | A large amount of small foaming |
| Comparative Examples 2 | MMA | 8.5 ppm | 21 quality % | 8.5 ppm | 3.0 ppm | 12 minutes | 20 quality % | Stainless steel | 6 | Small foaming is arranged |
| Comparative Examples 3 | MMA | 8.2 ppm | 3 quality % | 2.5 ppm | 25 ppm | 10 minutes | 20 quality % | Stainless steel | 8 | A large amount of small foaming |
| Comparative Examples 4 | MMA | 8.2 ppm | 21 quality % | 8.2 ppm | 2.0 ppm | 25 minutes | 22 quality % | Stainless steel | 8 | A large amount of small foaming |
| Comparative Examples 5 | MMA | 8.2 ppm | 21 quality % | 8.2 ppm | 0.3 ppm | 50 minutes | 30 quality % | Stainless steel | 8 | Well |
Table 2
| Monomeric species | Oxygen concentration | Reduce the dissolved oxygen concentration required time | The polymer content of slurry | Casting mold | Cured thickness (mm) | Outward appearance | ||||||
| Raw material before adding | The interior air of container (1) | The interior raw material of container (1) | The interior air of aggregation container (2) | The interior raw material of aggregation container (2) | Raw material before partially polymerized | |||||||
| Embodiment 3 | MMA/ BA | 9.0 ppm | 2.0 quality % | 2.0 ppm | 0.5 quality % | 0.9 ppm | 0.1 ppm | 55 minutes | 31 quality % | Toughened glass | 5 | Well |
| Comparative Examples 6 | MMA/ BA | 9.0 ppm | 1.9 quality % | 2.0 ppm | 21 quality % | 3.2 ppm | 3.2 ppm | 35 minutes | 20 quality % | Toughened glass | 5 | Small foaming is arranged |
| Comparative Examples 7 | MMA/ BA | 9.0 ppm | 1.9 quality % | 6.5 ppm | 0.4 quality % | 2.8 ppm | 2.0 ppm | 40 minutes | 21 quality % | Toughened glass | 5 | Small foaming is arranged |
| Comparative Examples 8 | MMA/ BA | 9.0 ppm | 21 quality % | 2.0 ppm | 0.4 quality % | 0.9 ppm | 0.1 ppm | 90 minutes | 31 quality % | Toughened glass | 5 | Well |
Claims (4)
1. the manufacture method of methyl acrylic ester slurry, it is characterized in that, this method comprises: concentration of oxygen is in 3 quality % or the aggregation container below the 3 quality % after feeding nitrogen in advance, the operation that adds methyl methacrylate or add the raw material that forms by 60 quality % or the methyl methacrylate more than the 60 quality % and 40 quality % or the acrylate monomer blend below the 40 quality % with
In the presence of radical initiator, polymerization partly takes place smaller or equal to the raw material of 0.5ppm in the concentration that makes dissolved oxygen in the aggregation container, and forming polymer content is the operation of the methyl acrylic ester slurry of 10 quality %～35 quality %.
2. the manufacture method of methyl acrylic ester slurry according to claim 1, it is characterized in that, this method comprises: concentration of oxygen is in 3 quality % or the aggregation container (1) below the 3 quality % after feeding nitrogen in advance, add methyl methacrylate or add the raw material that forms by 60 quality % or the methyl methacrylate more than the 60 quality % and 40 quality % or the acrylate monomer blend below the 40 quality %, until the supply operation of 25～67 volume % that account for container (1) cubic capacity with
Carry out nitrogen replacement by the gas phase partial pressure that feeds nitrogen in the raw material in being added on container (1) or reduce in the container (1), make in the container (1) the material dissolution oxygen concn greater than 0.5ppm smaller or equal to the operation of 3ppm with
With the concentration of the interior dissolved oxygen of container (1) raw material smaller or equal to 3ppm, add and to feed in advance that concentration of oxygen is in the following aggregation container (2) of 3 quality % or 3 quality % behind the nitrogen, make the concentration that is added on the material dissolution oxygen behind the aggregation container (2) operation smaller or equal to 0.5ppm.
3. the manufacture method of methyl acrylic ester slurry according to claim 1, it is characterized in that, it comprises: carry out nitrogen replacement by the gas phase portion pressure that feeds nitrogen in the raw material in being added on aggregation container or reduce in the aggregation container, make the operation of the interior material dissolution oxygen concn of aggregation container smaller or equal to 0.5ppm.
4. the manufacture method of a methyl acrylic ester resin board is characterized in that: will inject casting mold by the methyl acrylic ester slurry that any one manufacture method in the claim 1～3 obtains, and make its polymerization obtain the methyl acrylic ester resin board.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003017821A JP4286015B2 (en) | 2003-01-27 | 2003-01-27 | Method for producing methacrylate resin plate |
| JP2003017821 | 2003-01-27 |
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| CN1517369A CN1517369A (en) | 2004-08-04 |
| CN100339401C true CN100339401C (en) | 2007-09-26 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06128327A (en) * | 1992-10-15 | 1994-05-10 | Mitsubishi Rayon Co Ltd | High-purity methacrylic resin |
| JP2000026507A (en) * | 1998-07-14 | 2000-01-25 | Mitsubishi Rayon Co Ltd | Methacrylic polymer and its production |
| JP2002160228A (en) * | 2000-11-29 | 2002-06-04 | Sumitomo Chem Co Ltd | Method for producing methacrylic resin casting |
-
2003
- 2003-01-27 JP JP2003017821A patent/JP4286015B2/en not_active Expired - Lifetime
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2004
- 2004-01-29 CN CNB2004100004545A patent/CN100339401C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06128327A (en) * | 1992-10-15 | 1994-05-10 | Mitsubishi Rayon Co Ltd | High-purity methacrylic resin |
| JP2000026507A (en) * | 1998-07-14 | 2000-01-25 | Mitsubishi Rayon Co Ltd | Methacrylic polymer and its production |
| CN1303397A (en) * | 1998-07-14 | 2001-07-11 | 三菱丽阳株式会社 | Process for producing metha crylic polymer |
| JP2002160228A (en) * | 2000-11-29 | 2002-06-04 | Sumitomo Chem Co Ltd | Method for producing methacrylic resin casting |
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| CN1517369A (en) | 2004-08-04 |
| JP2004225011A (en) | 2004-08-12 |
| JP4286015B2 (en) | 2009-06-24 |
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