JP2005179609A - Method for producing water-soluble polyalkylene glycol (meth)acrylic ester - Google Patents
Method for producing water-soluble polyalkylene glycol (meth)acrylic ester Download PDFInfo
- Publication number
- JP2005179609A JP2005179609A JP2003426207A JP2003426207A JP2005179609A JP 2005179609 A JP2005179609 A JP 2005179609A JP 2003426207 A JP2003426207 A JP 2003426207A JP 2003426207 A JP2003426207 A JP 2003426207A JP 2005179609 A JP2005179609 A JP 2005179609A
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- JP
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- Prior art keywords
- meth
- water
- glycol
- reaction
- acrylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- -1 acrylic ester Chemical class 0.000 title claims abstract description 87
- 229920001515 polyalkylene glycol Polymers 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 170
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 97
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 34
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 33
- 239000010936 titanium Substances 0.000 claims abstract description 33
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 28
- 239000007795 chemical reaction product Substances 0.000 claims description 76
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 54
- 150000002148 esters Chemical class 0.000 claims description 40
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 33
- 239000002253 acid Substances 0.000 claims description 31
- 239000003463 adsorbent Substances 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 238000001179 sorption measurement Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002430 hydrocarbons Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 239000012535 impurity Substances 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 82
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 51
- 229940048053 acrylate Drugs 0.000 description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 28
- 238000001914 filtration Methods 0.000 description 28
- 238000006116 polymerization reaction Methods 0.000 description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 19
- 238000001816 cooling Methods 0.000 description 18
- 241001550224 Apha Species 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000002202 Polyethylene glycol Substances 0.000 description 12
- 229920001223 polyethylene glycol Polymers 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000003112 inhibitor Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 229920001451 polypropylene glycol Polymers 0.000 description 10
- 125000002947 alkylene group Chemical group 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 7
- 150000002334 glycols Chemical class 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000004811 liquid chromatography Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 5
- 229920001748 polybutylene Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000007259 addition reaction Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- PXDRFTPXHTVDFR-UHFFFAOYSA-N propane;titanium(4+) Chemical compound [Ti+4].C[CH-]C.C[CH-]C.C[CH-]C.C[CH-]C PXDRFTPXHTVDFR-UHFFFAOYSA-N 0.000 description 4
- 239000012264 purified product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 235000018185 Betula X alpestris Nutrition 0.000 description 2
- 235000018212 Betula X uliginosa Nutrition 0.000 description 2
- ZPGIVLOUVWCNHK-UHFFFAOYSA-N C(CC)[Zr] Chemical compound C(CC)[Zr] ZPGIVLOUVWCNHK-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 125000003547 cyclohexylalkoxy group Chemical group 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- SFUVLEGIZGPPNN-UHFFFAOYSA-N (2-pyridin-2-ylacetyl) 2-pyridin-2-ylacetate Chemical compound C=1C=CC=NC=1CC(=O)OC(=O)CC1=CC=CC=N1 SFUVLEGIZGPPNN-UHFFFAOYSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- RASBDVLERRNNLJ-UHFFFAOYSA-N CCCCO[Ti] Chemical compound CCCCO[Ti] RASBDVLERRNNLJ-UHFFFAOYSA-N 0.000 description 1
- RCZPHVPIOWNERS-UHFFFAOYSA-N CCCO[Ti] Chemical compound CCCO[Ti] RCZPHVPIOWNERS-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229940114077 acrylic acid Drugs 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical group [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- BCWYYHBWCZYDNB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O.CC(C)O.CC(C)O.CC(C)O BCWYYHBWCZYDNB-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 102220288073 rs151218932 Human genes 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Abstract
Description
本発明は、水溶性（メタ）アクリル酸ポリアルキレングリコールエステルの製造方法に関する。 The present invention relates to a method for producing a water-soluble (meth) acrylic acid polyalkylene glycol ester.
（メタ）アクリル酸ポリアルキレングリコールエステルを重合して得られる高分子化合物は、共重合するコモノマーの違いによって、石炭、カ−ボンブラック、顔料、石膏等の各種無機、有機物の分散剤、コンクリートの減水剤、帯電防止剤、樹脂硬化剤等の種々の用途に利用されている。例えば（メタ）アクリル酸ポリアルキレングリコールエステルとポリカルボン酸との共重合体は、粉流体の分散効果を有することが知られており、モルタルやコンクリート組成物の分散安定性に優れるためコンクリート混和剤として広く利用されている。 The polymer compound obtained by polymerizing the (meth) acrylic acid polyalkylene glycol ester is made of various inorganic and organic dispersants such as coal, carbon black, pigment, gypsum, and the like depending on the comonomer to be copolymerized. It is used for various applications such as water reducing agents, antistatic agents, resin curing agents and the like. For example, a copolymer of (meth) acrylic acid polyalkylene glycol ester and polycarboxylic acid is known to have a dispersion effect of powder fluid, and is excellent in dispersion stability of mortar and concrete composition. As widely used.
（メタ）アクリル酸ポリアルキレングリコールエステルは、アルコールにアルキレンオキシドを付加して得られるポリオキシアルキレングリコール等のポリアルキレングリコール化合物と、（メタ）アクリル酸とのエステル化や、ポリアルキレングリコール化合物と（メタ）アクリル酸エステルとのエステル交換等により得ることができ、酸触媒を用いたエステル化反応によって得た（メタ）アクリル酸ポリアルキレングリコールエステルの重合体に比べ、塩基性触媒によるエステル交換反応によって得た（メタ）アクリル酸ポリアルキレングリコールエステルの重合体は、セメント分散剤としての減水性が大幅に改善されると言われている（特許文献１）。 (Meth) acrylic acid polyalkylene glycol ester is an esterification of polyalkylene glycol compound such as polyoxyalkylene glycol obtained by adding alkylene oxide to alcohol and (meth) acrylic acid, or polyalkylene glycol compound ( Compared to the polymer of (meth) acrylic acid polyalkylene glycol ester, which can be obtained by transesterification with (meth) acrylic acid ester and obtained by esterification reaction using an acid catalyst, The obtained polymer of (meth) acrylic acid polyalkylene glycol ester is said to greatly improve water reduction as a cement dispersant (Patent Document 1).
特許文献１には、ポリアルキレングリコール化合物と（メタ）アクリル酸エステルとのエステル交換反応を行うに際して、塩基性触媒として水酸化ナトリウム等のアルカリ金属水酸化物、水酸化カルシウム等のアルカリ土類金属水酸化物、ナトリウムメトキシド、ナトリウムエトシド等のアルカリ金属アルコキシド、アンモニウム型アミンを交換基に持つ強塩基性イオン交換樹脂等を用いることが開示されている。しかしながらこれらの強塩基性触媒の存在下で反応性の高い二重結合を有する（メタ）アクリル酸エステルのエステル交換反応を行う場合には、二重結合へポリアルキレングリコール化合物が付加したものや、反応によって副生するアルコ−ルが二重結合へ付加したものなどの副生物が生成するという問題点を有していたり、例えばナトリウムアルコキシド等は反応途中で触媒が失活し易く反応率が上がりにくいという問題点も有していた。
In
本発明は上記の課題を解決すべくなされたもので、エステル交換法によって（メタ）アクリル酸ポリアルキレングリコールエステルを容易且つ効率よく得ることができる方法を提供することを目的とする。 The present invention has been made to solve the above problems, and an object of the present invention is to provide a method capable of easily and efficiently obtaining a (meth) acrylic acid polyalkylene glycol ester by a transesterification method.
即ち本発明は、
（１）グリコール化合物と、（メタ）アクリル酸エステルとを、チタンアルコキシド及び／又はジルコニウムのアルコキシドをエステル交換触媒として用いて反応させた後、水で処理して不溶性分を分離除去することを特徴とする水溶性（メタ）アクリル酸ポリアルキレングリコールエステルの製造方法、
（２）グリコール化合物が、エチレンオキシド成分２０重量％以上含有する下記（ａ）式で示されるグリコール化合物である上記（１）記載の水溶性（メタ）アクリル酸ポリアルキレングリコールエステルの製造方法、
Ｒ１Ｏ（ＡＯ）ｎＨ （ａ）
（但し、Ｒ１は水素、炭素数１〜３０の炭化水素基、ＡＯは炭素数２〜４のオキシアルキレン基、ｎは１〜３００の数を示す。）
（３）グリコール化合物と、（メタ）アクリル酸エステルとを、チタンアルコキシド及び／又はジルコニウムのアルコキシドをエステル交換触媒として用いて反応させて得た反応物を、水とともに吸着剤を用いて処理する上記（１）又は（２）記載の水溶性（メタ）アクリル酸ポリアルキレングリコールエステルの製造方法、
（４）吸着剤が水不溶性吸着剤である上記（３）記載の水溶性（メタ）アクリル酸ポリアルキレングリコールエステルの製造方法、
（５）水不溶性吸着剤が、酸化マグネシウム、酸化アルミニウム、二酸化ケイ素から選ばれた１種以上を含有する酸吸着能を持つ吸着剤及び／又は活性炭である上記（４）記載の水溶性（メタ）アクリル酸ポリアルキレングリコールエステルの製造方法、
を要旨とするものである。
That is, the present invention
(1) A glycol compound and (meth) acrylic acid ester are reacted using titanium alkoxide and / or zirconium alkoxide as a transesterification catalyst, and then treated with water to separate and remove insoluble components. A method for producing a water-soluble (meth) acrylic acid polyalkylene glycol ester,
(2) The method for producing a water-soluble (meth) acrylic acid polyalkylene glycol ester according to the above (1), wherein the glycol compound is a glycol compound represented by the following formula (a) containing 20% by weight or more of an ethylene oxide component:
R 1 O (AO) nH (a)
(However, R 1 is hydrogen, a hydrocarbon group having 1 to 30 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, and n is a number from 1 to 300.)
(3) The reaction product obtained by reacting a glycol compound with a (meth) acrylic acid ester using a titanium alkoxide and / or zirconium alkoxide as a transesterification catalyst, and using water and an adsorbent. (1) or a method for producing the water-soluble (meth) acrylic acid polyalkylene glycol ester according to (2),
(4) The method for producing a water-soluble (meth) acrylic acid polyalkylene glycol ester according to the above (3), wherein the adsorbent is a water-insoluble adsorbent,
(5) The water-soluble (meta) described in (4) above, wherein the water-insoluble adsorbent is an adsorbent having an acid adsorption ability and / or activated carbon containing at least one selected from magnesium oxide, aluminum oxide, and silicon dioxide. ) Method for producing acrylic acid polyalkylene glycol ester,
Is a summary.
本発明方法によれば、不純物含有量の少ない高純度の水溶性（メタ）アクリル酸ポリアルキレングリコールエステルを容易且つ安価に製造することができる。 According to the method of the present invention, a highly pure water-soluble (meth) acrylic acid polyalkylene glycol ester having a small impurity content can be produced easily and inexpensively.
本発明において用いるグリコール化合物としては、エチレンオキシド、プロピレンオキシド、ブチレンオキシド等のアルキレンオキシドの単独重合体や共重合体であるポリオキシアルキレングリコール、アルコール類に上記アルキレンオキシドの１種又は２種以上を付加重合させたり、上記ポリオキシアルキレングリコールにハロゲン化アルキルを反応させてポリオキシアルキレングリコールをアルコキシル化して得られるアルコキシポリオキシアルキレングリコール等が挙げられるが、一般式（ａ）
Ｒ１Ｏ（ＡＯ）ｎＨ （ａ）
（但し、Ｒ１は水素又は炭素数１〜３０の炭化水素基、ＡＯは炭素数２〜４のオキシアルキレン基、ｎは１〜３００の数）で示されるグリコール化合物が好ましい。好ましいポリオキシアルキレングリコールの一例としては、ポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコール、ポリエチレン−ポリプロピレングリコ−ル、ポリエチレン−ポリブチレングリコ−ル、ポリエチレン−ポリプロピレン−ポリブチレングリコール等が挙げられる。またアルコキシポリオキシアルキレングリコールの好ましい例としては、アルコキシ基が、メチルアルコール、エチルアルコール、プロピルアルコール、イソプロピルアルコール、ブチルアルコール、ヘキシルアルコール、オクチルアルコール、２−エチルへキシルアルコール、デシルアルコール、ラウリルアルコール、ミリスチルアルコール、セチルアルコール、ステアリルアルコール、オレイルアルコール等の飽和、不飽和の脂肪族アルコール類、シクロヘキシルアルコール等の脂環式アルコール類、オクチルフェノール、ノニルフェノール、ドデシルフェノール等の芳香族アルコ−ル類等の炭素数１〜３０の炭化水素基を持つアルコール由来の基であるものが挙げられる。例えば、メトキシポリオキシアルキレングリコール、エトキシポリオキシアルキレングリコール、プロポキシポリオキシアルキレングリコール、ブトキシポリオキシアルキレングリコール、ヘキシルアルコキシポリオキシアルキレングリコール、シクロへキシルアルコキシポリオキシアルキレングリコール、２−エチルへキシルアルコキシポリオキシアルキレングリコール、セチルアルコキシポリオキシアルキレングリコール、ステアリルアルコキシポリオキシアルキレングリコール、メチルフェノキシポリオキシアルキレングリコール、ノニルフェノキシポリオキシアルキレングリコール、デシルフェノキシポリオキシアルキレングリコール、ナフトキシポリオキシアルキレングリコール等が例示され、これらアルコキシポリオキシアルキレングリコール中のオキシアルキレン基としては、オキシエチレン、オキシプロピレン及び又はオキシブチレンが挙げられる。ここで、本発明の水溶性（メタ）アクリル酸ポリアルキレングリコールエステルの製造法では、エステル交換法により製造した反応物に水を添加した後、不純物を濾過処理するため、濾過処理工程において被濾過処理物が液状である必要がある。このため濾過処理工程において被濾過処理物を必要に応じて加熱するが、濾過処理は常温または少ない加熱で行うことが好ましい。上記一般式（ａ）で示すグリコール類のＲ１の炭素数が大きくなり過ぎると、濾過処理を高温で行わなければならなくなり、またアルキレンオキシドの付加モル数：ｎの数が多くなると、エステル交換反応時の反応性が低下するため、より効果的に本発明の（メタ）アクリル酸ポリアルキレングリコールエステルを得るためには、グリコール類として上記一般式（ａ）におけるＲ１が水素又は炭素数１から４の炭化水素基、ｎが５から５０であるものが好ましい。具体的には、ポリオキシエチレン（１０モル）グリコール、ポリオキシエチレン（２０モル）ポリオキシプロピレン（１０モル）グリコ−ル、メトキシポリオキシエチレン（１０モル）グリコール、メトキシポリオキシエチレン（３０モル）グリコール、メトキシポリオキシエチレン（２０モル）ポリオキシプロピレン（１０モル）グリコ−ル、エトキシポリオキシエチレン（１０モル）グリコール、プロポキシポリオキシエチレン（２５モル）グリコール、ブトキシポリオキシエチレン（１０モル）グリコール等が挙げられる。
As the glycol compound used in the present invention, one or more of the above alkylene oxides are added to polyoxyalkylene glycols and alcohols which are homopolymers or copolymers of alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide. Examples thereof include alkoxy polyoxyalkylene glycols obtained by polymerization or alkoxylation of polyoxyalkylene glycols by reacting alkyl halides with the above polyoxyalkylene glycols.
R 1 O (AO) nH (a)
(However, R 1 is hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, and n is a number from 1 to 300). Examples of preferred polyoxyalkylene glycols include polyethylene glycol, polypropylene glycol, polybutylene glycol, polyethylene-polypropylene glycol, polyethylene-polybutylene glycol, polyethylene-polypropylene-polybutylene glycol. In addition, as a preferable example of alkoxy polyoxyalkylene glycol, an alkoxy group is methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, Carbon such as saturated and unsaturated aliphatic alcohols such as myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, alicyclic alcohols such as cyclohexyl alcohol, and aromatic alcohols such as octylphenol, nonylphenol, and dodecylphenol. What is a group derived from an alcohol having a hydrocarbon group of 1 to 30 is exemplified. For example, methoxy polyoxyalkylene glycol, ethoxy polyoxyalkylene glycol, propoxy polyoxyalkylene glycol, butoxy polyoxyalkylene glycol, hexyl alkoxy polyoxyalkylene glycol, cyclohexyl alkoxy polyoxyalkylene glycol, 2-ethylhexyl alkoxy polyoxy Examples include alkylene glycol, cetyl alkoxy polyoxyalkylene glycol, stearyl alkoxy polyoxyalkylene glycol, methylphenoxy polyoxyalkylene glycol, nonylphenoxy polyoxyalkylene glycol, decylphenoxy polyoxyalkylene glycol, and naphthoxy polyoxyalkylene glycol. Alkoxypolyoxyalkyl The oxyalkylene groups in the glycol, polyoxyethylene, include oxypropylene and or oxybutylene. Here, in the production method of the water-soluble (meth) acrylic acid polyalkylene glycol ester of the present invention, after adding water to the reaction product produced by the transesterification method, the impurities are filtered, and thus filtered in the filtration step. The processed product needs to be liquid. For this reason, although the to-be-filtered object is heated as needed in the filtration treatment step, the filtration treatment is preferably performed at room temperature or with little heating. When the carbon number of R 1 of the glycols represented by the general formula (a) becomes too large, the filtration treatment must be performed at a high temperature, and when the number of added moles of alkylene oxide: n increases, transesterification occurs. Since the reactivity during the reaction is lowered, in order to obtain the (meth) acrylic acid polyalkylene glycol ester of the present invention more effectively, R 1 in the above general formula (a) is hydrogen or
アルコキシポリオキシアルキレングリコールを得るに当たり、アルコール類へアルキレンオキサイドを付加重合させる方法は、金属ナトリウム、金属カリウム等の金属類、水酸化ナトリウム、水酸化カリウム、水酸化リチウム等の各種金属水酸化物、水酸化マグネシウム、水酸化カルシウム等のアルカリ土類金属化合物、炭酸ナトリウム等の各種炭酸塩、ナトリウムメチラ−ト、カリウムメチラ−ト等の金属アルコラート類、三弗化ホウ素エーテル、塩化錫、ゼオライト等の塩基性触媒、プロトン酸、ルイス酸、固体酸等の酸性触媒等公知の重合触媒を用いて、アルコール類にアルキレンオキシドを５０〜２００℃程度の温度でアニオン重合、カチオン重合、配位アニオン重合等の公知の方法で付加重合させて得ることができる。 In obtaining alkoxy polyoxyalkylene glycol, the method of addition polymerization of alkylene oxide to alcohols includes metals such as metal sodium and metal potassium, various metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, Alkaline earth metal compounds such as magnesium hydroxide and calcium hydroxide, various carbonates such as sodium carbonate, metal alcoholates such as sodium methylate and potassium methylate, boron trifluoride ether, tin chloride, zeolite, etc. Using a known polymerization catalyst such as an acidic catalyst such as a basic catalyst, a protonic acid, a Lewis acid, and a solid acid, an alkylene oxide is converted to an alcohol at a temperature of about 50 to 200 ° C., anionic polymerization, cationic polymerization, coordination anionic polymerization, etc. It can be obtained by addition polymerization by a known method.
上記ポリオキシアルキレングリコールやアルコキシポリオキシアルキレングリコールのポリオキシアルキレン基が、２種以上のアルキレンオキシドで構成される場合、アルキレンオキシドがランダム重合していても、ブロック重合していても良いが、水溶性の良好な（メタ）アクリル酸ポリアルキレングリコールエステルを得る上でランダム重合していることが好ましい。また水溶性の良好な（メタ）アクリル酸ポリアルキレングリコールエステルを得る上で、ポリオキシアルキレン基を構成するアルキレンオキシド成分中に、エチレンオキサイド成分を２０重量％以上含むことが好ましい。 When the polyoxyalkylene group of the polyoxyalkylene glycol or alkoxy polyoxyalkylene glycol is composed of two or more alkylene oxides, the alkylene oxide may be randomly polymerized or block polymerized, In order to obtain a (meth) acrylic acid polyalkylene glycol ester having good properties, random polymerization is preferred. In order to obtain a (meth) acrylic acid polyalkylene glycol ester having good water solubility, the alkylene oxide component constituting the polyoxyalkylene group preferably contains 20% by weight or more of an ethylene oxide component.
（メタ）アクリル酸エステルとしては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル等の、（メタ）アクリル酸の低級アルコールエステルが挙げられる。 (Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate. And lower alcohol esters of (meth) acrylic acid.
本発明方法において、上記グリコール化合物と（メタ）アクリル酸エステルとのエステル交換触媒として用いるチタンアルコキシドとしては、テトラメトキシチタン、テトラエトキシチタン、テトラノルマルプロポキシチタン、テトライソプロポキシチタン、テトラノルマルブトキシチタン、テトライソブトキシチタンなどが挙げられる。またジルコニウムアルコキシドとしては、テトラメトキシジルコニウム、テトラエトキシジルコニウム、テトラノルマルプロポキシジルコニウム、テトライソプロポキシジルコニウム、テトラノルマルブトキシジルコニウム、テトライソブトキシジルコニウムなどが挙げられる。チタンアルコキシド、ジルコニウムアルコキシドは１種又は２種以上を混合して用いることができる。チタンアルコキシド、ジルコニウムアルコキシド等の触媒の添加量は、グリコ−ル化合物重量の０．０１〜１０重量％が好ましく、より好ましくは０．１〜５重量％である。触媒量がグリコール化合物重量の０．０１重量％未満であると、触媒としての効果が不充分であり、１０重量％を超えて添加しても添加量に比例したエステル交換反応効率の向上が見られず不経済である。また、ジルコニウムアルコキシドは、エステル交換反応による反応物の色相がチタンアルコキシドに対して優れるため、より色相の優れる水溶性（メタ）アクリル酸ポリアルキレングリコールエステルを得る上でジルコニウムアルコキシドを使用することが好ましい。 In the method of the present invention, titanium alkoxide used as a transesterification catalyst between the glycol compound and (meth) acrylic acid ester is tetramethoxy titanium, tetraethoxy titanium, tetra normal propoxy titanium, tetraisopropoxy titanium, tetra normal butoxy titanium, Examples include tetraisobutoxy titanium. Examples of the zirconium alkoxide include tetramethoxyzirconium, tetraethoxyzirconium, tetranormalpropoxyzirconium, tetraisopropoxyzirconium, tetranormalbutoxyzirconium, tetraisobutoxyzirconium and the like. Titanium alkoxide and zirconium alkoxide can be used alone or in combination of two or more. The addition amount of a catalyst such as titanium alkoxide or zirconium alkoxide is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the weight of the glycol compound. When the amount of the catalyst is less than 0.01% by weight of the glycol compound weight, the effect as a catalyst is insufficient, and even if the amount exceeds 10% by weight, the transesterification reaction efficiency is improved in proportion to the amount added. It is uneconomical. Moreover, since the hue of the reaction product by transesterification is superior to that of titanium alkoxide, zirconium alkoxide is preferably used for obtaining a water-soluble (meth) acrylic acid polyalkylene glycol ester having a more excellent hue. .
グリコール化合物と（メタ）アクリル酸エステルとのエステル交換反応には回分式、連続式のいずれの方法も採用することができ、通常、還流塔を備えた反応容器中にグリコール化合物、（メタ）アクリル酸エステル、触媒のチタンアルコキシド及び／又はジルコニウムアルコキシド、重合禁止剤と必要に応じて炭化水素類、ヘキサン、トルエン、シクロヘキサン等の溶媒を入れ加熱、還流させながら反応を行う。重合禁止剤としては、例えばハイドロキノン、ハイドロキノンモノメチルエーテル、フェノチアジン、フェノール誘導体、カテコール類、アミン類等が用いられ、グリコール化合物と（メタ）アクリル酸エステル合計量の５０〜５０００ｐｐｍの範囲で添加される。グリコール化合物と（メタ）アクリル酸エステルとの割合は、モル比でグリコール化合物：（メタ）アクリル酸エステル＝１：１〜１：２０が好ましく、１：３〜１：１０がより好ましい。（メタ）アクリル酸エステルの割合がグリコール化合物１モル当たり１モル未満の場合、未反応のグリコール化合物が不純物として残存する。２０モルを超える量の（メタ）アクリル酸エステルの使用は不経済となる。エステル交換反応は、反応温度８０〜１４０℃、還流比１：１〜１５：１、還流塔頂部温度は原料として使用する（メタ）アクリル酸エステルによって異なるが、過剰に存在する（メタ）アクリル酸エステルとエステル交換反応により生成するアルコ−ルを効率よく反応系外に留出させるため適切な共沸温度が好ましく、例えば（メタ）アクリル酸メチルとの反応では６０〜８０℃が好適である。反応温度８０℃未満では反応効率が悪く、１４０℃を超えると重合等の副反応が発生しやすくなる。また還流比が上記範囲を外れると、反応により生成するアルコ−ルを効率よく反応系外に留出できなくなる虞がある。エステル交換反応は常圧で行うことができるが、減圧下で行うことにより反応によって生じるアルコールを効率よく反応容器内から留出させることができる。エステル交換反応率は、液体クロマトグラフィ−、或いはヒドロキシル価を測定してグリコール化合物の残存量を求め、この値から算出することができる。反応時間は原料のモル比、触媒量、反応温度、還流比等によって異なるが、通常５〜１５時間程度でほぼ完結する。反応系内に残留する未反応の（メタ）アクリル酸エステルや、必要に応じて添加した溶媒は減圧蒸留することで除去することができる。 Both transesterification and continuous methods can be employed for the transesterification reaction between the glycol compound and the (meth) acrylic acid ester. Usually, the glycol compound and (meth) acrylic are contained in a reaction vessel equipped with a reflux tower. The reaction is conducted while heating and refluxing by adding an acid ester, a catalyst titanium alkoxide and / or zirconium alkoxide, a polymerization inhibitor and a solvent such as hydrocarbons, hexane, toluene, cyclohexane as necessary. As the polymerization inhibitor, for example, hydroquinone, hydroquinone monomethyl ether, phenothiazine, phenol derivatives, catechols, amines and the like are used, and added in the range of 50 to 5000 ppm of the total amount of glycol compound and (meth) acrylic acid ester. The molar ratio of the glycol compound to the (meth) acrylic acid ester is preferably glycol compound: (meth) acrylic acid ester = 1: 1 to 1:20, more preferably 1: 3 to 1:10. When the ratio of (meth) acrylic acid ester is less than 1 mole per mole of glycol compound, unreacted glycol compound remains as an impurity. The use of more than 20 moles of (meth) acrylic acid ester is uneconomical. The transesterification reaction has a reaction temperature of 80 to 140 ° C., a reflux ratio of 1: 1 to 15: 1, and the reflux tower top temperature varies depending on the (meth) acrylic acid ester used as a raw material, but (meth) acrylic acid is present in excess. An appropriate azeotropic temperature is preferable for efficiently distilling the alcohol produced by the ester exchange reaction with the ester out of the reaction system. For example, 60-80 ° C. is suitable for the reaction with methyl (meth) acrylate. If the reaction temperature is less than 80 ° C., the reaction efficiency is poor, and if it exceeds 140 ° C., side reactions such as polymerization tend to occur. On the other hand, if the reflux ratio is out of the above range, the alcohol produced by the reaction may not be efficiently distilled out of the reaction system. The transesterification reaction can be carried out at normal pressure, but the alcohol produced by the reaction can be efficiently distilled out from the reaction vessel by carrying out under reduced pressure. The transesterification rate can be calculated from this value by measuring the residual amount of glycol compound by measuring liquid chromatography or hydroxyl value. The reaction time varies depending on the molar ratio of raw materials, the amount of catalyst, the reaction temperature, the reflux ratio and the like, but is usually almost completed in about 5 to 15 hours. Unreacted (meth) acrylic acid ester remaining in the reaction system and the solvent added as necessary can be removed by distillation under reduced pressure.
上記反応が終了した後、水を添加し、グリコール化合物と（メタ）アクリル酸エステルとのエステル交換反応によって生成した水溶性（メタ）アクリル酸ポリアルキレングリコールエステルを水に溶解させる一方、濾過して水不溶性分を分離除去する。この処理によってエステル交換触媒として用いたチタンアルコキシドやジルコニウムアルコキシドが除去される。水の添加量は反応した（メタ）アクリル酸ポリアルキレングリコールエステルの種類によって適時選定されるが、チタンアルコキシド、ジルコニウムアルコキシド等の水不溶性分を分離除去するのに必要な、できるだけ少ない量を添加することが好ましい。水の添加量が少なすぎると、（メタ）アクリル酸ポリアルキレングリコールエステルの純度が低下する。通常、金属アルコキシド（チタンアルコキシド、ジルコニウムアルコキシドの合計）１モル当たりに対して等モル以上の水の添加が好ましく、また水の量が多いほど触媒が巨大分子化して除去が容易となることから、好ましくは重量で同量以上が、より好ましくは５倍量以上、更に好ましくは２０倍量以上である。水の量が金属アルコキシドに対して等モル未満の場合には、水に対する金属アルコキシドの不溶性化が不充分で、（メタ）アクリル酸ポリアルキレングリコールエステル中に不純物として残る虞がある。また水の添加量が多すぎると、不純物を除去した後必要に応じて（メタ）アクリル酸ポリアルキレングリコールエステルから水を除去する際の効率等の低下をきたす虞があるため、水の添加量は不純物が除ける範囲であればよく、添加量としては触媒量の２００倍以下が好ましい。 After the above reaction is completed, water is added, and the water-soluble (meth) acrylic acid polyalkylene glycol ester produced by the transesterification reaction between the glycol compound and the (meth) acrylic acid ester is dissolved in water, and filtered. Separate and remove water insolubles. By this treatment, titanium alkoxide and zirconium alkoxide used as a transesterification catalyst are removed. The amount of water added is appropriately selected depending on the type of the reacted (meth) acrylic acid polyalkylene glycol ester, but the smallest amount necessary to separate and remove water-insoluble components such as titanium alkoxide and zirconium alkoxide is added. It is preferable. When there is too little addition amount of water, the purity of the (meth) acrylic-acid polyalkylene glycol ester will fall. Usually, addition of an equimolar amount or more of water per mole of metal alkoxide (total of titanium alkoxide and zirconium alkoxide) is preferable, and the larger the amount of water, the easier the catalyst becomes and the removal becomes easier. Preferably, it is the same amount or more by weight, more preferably 5 times or more, still more preferably 20 times or more. When the amount of water is less than equimolar with respect to the metal alkoxide, the metal alkoxide is insufficiently insoluble in water and may remain as an impurity in the (meth) acrylic acid polyalkylene glycol ester. Also, if the amount of water added is too large, the efficiency when removing water from the (meth) acrylic acid polyalkylene glycol ester may be reduced as necessary after removing impurities. Is within a range that can remove impurities, and the addition amount is preferably 200 times or less of the catalyst amount.
本発明において水とともに吸着剤を併用すると、更に色相の改善や、残留する酸分を低下させることができ、更に品位の良好な水溶性（メタ）アクリル酸ポリアルキレングリコールエステルを得ることができるため好ましい。吸着剤としては酸吸着作用、アルカリ吸着作用、酸及びアルカリ吸着作用を有するものが用いられるが、水不溶性が好ましい。特に酸化マグネシウム、酸化アルミニウム、二酸化ケイ素から選ばれた１種以上を含有する酸吸着能を有する吸着剤や、木炭、泥炭、石炭、ヤシ殻などの原料を炭化後に二酸化炭素などのガス、或いは硫酸、燐酸等の薬品を用いて熱処理した微細孔を有する活性炭が好ましい。吸着剤の添加は、水と同時に行うこともでき、また水による処理を行った後、水不溶性分を濾過する前に添加することもできる。また水不溶性分の濾過をし易くするために必要に応じて濾過助剤を併用することができる。上記酸化マグネシウム、酸化アルミニウム、二酸化ケイ素から選ばれた１種類以上を含有する吸着剤としては、キョーワード１００、キョーワード２００、キョーワード３００、キョーワード４００、キョーワード５００、キョーワード６００Ｓ、キョーワード１０００、キョーワード２０００（以上協和化学工業株式会社製）等の市販の吸着剤を用いることができる。また市販の活性炭としては白鷺Ａ（武田薬品工業製）等が挙げられる。活性炭は、粉末状、粒状、繊維状、フェルト状、フィルタ−状、カ−トリッジ状等の種々形状を有するが、フェルト状、フィルター状、カートリッジ状の活性炭は、反応終了後に水を添加処理し、水不溶性分を濾過する際の濾過フィルターとして用いることができる。吸着剤の使用量は、（メタ）アクリル酸ポリアルキレングリコールエステルの品位向上効果と経済性を考慮すると、反応終了後の反応物合計重量の０．０１〜１０重量％が好ましく、より好ましくは０．０５〜５重量％である。水、または水と吸着剤による洗浄処理は、２０℃程度の所謂常温で行うことができるが、被処理物の粘度が高い場合は加熱して粘度を低下させて処理することもできる。しかしながら、（メタ）アクリル酸ポリアルキレングリコールエステルの加水分解、重合等の副反応を防ぐ意味で１００℃以下であることが好ましい。 In the present invention, when an adsorbent is used in combination with water, the hue can be further improved, the remaining acid content can be reduced, and a water-soluble (meth) acrylic acid polyalkylene glycol ester of better quality can be obtained. preferable. As the adsorbent, those having an acid adsorption action, an alkali adsorption action, an acid and an alkali adsorption action are used, and water-insoluble is preferable. In particular, an adsorbent having an acid adsorption ability containing at least one selected from magnesium oxide, aluminum oxide and silicon dioxide, a gas such as carbon dioxide after carbonizing raw materials such as charcoal, peat, coal and coconut shell, or sulfuric acid Activated carbon having fine pores heat-treated with a chemical such as phosphoric acid is preferred. The adsorbent can be added simultaneously with water, or after the treatment with water and before filtering the water-insoluble matter. Moreover, in order to make it easy to filter water-insoluble matter, a filter aid may be used in combination as necessary. Examples of the adsorbent containing one or more selected from magnesium oxide, aluminum oxide, and silicon dioxide include KYOWARD 100, KYOWARD 200, KYODWARD 300, KYOWARD 400, KYODWARD 500, KYODWARD 600S, Commercially available adsorbents such as 1000, KYOWARD 2000 (manufactured by Kyowa Chemical Industry Co., Ltd.) can be used. Examples of commercially available activated carbon include Shirakaba A (manufactured by Takeda Pharmaceutical). Activated carbon has various shapes such as powder, granular, fiber, felt, filter, cartridge, etc. However, felt, filter, cartridge-like activated carbon is treated by adding water after completion of the reaction. It can be used as a filtration filter for filtering water-insoluble matter. The amount of the adsorbent used is preferably 0.01 to 10% by weight of the total weight of the reaction product after completion of the reaction, more preferably 0, considering the quality improvement effect and economic efficiency of the (meth) acrylic acid polyalkylene glycol ester. 0.05 to 5% by weight. The washing treatment with water or water and an adsorbent can be performed at a so-called normal temperature of about 20 ° C. However, when the viscosity of the object to be treated is high, the treatment can be performed by heating to lower the viscosity. However, the temperature is preferably 100 ° C. or lower in order to prevent side reactions such as hydrolysis and polymerization of the (meth) acrylic acid polyalkylene glycol ester.
本発明方法によって、高品質の（メタ）アクリル酸ポリアルキレングリコールエステルが得られるのは、反応物中に均一に溶解しているエステル交換触媒のチタンアルコキシド、ジルコニウムアルコキシドが、水の添加によって加水分解され、水に不溶性な３次元的な巨大分子として反応物から分離し、この結果、触媒由来の不純物等を水不溶性物として析出させ、濾過処理することで反応物から分離除去されるものと推測される。 The high-quality (meth) acrylic acid polyalkylene glycol ester is obtained by the method of the present invention because the transesterification catalyst titanium alkoxide and zirconium alkoxide, which are uniformly dissolved in the reaction product, are hydrolyzed by adding water. And is separated from the reactant as a three-dimensional macromolecule that is insoluble in water. As a result, it is presumed that impurities derived from the catalyst, etc. are precipitated as a water-insoluble matter, and are separated and removed from the reactant by filtration. Is done.
本発明方法により得られる（メタ）アクリル酸ポリアルキレングリコールエステルの具体的な一例としては、メトキシポリエチレングリコールモノ（メタ）アクリレート、エトキシポリエチレングリコールモノ（メタ）アクリレート、プロポキシポリエチレングリコールモノ（メタ）アクリレート、ブトキシポリエチレングリコールモノ（メタ）アクリレート、メトキシポリエチレングリコールポリプロピレングリコールモノ（メタ）アクリレート、ヘキシルアルコキシポリエチレングリコール（メタ）アクリレート、シクロへキシルアルコキシポリエチレングリコール（メタ）アクリレート、２−エチルへキシルアルコキシポリエチレングリコール（メタ）アクリレ−ト、セチルアルコキシポリエチレングリコール（メタ）アクリレート、ステアリルアルコキシポリエチレングリコール（メタ）アクリレート、メチルフェノキシポリエチレングリコール（メタ）アクリレート、ノニルフェノキシポリエチレングリコール（メタ）アクリレート、デシルフェノキシポリエチレングリコール（メタ）アクリレート、ナフトキシポリエチレングリコール（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールポリプロピレングリコールモノ（メタ）アクリレート、ポリエチレングリコールポリプロピレングリコ−ルジ（メタ）アクリレート、ポリエチレングリコールポリブチレングリコールモノ（メタ）アクリレート、ポリエチレングリコールポリブチレングリコールジ（メタ）アクリレート等が挙げられる。 Specific examples of the (meth) acrylic acid polyalkylene glycol ester obtained by the method of the present invention include methoxypolyethylene glycol mono (meth) acrylate, ethoxypolyethylene glycol mono (meth) acrylate, propoxypolyethylene glycol mono (meth) acrylate, Butoxy polyethylene glycol mono (meth) acrylate, methoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, hexyl alkoxy polyethylene glycol (meth) acrylate, cyclohexyl alkoxy polyethylene glycol (meth) acrylate, 2-ethylhexyl alkoxy polyethylene glycol (meta ) Acrylate, cetyl alkoxy polyethylene glycol (meth) acrylate, Thearylalkoxypolyethyleneglycol (meth) acrylate, methylphenoxypolyethyleneglycol (meth) acrylate, nonylphenoxypolyethyleneglycol (meth) acrylate, decylphenoxypolyethyleneglycol (meth) acrylate, naphthoxypolyethyleneglycol (meth) acrylate, polyethyleneglycolmono ( (Meth) acrylate, polyethylene glycol di (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol di (meth) acrylate, polyethylene glycol polybutylene glycol mono (meth) acrylate, polyethylene glycol polybutylene glycol di (Meta) acryle Doors and the like.
本発明方法によって得られる水溶性（メタ）アクリル酸ポリアルキレングリコールエステルは種々の単量体と共重合して、石炭、カ−ボンブラック、顔料、石膏等の各種無機、有機物の分散剤、コンクリートの減水剤、帯電防止剤、樹脂硬化剤等として利用することができる。重合に使用される溶剤は一般的には、水、イソプロピルアルコ−ル等のアルコール類、シクロヘキサン、トルエン等の炭化水素類等が使用されるが、例えば重合物を水系分散剤等の用途として使用する場合には、水を溶媒として重合することが好ましい。本発明方法で得た水溶性（メタ）アクリル酸ポリアルキレングリコールエステルは、他の単量体と重合する際に水やアルコール等の水系溶媒を用いる場合、触媒等を濾過精製しただけの水を含む状態でも、そのまま重合に使用できる。重合に用いる場合、直ちに重合を行っても、水溶液の状態で保存した後、重合を行っても良い。 The water-soluble (meth) acrylic acid polyalkylene glycol ester obtained by the method of the present invention is copolymerized with various monomers to produce various inorganic and organic dispersants such as coal, carbon black, pigments and gypsum, and concrete. It can be used as a water reducing agent, antistatic agent, resin curing agent and the like. Generally, the solvent used for the polymerization is water, alcohols such as isopropyl alcohol, hydrocarbons such as cyclohexane and toluene, etc., but the polymer is used for applications such as aqueous dispersants. In this case, it is preferable to perform polymerization using water as a solvent. When water-soluble (meth) acrylic acid polyalkylene glycol ester obtained by the method of the present invention is used with an aqueous solvent such as water or alcohol when polymerizing with other monomers, water obtained by filtering and purifying the catalyst or the like is used. Even if it is contained, it can be used for polymerization as it is. When used for polymerization, polymerization may be performed immediately or polymerization may be performed after storage in an aqueous solution.
以下、実施例を挙げて本発明を更に詳細に説明する。
実施例１
２リットルの圧力反応装置にメタノ−ル３２ｇ（１モル）と触媒としてナトリウムメトキサイド０．５ｇを仕込み、反応容器内を窒素で充分置換した後、１００℃〜１３０℃でエチレンオキシド９６８ｇ（２２モル）を圧力５ｋｇ／ｃｍ２以下を保ちつつ、４時間かけて導入して付加反応を行った。導入終了後、１時間熟成を行い反応を終了し、引き続き、窒素導入下、温度１１０〜１１５℃において吸着剤としてキョーワード６００Ｓ（協和化学工業株式会社製）を１０ｇ添加して１時間吸着処理後、濾過を行ないエチレンオキシドが２２モル付加したメトキシポリエチレングリコ−ルを得た。続いて、攪拌装置、温度計、ガス導入管、還流管、冷却管を備えた２リットル反応フラスコに、上記メトキシポリエチレングリコ−ル（平均付加モル数２２モル）４４４ｇ（０．４４４モル）を仕込み、減圧下窒素を導入して１００〜１１０℃に加熱して水分を脱水した後、５０℃まで冷却してメタクリル酸メチル３５５ｇ（３．５５モル）、重合禁止剤としてハイドロキノンモノメチルエ−テルを１．２ｇ（１５００ｐｐｍ）、エステル交換触媒のテトライソプロピルチタン５ｇをいれ、攪拌下エステル交換反応により副生するメタノ−ルの留出が開始するまで徐々に加熱を行った。フラスコ内の反応温度が１００℃で留出を開始し、フラスコ内の反応温度１００℃〜１１５℃で副生するメタノ−ルを留出しながら反応を行い、共沸する留出物の塔頂温度は６５℃〜６８℃を保った。反応は６時間で終了し、反応物を冷却後、減圧下、未反応のメタクリル酸メチルを蒸留して除き、４６８ｇの粗反応物を得た。この粗反応物の色相はガードナーカラーで８、酸価は０．２４であった。この反応物２００ｇに水を８６ｇ（使用触媒重量に対して４１倍量）添加して４０℃で１時間攪拌を行った後、濾紙を用いて濾過を行なったところ、水分含有量２８．８重量％のメトキシポリエチレングリコール（エチレンオキシドの平均付加モル数２２）メタアクリル酸エステルが得られた。触媒由来のチタンの残存量を定量したところ、粗反応物中のチタン残存量は１３７４ｐｐｍで、水で処理後、濾過を行った後には２．８ｐｐｍであった。また、酸価は０．１２、色相はＡＰＨＡで１０、ヒドロキシル価は１．５であり、ヒドロキシル価から反応率を算出したところ９７．３％であった。触媒由来のチタン残存量、触媒由来のジルコニウムの残存量（以下、単にチタン残存量、ジルコニウム残存量と言う。）、反応率は以下のようにして求めた。
Hereinafter, the present invention will be described in more detail with reference to examples.
Example 1
A 2 liter pressure reactor was charged with 32 g (1 mol) of methanol and 0.5 g of sodium methoxide as a catalyst, and after sufficiently replacing the inside of the reaction vessel with nitrogen, 968 g (22 mol) of ethylene oxide at 100 to 130 ° C. Was added over 4 hours while maintaining a pressure of 5 kg / cm 2 or less to carry out an addition reaction. After completion of the introduction, the reaction was completed by aging for 1 hour. Subsequently, 10 g of KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added as an adsorbent at a temperature of 110 to 115 ° C. under introduction of nitrogen, and after 1 hour of adsorption treatment. Filtration was carried out to obtain methoxypolyethylene glycol to which 22 mol of ethylene oxide was added. Subsequently, 444 g (0.444 mol) of the methoxypolyethylene glycol (average added mole number: 22 mol) was charged into a 2-liter reaction flask equipped with a stirrer, a thermometer, a gas introduction tube, a reflux tube, and a cooling tube. After introducing nitrogen under reduced pressure and heating to 100 to 110 ° C. to dehydrate the water, it was cooled to 50 ° C. and 355 g (3.55 mol) of methyl methacrylate and 1 hydroquinone monomethyl ether as a polymerization inhibitor. .2 g (1500 ppm) and 5 g of tetraisopropyl titanium serving as a transesterification catalyst were added, and the mixture was gradually heated with stirring until distillation of methanol produced as a by-product by the transesterification reaction started. Distillation starts when the reaction temperature in the flask is 100 ° C., and the reaction is carried out while distilling methanol produced as a by-product at the reaction temperature of 100 ° C. to 115 ° C. in the flask. Maintained 65-68 ° C. The reaction was completed in 6 hours. After cooling the reaction product, unreacted methyl methacrylate was distilled off under reduced pressure to obtain 468 g of a crude reaction product. The crude reaction product had a Gardner color of 8 and an acid value of 0.24. After adding 86 g of water (41 times the amount of catalyst used) to 200 g of this reaction product and stirring at 40 ° C. for 1 hour, the mixture was filtered using a filter paper. The water content was 28.8 wt. % Methoxypolyethylene glycol (average added mole number of ethylene oxide 22) methacrylic acid ester was obtained. When the residual amount of titanium derived from the catalyst was quantified, the residual amount of titanium in the crude reaction product was 1374 ppm, and after treatment with water and filtration, it was 2.8 ppm. The acid value was 0.12, the hue was 10 with APHA, and the hydroxyl value was 1.5. The reaction rate was calculated from the hydroxyl value, which was 97.3%. The catalyst-derived titanium residual amount, the catalyst-derived zirconium residual amount (hereinafter simply referred to as titanium residual amount and zirconium residual amount), and the reaction rate were obtained as follows.
チタン、ジルコニウムの残存量
反応物試料を灰化した後、硝酸酸性の溶液にしてプラズマ発光分析装置を用いて標準液による検量線法でチタン、ジルコニウム含有量を測定した。
測定装置：プラズマ発光分析装置ＩＣＰＳ−１０００ＩＶ（島津製作所製）
標準液 ：チタン１０００ｍｇ／Ｌ標準液（関東化学株式会社製）
ジルコニウム１０００ｍｇ／Ｌ標準液（関東化学株式会社製）
Remaining amounts of titanium and zirconium After the reaction product sample was incinerated, the content of titanium and zirconium was measured by a calibration curve method using a standard solution using a plasma emission analyzer using a nitric acid acidic solution.
Measuring device: Plasma emission analyzer ICPS-1000IV (manufactured by Shimadzu Corporation)
Standard solution: Titanium 1000 mg / L standard solution (manufactured by Kanto Chemical Co., Inc.)
Zirconium 1000mg / L standard solution (manufactured by Kanto Chemical Co., Inc.)
反応率
日本油化学協会制定の基準油脂分析試験法（１９９６年版）のヒドロキシル価（ピリジン−無水酢酸法：２．３．６．２）測定方法に準拠して反応物のヒドロキシル価：ＯＨｒ（ｍｇＫＯＨ／ｇ）と、原料メトキシポリエチレングリコールのヒドロキシル価：ＯＨｍ（ｍｇＫＯＨ／ｇ）を測定し、これらの値から反応物中の未反応アルコキシポリアルキレングリコ−ルの含有量：Ａ（％）を下記（１）式より算出し、その値から下記（２）式により反応率：Ｂ（％）を算出する。
Ａ（％）＝ＯＨｒ÷ＯＨｍ×１００ （１）
Ｂ（％）＝１００−Ａ （２）
Reaction rate Hydroxyl number of reactants: OHr (mgKOH) in accordance with the hydroxyl number (pyridine-acetic anhydride method: 2.3.6.2) measurement method of the standard oil and fat analysis test method (1996 version) established by the Japan Oil Chemical Association / G) and the hydroxyl value of raw material methoxypolyethylene glycol: OHm (mgKOH / g), and from these values, the content of unreacted alkoxypolyalkylene glycol in the reaction product: A (%) Calculate from the formula (1), and the reaction rate: B (%) is calculated from the value by the following formula (2).
A (%) = OHr ÷ OHm × 100 (1)
B (%) = 100−A (2)
実施例２
実施例１と同様にして製造したエチレンオキシドの平均付加モル数２２モルのメトキシポリエチレングリコール（メタ）アクリル酸エステル粗反応物１００ｇに、４０℃で水を４３ｇ（使用触媒重量に対して４１倍量）添加して３０分攪拌を行った後、更に吸着剤としてキョーワード２０００（協和化学工業株式会社製）を１ｇ（粗反応物の１重量％）添加して同温度で３０分間攪拌した後、濾紙を用いて濾過を行なったところ、色相がＡＰＨＡで１０、水分含有量２８．４重量％のメトキシポリエチレングリコール（エチレンオキシドの平均付加モル数２２）メタアクリル酸エステルが得られ、このエステルのチタン残存量は０．２ｐｐｍ、酸価は０．０９であった。
Example 2
100 g of methoxypolyethylene glycol (meth) acrylic ester crude reaction product having an average addition mole number of 22 mol of ethylene oxide produced in the same manner as in Example 1, and 43 g of water at 40 ° C. (41 times the amount of catalyst used) After adding and stirring for 30 minutes, 1 g (1% by weight of the crude reaction product) of KYOWARD 2000 (manufactured by Kyowa Chemical Industry Co., Ltd.) as an adsorbent was added and stirred at the same temperature for 30 minutes, and then filter paper To obtain methoxypolyethylene glycol (average added mole number of ethylene oxide 22) methacrylate having a hue of APHA of 10 and a water content of 28.4% by weight, and the residual amount of titanium in this ester Was 0.2 ppm, and the acid value was 0.09.
実施例３
攪拌装置、温度計、ガス導入管、還流管、冷却管を備えた２リットル反応フラスコに実施例１と同様にして得たメトキシポリエチレングリコール（平均付加モル数２２モル）５００ｇ（０．５モル）を仕込み、メタクリル酸メチル３００ｇ（３モル）、重合禁止剤としてジエチルヒドロキシルアミン０．４ｇ（５００ｐｐｍ）、エステル交換触媒としてテトライソプロピルチタン２．０ｇ入れ、攪拌下徐々に加熱を開始し、副生するメタノールを留出しながら反応を行った。フラスコ内の反応温度は１１０℃〜１２２℃で、共沸する留出物の塔頂温度は６０℃〜７８℃を保った。反応は１０時間で終了し、反応物を冷却後、減圧下、未反応のメタクリル酸メチルを蒸留して除き、５３４ｇの粗反応物を得た。この粗反応物の色相はＡＰＨＡで１５０、酸価は０．１６であった。この反応物２００ｇに４０℃にて水８６ｇ（使用触媒重量に対して１１５倍量）を添加して１時間攪拌を行った後、更に吸着剤としてキョーワード２０００を２ｇ（粗反応物の１重量％）添加して同温度で３０分間攪拌を行い濾紙を用いて濾過を行なったところ、色相はＡＰＨＡで１０、水分含有量３０．６重量％のメトキシポリエチレングリコール（エチレンオキシドの平均付加モル数２２）メタアクリル酸エステルが得られた。チタン残存量の定量をおこなったところ、粗反応物中のチタン残存量は６１１ｐｐｍで、水とキョーワード２０００で処理後、濾過を行ったものは０．１ｐｐｍであった。また、精製物の酸価は０．０８、ヒドロキシル価は０．９で、ヒドロキシル価により算出した反応率は９８．４％であった。更に、この精製物１００ｇを攪拌装置、温度計、ガス導入管、冷却管を備えた１リットルの反応フラスコに入れ、８０〜９０℃で減圧脱水を行い水分を除いた。脱水物は水分含有量０．１重量％、脱水物の酸価は０．１４、色相はＡＰＨＡで３０であった。
Example 3
500 g (0.5 mol) of methoxypolyethylene glycol (average added mole number 22 mol) obtained in the same manner as in Example 1 in a 2 liter reaction flask equipped with a stirrer, thermometer, gas introduction tube, reflux tube, and cooling tube , 300 g (3 mol) of methyl methacrylate, 0.4 g (500 ppm) of diethylhydroxylamine as a polymerization inhibitor, and 2.0 g of tetraisopropyltitanium as a transesterification catalyst, gradually start heating with stirring and by-produce The reaction was conducted while distilling methanol. The reaction temperature in the flask was 110 ° C. to 122 ° C., and the top temperature of the azeotropic distillate was kept at 60 ° C. to 78 ° C. The reaction was completed in 10 hours, and after cooling the reaction product, unreacted methyl methacrylate was distilled off under reduced pressure to obtain 534 g of a crude reaction product. The crude reaction product had a hue of 150 APHA and an acid value of 0.16. After adding 86 g of water (115 times the weight of catalyst used) at 40 ° C. to 200 g of this reaction product and stirring for 1 hour, 2 g of Kyoward 2000 as an adsorbent (1 weight of the crude reaction product). The mixture was stirred at the same temperature for 30 minutes and filtered using a filter paper. The color was 10 APHA, and the moisture content was 30.6% by weight. Methoxypolyethylene glycol (average added mole number of ethylene oxide 22) A methacrylic acid ester was obtained. When the amount of remaining titanium was quantified, the amount of remaining titanium in the crude reaction product was 611 ppm, and the amount after filtration with water and Kyoward 2000 was 0.1 ppm. The acid value of the purified product was 0.08, the hydroxyl value was 0.9, and the reaction rate calculated by the hydroxyl value was 98.4%. Further, 100 g of this purified product was put into a 1 liter reaction flask equipped with a stirrer, a thermometer, a gas introduction tube, and a cooling tube, and dehydrated under reduced pressure at 80 to 90 ° C. to remove moisture. The dehydrated product had a water content of 0.1% by weight, the acid value of the dehydrated product was 0.14, and the hue was 30 with APHA.
実施例４
実施例３と同様にして得たエチレンオキシドの平均付加モル数２２モルのメトキシポリエチレングリコ−ル（メタ）アクリル酸エステル粗反応物１００ｇに、４０℃で水を２５ｇ（使用触媒重量に対して６８倍量）添加して３０分攪拌を行った後、更に吸着剤としてキョーワード２０００を０．５ｇ（粗反応物の０．５重量％）添加して同温度で３０分間攪拌を行い濾紙を用いて濾過を行なったところ、色相がＡＰＨＡで３０、水分含有量１７．７重量％のメトキシポリエチレングリコール（エチレンオキシドの平均付加モル数２２）メタアクリル酸エステルが得られ、チタン残存量の定量をおこなったところ０．７ｐｐｍであり、酸価は０．０９であった。
Example 4
100 g of methoxypolyethylene glycol (meth) acrylate crude reaction product having an average addition mole number of ethylene oxide of 22 mol obtained in the same manner as in Example 3 was added to 25 g of water at 40 ° C. (68 times the weight of catalyst used). After adding and stirring for 30 minutes, 0.5 g of Kyoward 2000 (0.5% by weight of the crude reaction product) was further added as an adsorbent, stirred for 30 minutes at the same temperature, and using filter paper. As a result of filtration, methoxypolyethylene glycol (average added mole number of ethylene oxide 22) methacrylate having a hue of 30 with APHA and a water content of 17.7% by weight was obtained, and the residual amount of titanium was determined. The acid value was 0.79.
実施例５
２リットルの圧力反応装置にメタノール３２ｇ（１モル）と触媒としてナトリウムメトキサイド０．２ｇを仕込み、反応容器内を窒素で充分置換した後、１００℃〜１３０℃でエチレンオキシド４４０ｇ（１０モル）を圧力５ｋｇ／ｃｍ２以下を保ちつつ、３時間かけて導入して付加反応を行った。導入終了後、１時間熟成を行って反応を終了し、引き続き、窒素導入下、温度１１０〜１１５℃で吸着剤としてキョーワード６００Ｓ（協和化学工業株式会社製）を５ｇ添加して１時間吸着処理後、濾過を行ないエチレンオキシドが１０モル付加したメトキシポリエチレングリコールを得た。続いて、攪拌装置、温度計、ガス導入管、還流管、冷却管を備えた、２リットル反応フラスコにメトキシポリエチレングリコール（平均付加モル数１０モル）４７２ｇ（１モル）を仕込み、メタクリル酸メチル４００ｇ（４モル）、重合禁止剤としてハイドロキノンモノメチルエーテルを１．３ｇ（１５００ｐｐｍ）、エステル交換触媒としてテトラノルマルプロピルジルコニウム４．４ｇをいれ、攪拌下徐々に加熱を開始し、副生するメタノールを留出しながら反応を行った。フラスコ内の反応温度は１０８℃〜１２３℃で、共沸する留出物の塔頂温度は６３℃〜６９℃を保った。反応は１０時間で終了し、反応物を冷却後、減圧下、未反応のメタクリル酸メチルを蒸留して除き、５３２ｇの粗反応物を得た。この粗反応物の色相はガードナーカラーで３、酸価は０．１７であった。この反応物を３０℃まで冷却し、反応物２００ｇに水を３５ｇ（使用触媒量に対して２１倍）添加して６０分攪拌を行った後、濾紙を用いて濾過を行なったところ、色相はＡＰＨＡで４０、水分含有量１４．２重量％のメトキシポリエチレングリコール（エチレンオキシドの平均付加モル数１０）メタアクリル酸エステルが得られた。ジルコニウム残存量の定量を行ったところ、粗反応物中のジルコニウム残存量は３２４０ｐｐｍで、水で処理後、濾過を行ったものではジルコニウム残存量１．７ｐｐｍであった。また、酸価は０．１０、ヒドロキシル価は１．１で、ヒドロキシル価により算出した反応率は９９．１％であった。
Example 5
A 2 liter pressure reactor was charged with 32 g (1 mol) of methanol and 0.2 g of sodium methoxide as a catalyst. After sufficiently replacing the inside of the reaction vessel with nitrogen, 440 g (10 mol) of ethylene oxide was pressurized at 100 to 130 ° C. While maintaining at 5 kg / cm 2 or less, the addition reaction was carried out over 3 hours. After completion of the introduction, the reaction was terminated by aging for 1 hour, followed by addition of 5 g of Kyoward 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) as an adsorbent at a temperature of 110 to 115 ° C. under nitrogen introduction, and an adsorption treatment for 1 hour. Thereafter, filtration was performed to obtain methoxypolyethylene glycol to which 10 mol of ethylene oxide had been added. Subsequently, 472 g (1 mol) of methoxypolyethylene glycol (average number of moles added: 10 mol) was charged into a 2 liter reaction flask equipped with a stirrer, a thermometer, a gas introduction tube, a reflux tube, and a cooling tube, and 400 g of methyl methacrylate was charged. (4 mol), 1.3 g (1500 ppm) of hydroquinone monomethyl ether as a polymerization inhibitor, and 4.4 g of tetranormal propylzirconium as a transesterification catalyst, gradually start heating with stirring, and distill off the by-produced methanol. The reaction was carried out. The reaction temperature in the flask was 108 ° C to 123 ° C, and the top temperature of the azeotropic distillate was kept at 63 ° C to 69 ° C. The reaction was completed in 10 hours. After cooling the reaction product, unreacted methyl methacrylate was distilled off under reduced pressure to obtain 532 g of a crude reaction product. The crude reaction product had a Gardner color of 3 and an acid value of 0.17. The reaction product was cooled to 30 ° C., 35 g of water (200 times the amount of catalyst used) was added to 200 g of the reaction product, stirred for 60 minutes, and then filtered using filter paper. A methoxypolyethylene glycol (average added mole number of ethylene oxide: 10) methacrylate having an APHA of 40 and a water content of 14.2% by weight was obtained. When the amount of zirconium remaining was quantified, the amount of zirconium remaining in the crude reaction product was 3240 ppm, and the amount of zirconium remaining after treatment with water and filtration was 1.7 ppm. The acid value was 0.10, the hydroxyl value was 1.1, and the reaction rate calculated by the hydroxyl value was 99.1%.
実施例６
攪拌装置、温度計、ガス導入管、還流管、冷却管を備えた２リットル反応フラスコに実施例５と同様にして得たメトキシポリエチレングリコール（平均付加モル数１０モル）４７２ｇ（１モル）を仕込み、メタクリル酸メチル４００ｇ（４モル）、重合禁止剤としてハイドロキノンモノメチルエーテルを１．７４ｇ（２０００ｐｐｍ）、エステル交換触媒としてテトライソプロピルチタン４．４ｇをいれ、攪拌下徐々に加熱を開始し、副生するメタノールを留出しながら反応を行った。フラスコ内の反応温度は１０５℃〜１２０℃で、共沸する留出物の塔頂温度は６６℃〜６９℃を保った。反応は６時間で終了し、反応物を冷却後、減圧下、未反応のメタクリル酸メチルを蒸留して除き、５３０ｇの粗反応物を得た。この粗反応物の色相はガードナーカラーで５、酸価０．２３であった。この反応物を３０℃まで冷却し、反応物２００ｇに水を１０ｇ（使用触媒量に対して６倍）添加して３０分攪拌を行った後、更に吸着剤としてキョーワード５００（協和化学工業株式会社製）を２．０ｇ（反応物の１重量％）添加して同温度で３０分間攪拌を行い濾紙を用いて濾過を行なったところ、色相はＡＰＨＡで７０、水分含有量４．０重量％のメトキシポリエチレングリコール（エチレンオキシドの平均付加モル数１０）メタアクリル酸エステルが得られた。チタン残存量の定量をおこなったところ、粗反応物中のチタン残存量は１３７２ｐｐｍで、水と吸着剤で処理後、濾過を行ったものではチタン残存量５．７ｐｐｍであった。また、酸価は０．１１、ヒドロキシル価は２．９で、ヒドロキシル価により算出した反応率は９７．６％であった。
Example 6
Into a 2-liter reaction flask equipped with a stirrer, thermometer, gas introduction tube, reflux tube, and cooling tube was charged 472 g (1 mol) of methoxypolyethylene glycol (average number of moles added: 10 mol) obtained in the same manner as in Example 5. , 400 g (4 mol) of methyl methacrylate, 1.74 g (2000 ppm) of hydroquinone monomethyl ether as a polymerization inhibitor, and 4.4 g of tetraisopropyl titanium as a transesterification catalyst, gradually start heating with stirring and by-produce The reaction was conducted while distilling methanol. The reaction temperature in the flask was 105 ° C to 120 ° C, and the top temperature of the azeotropic distillate was kept at 66 ° C to 69 ° C. The reaction was completed in 6 hours. After cooling the reaction product, unreacted methyl methacrylate was distilled off under reduced pressure to obtain 530 g of a crude reaction product. The crude reaction product had a hue of 5 in Gardner color and an acid value of 0.23. The reaction product was cooled to 30 ° C., 10 g of water (6 times the amount of catalyst used) was added to 200 g of the reaction product, and the mixture was stirred for 30 minutes. 2.0 g (1% by weight of the reaction product) was added and stirred at the same temperature for 30 minutes and filtered using filter paper. The hue was 70 with APHA and the water content was 4.0% by weight. Methoxypolyethylene glycol (average number of moles of ethylene oxide added 10) methacrylic acid ester was obtained. When the amount of remaining titanium was quantified, the amount of remaining titanium in the crude reaction product was 1372 ppm, and the amount of remaining titanium was 5.7 ppm after filtration with water and an adsorbent. The acid value was 0.11, the hydroxyl value was 2.9, and the reaction rate calculated by the hydroxyl value was 97.6%.
実施例７
実施例６と同様にして製造したエチレンオキシドの平均付加モル数１０モルのメトキシポリエチレングリコール（メタ）アクリル酸エステル粗反応物２００ｇに３０℃で水を１０ｇ（使用触媒重量に対して６倍量）添加して３０分攪拌を行った後、更に吸着剤として活性炭白鷺Ａを１．０ｇ（粗反応物の０．５重量％）添加して同温度で３０分間攪拌を行った後、濾紙を用いて濾過を行なったところ、色相がＡＰＨＡで３０、水分含有量４．４重量％のメトキシポリエチレングリコール（エチレンオキシドの平均付加モル数１０）メタアクリル酸エステルが得られ、チタン残存量の定量をおこなったところ３．２ｐｐｍであり、酸価は０．０４であった。
Example 7
10 g of water (30 times the amount of catalyst used) was added to 200 g of a crude reaction product of methoxypolyethylene glycol (meth) acrylic ester having an average addition mole number of 10 mol of ethylene oxide produced in the same manner as in Example 6. After stirring for 30 minutes, 1.0 g (0.5% by weight of the crude reaction product) of activated carbon birch A was further added as an adsorbent and stirred at the same temperature for 30 minutes. As a result of filtration, a methoxypolyethylene glycol (average added mole number of ethylene oxide: 10) methacrylic acid ester having a hue of APHA of 30 and a water content of 4.4% by weight was obtained, and the residual amount of titanium was determined. It was 3.2 ppm and the acid value was 0.04.
実施例８
攪拌装置、温度計、ガス導入管、還流管、冷却管を備えた２リットル反応フラスコに実施例１と同様にして得たメトキシポリエチレングリコール（平均付加モル数２２モル）５００ｇ（０．５モル）を仕込み、メタクリル酸メチル４００ｇ（４モル）、重合禁止剤としてジエチルヒドロキシルアミン０．４５ｇ（５００ｐｐｍ）、エステル交換触媒としてテトラノルマルプロピルジルコニウム４．５ｇ入れ、攪拌下徐々に加熱を開始し、副生するメタノールを留出しながら反応を行った。フラスコ内の反応温度は１１３℃〜１２５℃で、共沸する留出物の塔頂温度は６５℃〜７２℃を保った。反応は１２時間で終了し、反応物を冷却後、減圧下、未反応のメタクリル酸メチルを蒸留して除き、５３１ｇの粗反応物を得た。この粗反応物の色相はＡＰＨＡで１１０、酸価０．１５であった。この反応物２００ｇに４０℃にて水４０ｇ（使用触媒重量に対して２４倍量）を添加して１時間攪拌を行った後、濾紙を用いて濾過を行なったところ、色相はＡＰＨＡで１５、水分含有量１６．４重量％のメトキシポリエチレングリコール（エチレンオキシドの平均付加モル数２２）メタアクリル酸エステルが得られた。ジルコニウム残存量の定量をおこなったところ、粗反応物中のジルコニウム残存量は３３６０ｐｐｍで、水で処理後、濾過を行ったものは１．９ｐｐｍであった。また、精製物の酸価は０．０８、ヒドロキシル価は１．０で、ヒドロキシル価により算出した反応率は９８．２％であった。
Example 8
500 g (0.5 mol) of methoxypolyethylene glycol (average added mole number 22 mol) obtained in the same manner as in Example 1 in a 2 liter reaction flask equipped with a stirrer, thermometer, gas introduction tube, reflux tube, and cooling tube , 400 g (4 mol) of methyl methacrylate, 0.45 g (500 ppm) of diethylhydroxylamine as a polymerization inhibitor, and 4.5 g of tetranormalpropylzirconium as a transesterification catalyst, gradually start heating with stirring, The reaction was carried out while distilling off methanol. The reaction temperature in the flask was 113 ° C to 125 ° C, and the top temperature of the azeotropic distillate was kept at 65 ° C to 72 ° C. The reaction was completed in 12 hours, and after cooling the reaction product, unreacted methyl methacrylate was distilled off under reduced pressure to obtain 531 g of a crude reaction product. The color of this crude reaction product was 110 by APHA and the acid value was 0.15. After adding 40 g of water (24 times the amount of the catalyst used) to 200 g of this reaction product and stirring for 1 hour, the mixture was filtered using filter paper. As a result, the hue was 15 for APHA. A methoxypolyethylene glycol (average added mole number of ethylene oxide 22) methacrylic acid ester having a water content of 16.4% by weight was obtained. When the amount of zirconium remaining was quantified, the amount of zirconium remaining in the crude reaction product was 3360 ppm, and the amount after filtration with water was 1.9 ppm. The acid value of the purified product was 0.08, the hydroxyl value was 1.0, and the reaction rate calculated by the hydroxyl value was 98.2%.
実施例９
実施例８と同様にして製造したエチレンオキシドの平均付加モル数２２モルのメトキシポリエチレングリコール（メタ）アクリル酸エステル粗反応物２００ｇに３０℃で水を４０ｇ（使用触媒重量に対して２４倍量）添加して３０分攪拌を行った後、更に吸着剤としてキョーワード６００Ｓを２．０ｇ（粗反応物の１．０重量％）添加して同温度で３０分間攪拌を行った後、濾紙を用いて濾過を行なったところ、色相がＡＰＨＡで５、水分含有量１６．６重量％のメトキシポリエチレングリコール（エチレンオキシドの平均付加モル数２２）メタアクリル酸エステルが得られ、ジルコニウム残存量の定量をおこなったところ０．５ｐｐｍであり、酸価は０．０４であった。
Example 9
40 g of water (24 times the amount of catalyst used) was added at 30 ° C. to 200 g of a crude reaction product of methoxypolyethylene glycol (meth) acrylate ester having an average addition mole number of 22 moles of ethylene oxide produced in the same manner as in Example 8. After stirring for 30 minutes, 2.0 g of Kyoward 600S (1.0% by weight of the crude reaction product) was further added as an adsorbent and stirred for 30 minutes at the same temperature. As a result of filtration, methoxypolyethylene glycol (average added mole number of ethylene oxide 22) methacrylate having a hue of APHA of 5 and a water content of 16.6% by weight was obtained, and the amount of zirconium remaining was determined. The acid value was 0.54.
実施例１０
２リットルの圧力反応装置にメタノール３２ｇ（１モル）と触媒としてナトリウムメトキサイド０．２ｇを仕込み、反応容器内を窒素で充分置換した後、１００℃〜１３０℃でエチレンオキシド６６０ｇ（１５モル）を圧力５ｋｇ／ｃｍ２以下を保ちつつ、３．５時間かけて導入して付加反応を行った。導入終了後、１時間熟成を行って反応を終了し、引き続き、窒素導入下、温度１１０〜１１５℃で吸着剤としてキョーワード６００Ｓ（協和化学工業株式会社製）を７ｇ添加して１時間吸着処理後、濾過を行ないエチレンオキシドが１５モル付加したメトキシポリエチレングリコールを得た。続いて、攪拌装置、温度計、ガス導入管、還流管、冷却管を備えた２リットル反応フラスコに、メトキシポリエチレングリコール（平均付加モル数１５モル）５１９ｇ（０．７５モル）を仕込み、メタクリル酸メチル４５０ｇ（４．５モル）、重合禁止剤としてジエチルヒドロキシルアミン０．５ｇ（５１６ｐｐｍ）、エステル交換触媒としてテトラノルマルプロピルジルコニウム４．８ｇ入れ、攪拌下徐々に加熱を開始し、副生するメタノールを留出しながら反応を行った。フラスコ内の反応温度は１１２℃〜１２４℃で、共沸する留出物の塔頂温度は６４℃〜７３℃を保った。反応は１１時間で終了し、反応物を冷却後、減圧下、未反応のメタクリル酸メチルを蒸留して除き、５６５ｇの粗反応物を得た。この粗反応物の色相はＡＰＨＡで２５０、酸価０．１４であった。この反応物２００ｇに４０℃にて水８６ｇ（使用触媒重量に対して５１倍量）を添加して１時間攪拌を行った後、更に吸着剤としてキョーワード２０００を４ｇ（粗反応物の２重量％）添加して同温度で１時間攪拌を行い濾紙を用いて濾過を行なったところ、色相はＡＰＨＡで５、水分含有量２９．７重量％のメトキシポリエチレングリコール（エチレンオキシドの平均付加モル数１５）メタアクリル酸エステルが得られた。残存触媒の定量をおこなったところ、粗反応物中のジルコニウム残存量は３２９０ｐｐｍで、水とキョーワード２０００で処理後、濾過を行ったものは０．１ｐｐｍであった。また、精製物の酸価は０．０５、ヒドロキシル価は１．１で、ヒドロキシル価により算出した反応率は９８．６％であった。
Example 10
A 2 liter pressure reactor was charged with 32 g (1 mol) of methanol and 0.2 g of sodium methoxide as a catalyst. After sufficiently replacing the inside of the reaction vessel with nitrogen, 660 g (15 mol) of ethylene oxide was pressurized at 100 to 130 ° C. While maintaining at 5 kg / cm 2 or less, the addition reaction was carried out by introducing over 3.5 hours. After completion of the introduction, the reaction was terminated by aging for 1 hour. Subsequently, 7 g of KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added as an adsorbent at a temperature of 110 to 115 ° C. under nitrogen introduction, followed by an adsorption treatment for 1 hour. Thereafter, filtration was performed to obtain methoxypolyethylene glycol to which 15 mol of ethylene oxide was added. Subsequently, 519 g (0.75 mol) of methoxypolyethylene glycol (average added mole number of 15 mol) was charged into a 2 liter reaction flask equipped with a stirrer, a thermometer, a gas introduction tube, a reflux tube, and a cooling tube, and methacrylic acid was added. 450 g (4.5 mol) of methyl, 0.5 g (516 ppm) of diethylhydroxylamine as a polymerization inhibitor, 4.8 g of tetranormal propylzirconium as a transesterification catalyst, gradually start heating with stirring, and by-produce methanol. The reaction was carried out while distilling. The reaction temperature in the flask was 112 ° C to 124 ° C, and the top temperature of the azeotropic distillate was kept at 64 ° C to 73 ° C. The reaction was completed in 11 hours. After cooling the reaction product, unreacted methyl methacrylate was distilled off under reduced pressure to obtain 565 g of a crude reaction product. The crude reaction product had a hue of 250 by APHA and an acid value of 0.14. To 200 g of this reaction product, 86 g of water (51 times the amount of catalyst used) was added at 40 ° C. and stirred for 1 hour, and 4 g of Kyoward 2000 as an adsorbent (2% of the crude reaction product). The mixture was stirred at the same temperature for 1 hour and filtered using filter paper. The color was 5 APHA and the moisture content was 29.7% by weight. Methoxypolyethylene glycol (average added mole number of ethylene oxide 15) A methacrylic acid ester was obtained. When the residual catalyst was quantified, the amount of zirconium remaining in the crude reaction product was 3290 ppm, and the amount after filtration with water and Kyoward 2000 was 0.1 ppm. Further, the acid value of the purified product was 0.05, the hydroxyl value was 1.1, and the reaction rate calculated by the hydroxyl value was 98.6%.
実施例１１
実施例１０と同様にして製造したエチレンオキシドの平均付加モル数１５モルのメトキシポリエチレングリコール（メタ）アクリル酸エステル粗反応物２００ｇに３０℃で水を８６ｇ（使用触媒重量に対して５１倍量）添加して３０分攪拌を行った後、更に吸着剤として活性炭白鷺Ａを１．０ｇ（粗反応物の０．５重量％）添加して同温度で３０分間攪拌を行った後、濾紙を用いて濾過を行なったところ、色相がＡＰＨＡで５、水分含有量２９．９重量％のメトキシポリエチレングリコール（エチレンオキシドの平均付加モル数１５）メタアクリル酸エステルが得られ、ジルコニウム残存量の定量をおこなったところ０．５ｐｐｍであり、酸価は０．０４であった。
Example 11
86 g of water (51 times the amount of catalyst used) was added to 200 g of a crude reaction product of methoxypolyethylene glycol (meth) acrylate ester having an average addition mole number of 15 moles of ethylene oxide produced in the same manner as in Example 10 at 30 ° C. After stirring for 30 minutes, 1.0 g (0.5% by weight of the crude reaction product) of activated carbon birch A was further added as an adsorbent and stirred at the same temperature for 30 minutes. As a result of filtration, a methoxypolyethylene glycol (average added mole number of ethylene oxide 15) methacrylate having a hue of APHA of 5 and a water content of 29.9% by weight was obtained, and the residual amount of zirconium was determined. The acid value was 0.54.
実施例１２
２リットルの圧力反応装置にメタノール３２ｇ（１モル）と触媒としてナトリウムメトキサイド０．５ｇを仕込み、反応容器内を窒素で充分置換した後、１００℃〜１３０℃でエチレンオキシド７０４ｇ（１６モル）とプロピレンオキシド２９０ｇ（５モル）を圧力５ｋｇ／ｃｍ２以下を保ちつつ、４時間かけて導入してランダム付加反応を行った。導入終了後、１時間熟成を行って反応を終了し、引き続き、窒素導入下、温度１１０〜１１５℃で吸着剤としてキョーワード６００Ｓ（協和化学工業株式会社製）を５ｇ添加して１時間吸着処理後、濾過を行ないエチレンオキシドが１６モル、プロピレンオキシドが５モル付加したメトキシポリエチレングリコール（１６モル）ポリプロピレングリコ−ル（５モル）ランダム付加体を得た。続いて、攪拌装置、温度計、ガス導入管、還流管、冷却管を備えた、２リットル反応フラスコにメトキシポリエチレングリコール（１６モル）ポリプロピレングリコール（５モル）ランダム付加体５１３ｇ（０．５モル）を仕込み、メタクリル酸メチル４００ｇ（４モル）、重合禁止剤としてジエチルヒドロキシルアミンを０．４６ｇ（５００ｐｐｍ）、エステル交換触媒としてテトライソプロピルチタン４．６ｇをいれ、攪拌下徐々に加熱を開始し、副生するメタノールを留出しながら反応を行った。フラスコ内の反応温度は１１０℃〜１２５℃で、共沸する留出物の塔頂温度は６５℃〜７１℃を保った。反応は１１時間で終了し、反応物を冷却後、減圧下、未反応のメタクリル酸メチルを蒸留して除き、５４０ｇの粗反応物を得た。この粗反応物の色相はガードナーカラーで８、酸価は０．３２であった。この反応物を３０℃まで冷却し、反応物２００ｇに水を８６ｇ（使用触媒量に対して５０倍）添加して６０分攪拌を行った後、濾紙を用いて濾過を行なったところ、色相はＡＰＨＡで５０、水分含有量２９．０重量％のメトキシポリエチレングリコール（１６モル）ポリプロピレングリコール（５モル）メタアクリル酸エステルが得られた。残存触媒の定量をおこなったところ、粗反応物中のチタン残存量は１４１１ｐｐｍで、水で処理後、濾過を行ったものではチタン残存量２．９ｐｐｍであった。また、酸価は０．１０、ヒドロキシル価は１．４で、ヒドロキシル価により算出した反応率は９７．４％であった。
Example 12
A 2 liter pressure reactor was charged with 32 g (1 mol) of methanol and 0.5 g of sodium methoxide as a catalyst, and the reaction vessel was sufficiently replaced with nitrogen, and then 704 g (16 mol) of ethylene oxide and propylene at 100 to 130 ° C. Random addition reaction was carried out by introducing 290 g (5 mol) of oxide over 4 hours while maintaining the pressure at 5 kg / cm 2 or less. After completion of the introduction, the reaction was terminated by aging for 1 hour, followed by addition of 5 g of Kyoward 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) as an adsorbent at a temperature of 110 to 115 ° C. under nitrogen introduction, and an adsorption treatment for 1 hour. Thereafter, filtration was performed to obtain a random adduct of methoxypolyethylene glycol (16 mol) polypropylene glycol (5 mol) to which 16 mol of ethylene oxide and 5 mol of propylene oxide were added. Subsequently, 513 g (0.5 mol) of a random adduct of methoxypolyethylene glycol (16 mol), polypropylene glycol (5 mol) was added to a 2-liter reaction flask equipped with a stirrer, a thermometer, a gas introduction tube, a reflux tube, and a cooling tube. , 400 g (4 mol) of methyl methacrylate, 0.46 g (500 ppm) of diethylhydroxylamine as a polymerization inhibitor, and 4.6 g of tetraisopropyl titanium as a transesterification catalyst, gradually start heating with stirring. The reaction was carried out while distilling the produced methanol. The reaction temperature in the flask was 110 ° C to 125 ° C, and the top temperature of the azeotropic distillate was kept at 65 ° C to 71 ° C. The reaction was completed in 11 hours. After cooling the reaction product, unreacted methyl methacrylate was distilled off under reduced pressure to obtain 540 g of a crude reaction product. The crude reaction product had a Gardner color of 8 and an acid value of 0.32. The reaction product was cooled to 30 ° C., 86 g of water (50 times the amount of catalyst used) was added to 200 g of the reaction product, stirred for 60 minutes, and then filtered using filter paper. A methoxypolyethylene glycol (16 mol) polypropylene glycol (5 mol) methacrylate with 50 APHA and a water content of 29.0% by weight was obtained. When the residual catalyst was quantified, the residual amount of titanium in the crude reaction product was 1411 ppm, and the amount of residual titanium after treatment with water and filtration was 2.9 ppm. The acid value was 0.10, the hydroxyl value was 1.4, and the reaction rate calculated by the hydroxyl value was 97.4%.
比較例１
実施例１と同様にして製造したエチレンオキシドの平均付加モル数２２モルのメトキシポリエチレングリコール（メタ）アクリル酸エステル粗反応物１００ｇにキョーワード２０００を１ｇ（粗反応物の１重量％）と活性白土１ｇ（粗反応物の１重量％）入れ、１００℃で１時間処理を行ない、セルロ−ス系濾過助剤ＫＣ−フロックＷ−５０（日本製紙ケミカル株式会社製）を粗反応物重量に対して１重量％添加して濾紙を用いて濾過を行なった。濾過後の色相はガードナーカラーで７、酸価０．２３、チタン残存量の定量を行ったところ５８６ｐｐｍであった。
Comparative Example 1
100 g of methoxypolyethylene glycol (meth) acrylate crude reaction product having an average addition mole number of 22 moles of ethylene oxide produced in the same manner as in Example 1 was added to 1 g of Kyoward 2000 (1% by weight of the crude reaction product) and 1 g of activated clay. (1% by weight of the crude reaction product) was added and treated at 100 ° C. for 1 hour. Cellulose filter aid KC-Flock W-50 (manufactured by Nippon Paper Chemicals Co., Ltd.) was added to the crude reaction product weight by 1 The mixture was added by weight% and filtered using filter paper. The hue after filtration was 7 in Gardner color, the acid value was 0.23, and the remaining amount of titanium was determined to be 586 ppm.
比較例２
実施例８と同様にして製造したエチレンオキシドの平均付加モル数２２モルのメトキシポリエチレングリコール（メタ）アクリル酸エステル粗反応物１００ｇにキョーワード６００Ｓを２ｇ（粗反応物の２重量％）入れ、８０℃で１時間処理を行ない、セルロ−ス系濾過助剤ＫＣ−フロックＷ−５０（日本製紙ケミカル株式会社製）を粗反応物重量に対して０．５重量％添加して濾紙を用いて濾過を行なった。濾過後の色相はＡＰＨＡで６０、酸価０．１６、ジルコニウム残存量の定量を行ったところ９８０ｐｐｍであった。
Comparative Example 2
100 g of methoxypolyethylene glycol (meth) acrylate ester crude reaction product having an average addition mole number of ethylene oxide produced in the same manner as in Example 8 was added to 2 g of Kyoward 600S (2% by weight of the crude reaction product), and 80 ° C. For 1 hour, adding 0.5% by weight of cellulose-based filter aid KC-Flock W-50 (Nippon Paper Chemical Co., Ltd.) to the weight of the crude reaction product, and filtering using filter paper. I did it. The hue after filtration was 60 with APHA, the acid value was 0.16, and the amount of zirconium remaining was determined to be 980 ppm.
比較例３
攪拌装置、温度計、ガス導入管、還流管、冷却管を備えた、１リットル反応フラスコに実施例５と同様にして製造したエチレンオキシドの平均付加モル数１０モルのメトキシポリエチレングリコールメトキシポリエチレングリコール（平均付加モル数１０モル）４７２ｇ（１モル）を仕込み、メタクリル酸メチル４００ｇ（４モル）、重合禁止剤としてハイドロキノンモノメチルエーテルを０．４４ｇ（５００ｐｐｍ）、エステル交換触媒としてナトリウムメチラート（純度９８％）４．４ｇをいれ、攪拌下徐々に加熱を開始し、副生するメタノールを留出しながら反応を行った。フラスコ内の反応温度１０１℃から留出が開始し、共沸する留出物を除きながら反応を行ったところフラスコ内の反応温度の上昇が激しく１時間経過後にはフラスコ内温度が１２６℃に達した。反応を６時間で終了し、反応物を冷却後、減圧下、未反応のメタクリル酸メチルを蒸留して除き、５２５ｇの粗反応物を得た。この反応物２００ｇに水を６７ｇ（使用触媒量に対して４０倍）添加して３０分攪拌を行った後、濾紙を用いて濾過を行なったところ、色相はガードナーカラーで６、水分含有量２４．８重量％のメトキシポリエチレングリコール（エチレンオキシドの平均付加モル数１０）メタアクリル酸エステルが得られた。触媒に由来するナトリウムの定量を原子吸光法によりおこなったところ、水処理前の粗反応物中のナトリウム量は３３９０ｐｐｍで、水で処理後、濾過を行ったものは２３２４ｐｐｍで触媒に由来するナトリウムは除かれていなかった。水分含有量２４．８重量％の処理品のヒドロキシル価を測定したところ１３．３で未反応のメトキシポリエチレングリコールメトキシポリエチレングリコール（平均付加モル数１０モル）が処理品中に１１．１％残存しており、反応率は８５．１％であった。
Comparative Example 3
Methoxypolyethylene glycol methoxypolyethylene glycol having an average addition mole number of 10 moles of ethylene oxide produced in the same manner as in Example 5 in a 1-liter reaction flask equipped with a stirrer, a thermometer, a gas introduction tube, a reflux tube, and a cooling tube (average 472 g (1 mol) of addition mole number 10 mol), 400 g (4 mol) of methyl methacrylate, 0.44 g (500 ppm) of hydroquinone monomethyl ether as a polymerization inhibitor, sodium methylate as a transesterification catalyst (purity 98%) 4.4 g was added, heating was started gradually with stirring, and the reaction was carried out while distilling off by-produced methanol. Distillation started from a reaction temperature of 101 ° C. in the flask, and the reaction was carried out while removing the azeotropic distillate. The reaction temperature in the flask increased so rapidly that the temperature in the flask reached 126 ° C. after 1 hour. did. The reaction was completed in 6 hours, and after cooling the reaction product, unreacted methyl methacrylate was distilled off under reduced pressure to obtain 525 g of a crude reaction product. 67 g of water (40 times the amount of catalyst used) was added to 200 g of this reaction product and stirred for 30 minutes, followed by filtration using filter paper. As a result, the hue was 6 in Gardner color and the water content was 24. 8% by weight of methoxypolyethylene glycol (average added mole number of ethylene oxide 10) methacrylic acid ester was obtained. When the sodium derived from the catalyst was quantified by atomic absorption spectrometry, the amount of sodium in the crude reaction product before water treatment was 3390 ppm, and after treatment with water, filtered was 2324 ppm, and sodium derived from the catalyst was It was not removed. When the hydroxyl value of the treated product having a water content of 24.8% by weight was measured, unreacted methoxypolyethyleneglycolmethoxypolyethyleneglycol (average number of moles of 10 mol) was 13.3% in the treated product at 13.3. The reaction rate was 85.1%.
比較例４
攪拌装置、温度計、ガス導入管、還流管、冷却管を備えた、１リットル反応フラスコに実施例１と同様にして製造したエチレンオキシドの平均付加モル数２２モルのメトキシポリエチレングリコールメトキシポリエチレングリコール（平均付加モル数２２モル）５００ｇ（０．５モル）を仕込み、メタクリル酸メチル３００ｇ（３モル）、重合禁止剤としてジエチルヒドロキシルアミンを０．４ｇ（５００ｐｐｍ）、エステル交換触媒としてナトリウムメチラート（純度９８％）２ｇをいれ、攪拌下徐々に加熱を開始した、副生するメタノールを留出しながら反応を行った。フラスコ内の反応温度１１０℃から留出が開始し、反応を行ったところフラスコ内の反応温度の上昇が激しく１時間３０分経過後にはフラスコ内温度が１３０℃に達し、メタノールを留出が停止したため反応を終了した。反応物を冷却後、減圧下、未反応のメタクリル酸メチルを蒸留して除き反応物を取り出したところやや粘性を呈していた。この反応物２００ｇに４０℃にて水８５ｇ（使用触媒重量に対して１１５倍量）を添加して濾過を行ったものは水分含有量２９．２重量％のやや白濁の液状であった。水分含有量２９．２重量％の処理品のヒドロキシル価を測定したところ測定途中でゲル状を呈し、測定できなかった。
Comparative Example 4
Methoxypolyethylene glycol methoxypolyethylene glycol having an average addition mole number of 22 moles of ethylene oxide produced in the same manner as in Example 1 in a 1-liter reaction flask equipped with a stirrer, a thermometer, a gas introduction pipe, a reflux pipe, and a cooling pipe (average (Additional mole number 22 mol) 500 g (0.5 mol) was charged, methyl methacrylate 300 g (3 mol), diethylhydroxylamine 0.4 g (500 ppm) as a polymerization inhibitor, and sodium methylate (purity 98) as a transesterification catalyst. %) 2 g was added, and the reaction was carried out while distilling off by-produced methanol, which was gradually heated under stirring. Distillation started at a reaction temperature of 110 ° C in the flask, and when the reaction was carried out, the reaction temperature in the flask increased rapidly, and after 1 hour and 30 minutes, the temperature in the flask reached 130 ° C and the distillation of methanol stopped. The reaction was terminated. After the reaction product was cooled, unreacted methyl methacrylate was distilled off under reduced pressure, and the reaction product was taken out. When 200 g of this reaction product was added with 85 g of water (115 times the amount of catalyst used) at 40 ° C. and filtered, it was a slightly cloudy liquid with a water content of 29.2 wt%. When the hydroxyl value of the treated product having a water content of 29.2% by weight was measured, it showed a gel during measurement and could not be measured.
実施例３において粗反応物を処理した後の製品と、比較例３において粗反応物を処理した後の製品について、以下の条件で液体クロマトグラフィーによる分析を行ったところ、比較例３のものは副生成物と思われる不明成分のピークが多数検出された。 When the product after processing the crude reaction product in Example 3 and the product after processing the crude reaction product in Comparative Example 3 were analyzed by liquid chromatography under the following conditions, the product of Comparative Example 3 was Many peaks of unknown components that seemed to be by-products were detected.
液体クロマトグラフィー測定条件
測定機器 ：日本分光株式会社製液体クロマト測定装置
溶離液 ：メチルアルコール／水＝８０／２０（容量比）
流量 ：０．５ｍｌ／分
カラム ：Ｆｉｎｅｐａｋ ＳＩＬ Ｃ１８Ｓ（日本分光株式会社）４．６ｍｍ（径）×１５０ｍｍ（長さ）＋ＴＳＫ ＧＥＬ（東ソー株式会社）４．６ｍｍ（径）×１５０ｍｍ（長さ）
検出器 ：屈折率計
カラム温度 ：４０℃
Liquid Chromatography Measurement Condition Measuring Device: JASCO Corporation Liquid Chromatography Measuring Device Eluent: Methyl alcohol / water = 80/20 (volume ratio)
Flow rate: 0.5 ml / min
Column: Finepak SIL C18S (JASCO Corporation) 4.6 mm (diameter) x 150 mm (length) + TSK GEL (Tosoh Corporation) 4.6 mm (diameter) x 150 mm (length)
Detector: Refractometer column temperature: 40 ° C
実施例３の製品の液体クロマトグラフを図１に、比較例３の製品の液体クロマトグラフを図２にそれぞれ示す。図１のクロマトグラフでリテンションタイム８．５分は未反応原料のメトキシポリエチレングリコール、９．９分は反応生成物のメトキシポリエチレングリコールメタクリレートである。一方、図２のクロマトグラフでは、リテンションタイム８．５分に未反応原料のメトキシポリエチレングリコールが検出されたが、それ以降にはメトキシポリエチレングリコールメタクリレートと異なる多数の不明成分が検出された。 A liquid chromatograph of the product of Example 3 is shown in FIG. 1, and a liquid chromatograph of the product of Comparative Example 3 is shown in FIG. In the chromatograph of FIG. 1, the retention time of 8.5 minutes is methoxypolyethylene glycol as an unreacted raw material, and 9.9 minutes is methoxypolyethyleneglycol methacrylate as a reaction product. On the other hand, in the chromatograph of FIG. 2, unreacted methoxypolyethylene glycol was detected at a retention time of 8.5 minutes, but many unknown components different from methoxypolyethylene glycol methacrylate were detected thereafter.
Claims (5)
Ｒ１Ｏ（ＡＯ）ｎＨ （ａ）
（但し、Ｒ１は水素、炭素数１〜３０の炭化水素基、ＡＯは炭素数２〜４のオキシアルキレン基、ｎは１〜３００の数を示す。） The method for producing a water-soluble (meth) acrylic acid polyalkylene glycol ester according to claim 1, wherein the glycol compound is a glycol compound represented by the following formula (a) containing 20% by weight or more of an ethylene oxide component.
R 1 O (AO) nH (a)
(However, R 1 represents hydrogen, a hydrocarbon group having 1 to 30 carbon atoms, AO represents an oxyalkylene group having 2 to 4 carbon atoms, and n represents a number of 1 to 300.)
5. The water-soluble (meth) acrylic acid poly according to claim 4, wherein the water-insoluble adsorbent is an adsorbent having an acid adsorption ability and / or activated carbon containing at least one selected from magnesium oxide, aluminum oxide, and silicon dioxide. A method for producing an alkylene glycol ester.
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