JPH0341051A - Preparation of acrylate or methacrylate ester - Google Patents
Preparation of acrylate or methacrylate esterInfo
- Publication number
- JPH0341051A JPH0341051A JP1173931A JP17393189A JPH0341051A JP H0341051 A JPH0341051 A JP H0341051A JP 1173931 A JP1173931 A JP 1173931A JP 17393189 A JP17393189 A JP 17393189A JP H0341051 A JPH0341051 A JP H0341051A
- Authority
- JP
- Japan
- Prior art keywords
- lead
- compound
- compounds
- catalyst
- methacrylic 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.)
- Pending
Links
- -1 methacrylate ester Chemical class 0.000 title claims abstract description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title abstract 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 41
- 150000002440 hydroxy compounds Chemical class 0.000 claims abstract description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 32
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 26
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002611 lead compounds Chemical class 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 10
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 16
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 10
- 150000003606 tin compounds Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 10
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000000976 ink Substances 0.000 abstract description 3
- 239000000565 sealant Substances 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 238000007792 addition Methods 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract 1
- 239000000314 lubricant Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 239000002904 solvent Substances 0.000 description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 7
- 125000005395 methacrylic acid group Chemical group 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 229920001515 polyalkylene glycol Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229910021514 lead(II) hydroxide Inorganic materials 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000004885 piperazines Chemical class 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- ALHBQZRUBQFZQV-UHFFFAOYSA-N tin;tetrahydrate Chemical compound O.O.O.O.[Sn] ALHBQZRUBQFZQV-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- JJWLMSCSLRJSAN-TYYBGVCCSA-L (e)-but-2-enedioate;lead(2+) Chemical compound [Pb+2].[O-]C(=O)\C=C\C([O-])=O JJWLMSCSLRJSAN-TYYBGVCCSA-L 0.000 description 1
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 1
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-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
- SZSSMFVYZRQGIM-UHFFFAOYSA-N 2-(hydroxymethyl)-2-propylpropane-1,3-diol Chemical group CCCC(CO)(CO)CO SZSSMFVYZRQGIM-UHFFFAOYSA-N 0.000 description 1
- KKFDCBRMNNSAAW-UHFFFAOYSA-N 2-(morpholin-4-yl)ethanol Chemical compound OCCN1CCOCC1 KKFDCBRMNNSAAW-UHFFFAOYSA-N 0.000 description 1
- SEWORRWYWLQQNW-UHFFFAOYSA-L 2-[dibutyl-(2-carboxyphenoxy)stannyl]oxybenzoic acid Chemical compound C=1C=CC=C(O)C=1C(=O)O[Sn](CCCC)(CCCC)OC(=O)C1=CC=CC=C1O SEWORRWYWLQQNW-UHFFFAOYSA-L 0.000 description 1
- WSNAAHWRJMRVCU-UHFFFAOYSA-N 2-tert-butyl-3,4-dimethylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1C WSNAAHWRJMRVCU-UHFFFAOYSA-N 0.000 description 1
- VZKSLWJLGAGPIU-UHFFFAOYSA-N 3-morpholin-4-ylpropan-1-ol Chemical compound OCCCN1CCOCC1 VZKSLWJLGAGPIU-UHFFFAOYSA-N 0.000 description 1
- MIHQWNKDHBLQEZ-UHFFFAOYSA-N 3-tert-butyl-2-methylphenol Chemical compound CC1=C(O)C=CC=C1C(C)(C)C MIHQWNKDHBLQEZ-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- URFFPMJFOHTCLI-UHFFFAOYSA-N 4-morpholin-4-ylbutan-1-ol Chemical compound OCCCCN1CCOCC1 URFFPMJFOHTCLI-UHFFFAOYSA-N 0.000 description 1
- QXHSPHQXZGHRFK-UHFFFAOYSA-N 5-morpholin-4-ylpentan-1-ol Chemical compound OCCCCCN1CCOCC1 QXHSPHQXZGHRFK-UHFFFAOYSA-N 0.000 description 1
- FVCQUNUNTADJFP-UHFFFAOYSA-N 6-morpholin-4-ylhexan-1-ol Chemical compound OCCCCCCN1CCOCC1 FVCQUNUNTADJFP-UHFFFAOYSA-N 0.000 description 1
- PTOIVRQTAPWSDD-UHFFFAOYSA-N 8-morpholin-4-yloctan-1-ol Chemical compound OCCCCCCCCN1CCOCC1 PTOIVRQTAPWSDD-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- GXBQZWKLQLMKDM-UHFFFAOYSA-N C(C1=CC=CC=C1)O[Sn](CCCCCCCC)CCCCCCCC Chemical compound C(C1=CC=CC=C1)O[Sn](CCCCCCCC)CCCCCCCC GXBQZWKLQLMKDM-UHFFFAOYSA-N 0.000 description 1
- PGBJBWVWDQWURI-UHFFFAOYSA-N C(CCC)O[Sn](CCCCCCCC)CCCCCCCC Chemical compound C(CCC)O[Sn](CCCCCCCC)CCCCCCCC PGBJBWVWDQWURI-UHFFFAOYSA-N 0.000 description 1
- XXHWADDYNOPSDY-UHFFFAOYSA-N C(CCCCCCC)[Sn](OC)CCCCCCCC Chemical compound C(CCCCCCC)[Sn](OC)CCCCCCCC XXHWADDYNOPSDY-UHFFFAOYSA-N 0.000 description 1
- IUIBLDHUYCIQPB-UHFFFAOYSA-N C(CCCCCCC)[Sn](OCCC)CCCCCCCC Chemical compound C(CCCCCCC)[Sn](OCCC)CCCCCCCC IUIBLDHUYCIQPB-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- QNXNBZAWAJBBNX-UHFFFAOYSA-M O(C1=CC=CC=C1)[Pb] Chemical compound O(C1=CC=CC=C1)[Pb] QNXNBZAWAJBBNX-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- AYPZCTCULRIASE-ZVGUSBNCSA-L [Pb+2].C([C@H](O)[C@@H](O)C(=O)[O-])(=O)[O-] Chemical compound [Pb+2].C([C@H](O)[C@@H](O)C(=O)[O-])(=O)[O-] AYPZCTCULRIASE-ZVGUSBNCSA-L 0.000 description 1
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 description 1
- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 description 1
- LHFURYICKMKJHJ-UHFFFAOYSA-L [benzoyloxy(dibutyl)stannyl] benzoate Chemical compound CCCC[Sn+2]CCCC.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 LHFURYICKMKJHJ-UHFFFAOYSA-L 0.000 description 1
- UFYYBMYIZKRDCG-UHFFFAOYSA-L [benzoyloxy(dioctyl)stannyl] benzoate Chemical compound [O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.CCCCCCCC[Sn+2]CCCCCCCC UFYYBMYIZKRDCG-UHFFFAOYSA-L 0.000 description 1
- DWRBCWYHLKHQAP-UHFFFAOYSA-L [butanoyloxy(dibutyl)stannyl] butanoate Chemical compound CCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCC DWRBCWYHLKHQAP-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000006177 alkyl benzyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- CNVULGHYDPMIHD-UHFFFAOYSA-L bis[(2-hydroxybenzoyl)oxy]lead Chemical compound [Pb+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O CNVULGHYDPMIHD-UHFFFAOYSA-L 0.000 description 1
- HUTDDBSSHVOYJR-UHFFFAOYSA-H bis[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphaplumbetan-2-yl)oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O HUTDDBSSHVOYJR-UHFFFAOYSA-H 0.000 description 1
- HOQPTLCRWVZIQZ-UHFFFAOYSA-H bis[[2-(5-hydroxy-4,7-dioxo-1,3,2$l^{2}-dioxaplumbepan-5-yl)acetyl]oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HOQPTLCRWVZIQZ-UHFFFAOYSA-H 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- PZGVVCOOWYSSGB-UHFFFAOYSA-L but-2-enedioate;dioctyltin(2+) Chemical compound CCCCCCCC[Sn]1(CCCCCCCC)OC(=O)C=CC(=O)O1 PZGVVCOOWYSSGB-UHFFFAOYSA-L 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- ODUCJAXGIAXRJA-UHFFFAOYSA-L butanoate;dioctyltin(2+) Chemical compound CCCCCCCC[Sn](OC(=O)CCC)(OC(=O)CCC)CCCCCCCC ODUCJAXGIAXRJA-UHFFFAOYSA-L 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- YFTLVZQVJXTBJO-UHFFFAOYSA-N butoxy(dibutyl)tin Chemical compound CCCCO[Sn](CCCC)CCCC YFTLVZQVJXTBJO-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- FWGNBHVCSBZRDK-UHFFFAOYSA-N cyclodecane-1,1-diol Chemical compound OC1(O)CCCCCCCCC1 FWGNBHVCSBZRDK-UHFFFAOYSA-N 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-M decanoate Chemical compound CCCCCCCCCC([O-])=O GHVNFZFCNZKVNT-UHFFFAOYSA-M 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- HEYYNPBHZQPMJJ-UHFFFAOYSA-L dibenzoyloxylead Chemical compound C=1C=CC=CC=1C(=O)O[Pb]OC(=O)C1=CC=CC=C1 HEYYNPBHZQPMJJ-UHFFFAOYSA-L 0.000 description 1
- ZUGYUQJYHHIVGH-UHFFFAOYSA-N dibutyl(ethoxy)tin Chemical compound CCCC[Sn](OCC)CCCC ZUGYUQJYHHIVGH-UHFFFAOYSA-N 0.000 description 1
- ZJSHPGQWOSGTJD-UHFFFAOYSA-N dibutyl(methoxy)tin Chemical compound CCCC[Sn](OC)CCCC ZJSHPGQWOSGTJD-UHFFFAOYSA-N 0.000 description 1
- UDSMOEAHRBVXFA-UHFFFAOYSA-M dibutyl(phenoxy)tin Chemical compound CCCC[Sn](CCCC)OC1=CC=CC=C1 UDSMOEAHRBVXFA-UHFFFAOYSA-M 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- XRVUFNZZLJWIBD-UHFFFAOYSA-N hex-1-ene-1,1-diol Chemical compound CCCCC=C(O)O XRVUFNZZLJWIBD-UHFFFAOYSA-N 0.000 description 1
- SRYDOKOCKWANAE-UHFFFAOYSA-N hexadecane-1,1-diol Chemical compound CCCCCCCCCCCCCCCC(O)O SRYDOKOCKWANAE-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-UHFFFAOYSA-N hexane-1,2,3,4,5,6-hexol Chemical compound OCC(O)C(O)C(O)C(O)CO FBPFZTCFMRRESA-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 229940056932 lead sulfide Drugs 0.000 description 1
- 229910052981 lead sulfide Inorganic materials 0.000 description 1
- VLOJXAQYHIVPFI-UHFFFAOYSA-H lead(2+);diacetate;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].CC([O-])=O.CC([O-])=O VLOJXAQYHIVPFI-UHFFFAOYSA-H 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- VRNINGUKUJWZTH-UHFFFAOYSA-L lead(2+);dithiocyanate Chemical compound [Pb+2].[S-]C#N.[S-]C#N VRNINGUKUJWZTH-UHFFFAOYSA-L 0.000 description 1
- ZPPSOOVFTBGHBI-UHFFFAOYSA-N lead(2+);oxido(oxo)borane Chemical compound [Pb+2].[O-]B=O.[O-]B=O ZPPSOOVFTBGHBI-UHFFFAOYSA-N 0.000 description 1
- FYDIWJWWROEQCB-UHFFFAOYSA-L lead(2+);propanoate Chemical compound [Pb+2].CCC([O-])=O.CCC([O-])=O FYDIWJWWROEQCB-UHFFFAOYSA-L 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 150000002780 morpholines Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- VJQGGZWPOMJLTP-UHFFFAOYSA-N octadecane-1,1-diol Chemical compound CCCCCCCCCCCCCCCCCC(O)O VJQGGZWPOMJLTP-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- PHDLVPNTLJTMFA-UHFFFAOYSA-N phenylmethoxylead Chemical compound [Pb]OCC1=CC=CC=C1 PHDLVPNTLJTMFA-UHFFFAOYSA-N 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- CQTBQILMJBCTRS-UHFFFAOYSA-N tetradecane-1,1-diol Chemical compound CCCCCCCCCCCCCC(O)O CQTBQILMJBCTRS-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野コ
本発明はアクリル酸エステｌシ又はメタクリル酸エステ
ルの製造方法の改良；こ関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to improvements in the production method of acrylic acid esters or methacrylic acid esters.
さらに詳しくいえば、本発明は、プラスチック、塗料、
接着剤、粘着剤、紙加工処理剤、潤滑油添加剤、建築用
シーラント、インキなど多岐にわたる用途の重合体原料
として有用なアクリル酸エステル又はメタクリル酸エス
テルを効率よく製造する方法に関するものである。More specifically, the present invention relates to plastics, paints,
The present invention relates to a method for efficiently producing acrylic esters or methacrylic esters useful as polymer raw materials for a wide variety of uses such as adhesives, pressure-sensitive adhesives, paper processing agents, lubricating oil additives, architectural sealants, and inks.
［従来の技術］
従来、アクリル酸エステルやメタクリル酸エステルは、
分子内にエチレン性不飽和結合を有し、重合体原料とし
て種々の用途、例えばプラスチック、塗料、接着剤、粘
着剤、紙加工処理剤、潤滑油添加剤、建築用シーラント
、インキなどに幅広く用いられている。[Conventional technology] Conventionally, acrylic esters and methacrylic esters
It has an ethylenically unsaturated bond in its molecule and is widely used as a polymer raw material in various applications such as plastics, paints, adhesives, pressure-sensitive adhesives, paper processing agents, lubricating oil additives, architectural sealants, and inks. It is being
特にアクリル酸又はメタクリル酸と、ヒドロキシル基を
２個以上有する化合物とのエステルは、１分子中に最大
ヒドロキシル基の数だけ重合性のビニル基を導入するこ
とができ、これを他の重合性ビニル化合物と共重合する
ことにより、架橋構造を形成しうろことから、物理的強
度、耐熱性、耐候性、耐薬品性などの向上効果を付与し
うる機能性モノマーとして有用である外、紫外線硬化型
樹脂の反応性希釈剤としても有用である。In particular, esters of acrylic acid or methacrylic acid and a compound having two or more hydroxyl groups can introduce as many polymerizable vinyl groups as the maximum number of hydroxyl groups into one molecule, and can be used to create other polymerizable vinyl groups. Since it forms a crosslinked structure by copolymerizing with other compounds, it is useful as a functional monomer that can improve physical strength, heat resistance, weather resistance, chemical resistance, etc. It is also useful as a reactive diluent for resins.
さらに、ヒドロキシル基をエステル鎖中に残したアクリ
ル酸エステル又はメタクリル酸エステルは、良好な親水
性を有し、コンタクトレンズや防曇レンズ用プラスチッ
クの原料として使用しうるとともに、紫外線硬化型樹脂
の反応性希釈剤としても有用である。In addition, acrylic esters or methacrylic esters with hydroxyl groups left in the ester chain have good hydrophilicity and can be used as raw materials for contact lenses and anti-fog lens plastics, as well as for reaction in ultraviolet curing resins. It is also useful as a sex diluent.
一方、エステル鎖に酸素原子及び／又は窒素原子を有す
るアクリル酸エステル又はメタクリル酸エステルは、他
のビニル化合物と共重合することにより、親水性、接着
性・粘着性、無機充填剤との相溶性、潤滑油中のスラッ
ジ分散性、溶媒への溶解性などの向上効果を付与しうろ
ことから、各種重合体の改質用モノマーとして、その利
用価値は高い。On the other hand, acrylic esters or methacrylic esters having an oxygen atom and/or nitrogen atom in the ester chain can be copolymerized with other vinyl compounds to improve hydrophilicity, adhesiveness/tackiness, and compatibility with inorganic fillers. Since it has the effect of improving sludge dispersibility in lubricating oil and solubility in solvents, it has high utility value as a monomer for modifying various polymers.
このようなアクリル酸エステルやメタクリル酸エステル
の製造方法としては、従来、触媒として、例えば硫酸、
塩酸、硝酸、リン酸などの鉱ｆｉ、ｐ−トルエンスルホ
ン酸、ベンゼンスルホン酸、メタンスルホン酸、キシレ
ンスルホン酸などの有機酸、あるいは酸性イオン交換樹
脂などを用いて、アクリル酸又はメタクリル酸とヒドロ
キシ化合物とを反応させる直接エルテル化法が一般に広
く知られている。Conventionally, methods for producing such acrylic esters and methacrylic esters use catalysts such as sulfuric acid,
Acrylic acid or methacrylic acid and hydroxy A direct ertherization method in which a compound is reacted with a compound is generally widely known.
しかしながら、これらの触媒を用いる方法は、例えば着
色したり、副生成物が多かったり、あるいは収率が低い
などの欠点を有し、必ずしも満足しうるものではなく、
さらに、３個以上のヒドロキシル基を有する化合物のエ
ルテル化の場合には、すべてのヒドロキシル基にアクリ
ル酸又はメタクリル酸を導入することが困難であるし、
またアミノアルコール類に対しては酸触媒は全く不活性
であって、反応しないなどの欠点があった。However, methods using these catalysts have drawbacks such as coloring, large amounts of by-products, or low yields, and are not necessarily satisfactory.
Furthermore, in the case of ertherization of compounds having three or more hydroxyl groups, it is difficult to introduce acrylic acid or methacrylic acid into all hydroxyl groups,
Furthermore, acid catalysts are completely inactive and have the disadvantage of not reacting with amino alcohols.
このように、アクリル酸又はメタクリル酸と前記ヒドロ
キシ化合物との直接エステル化反応については、今だに
満足しうる方法は見い出されておらず、もっばらアクリ
ル酸又はメタクリル酸の低級脂肪族アルキルエステルを
いったん得たのち、これをエステル交換法により、所望
のアクリル酸エステル又はメタクリル酸エステルに誘導
するという煩雑なプロセスを用いているのが現状である
。As described above, no satisfactory method has yet been found for the direct esterification reaction of acrylic acid or methacrylic acid with the above-mentioned hydroxyl compounds, and it is preferable to use lower aliphatic alkyl esters of acrylic acid or methacrylic acid. At present, a complicated process is used in which, once obtained, this is induced into the desired acrylic ester or methacrylic ester by transesterification.
［発明が解決しようとする課題］
本発明は、このような事情のもとで、アクリル酸又はメ
タクリル酸と、ヒドロキシル基を少なくとも２個有する
ヒドロキシ化合物、あるいはヒドロキシル基の酸素原子
以外の酸素原子及び／又は窒素原子を少なくとも１＠有
するヒドロキシ化合物とを用い、直接エステル化法によ
り、着色や副反応がほとんどなく、高収率でかつ工業的
有利にアクリル酸エステル又はメタクリル酸エステルを
製造する方法を提供することを目的としてなされたもの
である。[Problems to be Solved by the Invention] Under these circumstances, the present invention provides a combination of acrylic acid or methacrylic acid and a hydroxy compound having at least two hydroxyl groups, or an oxygen atom other than the oxygen atom of the hydroxyl group and A method for producing acrylic esters or methacrylic esters in a high yield and industrially advantageously with almost no coloring or side reactions by direct esterification using / or a hydroxy compound having at least one nitrogen atom. It was made for the purpose of providing.
［課題を解決するための手段］
本発明者は前記目的を達成するために鋭意研究を重ねた
結果、特定の触媒を用いることにより、その目的を達成
しうろことを見い出し、この知見に基づいて本発明を完
成するに−°１−）た。[Means for Solving the Problem] As a result of intensive research to achieve the above object, the present inventor discovered that the object could be achieved by using a specific catalyst, and based on this knowledge, In order to complete the present invention -°1-).
すなわち、本発明は、（Ａ）アクリル酸又はメタクリル
酸と、（Ｂ）ヒドロキシル基を少なくとも２個有するか
、あるいはヒドロキシル基の酸素原子以外の酸素原子及
び／又は窒素原子を少なくとも１個有するヒドロキシ化
合物とを反応させてアクリル酸エステル又はメタクリル
酸エステルを製造するに当たり、触媒として金属スズ、
金属鉛、スズ化合物及び鉛化合物の中から選ばれｔ；少
なくとも１８ｉを用いることを特徴とするアクリル酸エ
ステル又はメタクリル酸エステルの製造方法を提供する
ものである。That is, the present invention provides (A) acrylic acid or methacrylic acid and (B) a hydroxy compound having at least two hydroxyl groups or having at least one oxygen atom and/or nitrogen atom other than the oxygen atom of the hydroxyl group. In producing acrylic ester or methacrylic ester by reacting with metal tin,
The present invention provides a method for producing an acrylic ester or a methacrylic ester, characterized in that at least 18i selected from metallic lead, tin compounds, and lead compounds is used.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明方法においては、（Ｂ）［料戊分のヒドロキシ化
合物として、ヒドロキシル基を少なくとも２個有するヒ
ドロキシ化合物、あるいはヒドロキシル基の酸素原子以
外の酸素原子及び／又は窒素原子を少なくとも１個有す
るヒドロキシ化合物が用いられる。これらのヒドロキシ
化合物は脂肪族、脂環式、芳香族系のいずれであっても
よいし、また不飽和結合を有するものであってもよい。In the method of the present invention, (B) a hydroxy compound having at least two hydroxyl groups, or a hydroxy compound having at least one oxygen atom and/or nitrogen atom other than the oxygen atom of the hydroxyl group; is used. These hydroxy compounds may be aliphatic, alicyclic, or aromatic, or may have an unsaturated bond.
ヒドロキシル基を少なくとも２個有するヒドロキシ化合
物としては、例えばエチレングリコール、プロピレング
リコール、ネオペンチルグリコール、ブタンジオール、
ベンタンジオール、ヘキサンジオール、オクタンジオー
ル、デカンジオール、ドデカンジオール、テトラデカン
ジオール、ヘキサデカンジオール、オクタデカンジオー
ル、シクロヘキサンジオール、シクロデカンジオール、
トリシクロデカンジオール、ブチンジオール、ブチンジ
オール、ヘキセンジオール、オクテンジオール、デセン
ジオールなどのヒドロキシル基２個を有するもの、ヘキ
サントリオール、オクタントリオール、デカントリオー
ル、トリメチロール円タン、トリメチロールプロパン、
トリメチロールブタン、グリセリンなどのヒドロキシル
基３個を有するもの、ペンタエリスリトール、ヘキシト
ール、ソルビトール、マンニトールなどのヒドロキシル
基４個以上を有するものなどが挙げられる。Examples of hydroxy compounds having at least two hydroxyl groups include ethylene glycol, propylene glycol, neopentyl glycol, butanediol,
Bentanediol, hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, hexadecanediol, octadecanediol, cyclohexanediol, cyclodecanediol,
Those with two hydroxyl groups such as tricyclodecanediol, butynediol, butynediol, hexenediol, octenediol, decenediol, hexanetriol, octanetriol, decanetriol, trimethylol yentan, trimethylol propane,
Examples include those having three hydroxyl groups such as trimethylolbutane and glycerin, and those having four or more hydroxyl groups such as pentaerythritol, hexitol, sorbitol, and mannitol.
ヒドロキシル基の酸素原子以外の酸素原子を少なくとも
１個有するとドロキシ化合物としては、例えば−数式
％式％（）
（式中のＲ１は炭素数２〜８のアルキレン基、ｍは２以
上の整数である）
で表されるヒドロキシル基２個を有するポリアルキレン
グリコール類、−数式
％式％（）
（式中のＲ２は炭素数２〜８のアルキレン基、Ｒ３は炭
素数１〜１８のアルキル基又は置換基を有しない若しく
は炭素数１〜１８のアルキル基を有するベンジル基やフ
ェニル基などのアリール基、ｎは１以上の整数である）
で表されるヒドロキシル基１個を有するアルキレングリ
コールモノアルキルエーテル類、及びテトラヒドロフル
フリルアルコール、フルフリルアルコール、キシロース
などが挙げられる。If the compound has at least one oxygen atom other than the oxygen atom of the hydroxyl group, for example, - formula % formula % () (R1 in the formula is an alkylene group having 2 to 8 carbon atoms, m is an integer of 2 or more Polyalkylene glycols having two hydroxyl groups represented by - formula % formula % () (in the formula, R2 is an alkylene group having 2 to 8 carbon atoms, R3 is an alkyl group having 1 to 18 carbon atoms, or An alkylene glycol monoalkyl ether having one hydroxyl group represented by an aryl group such as a benzyl group or a phenyl group that has no substituent or has an alkyl group having 1 to 18 carbon atoms, where n is an integer of 1 or more. and tetrahydrofurfuryl alcohol, furfuryl alcohol, xylose, and the like.
前記−数式（Ｉ）で表されるポリアルキレングリコール
類としては、例えばＲ１のアルキレン基がエチレン、プ
ロピレン、ブチレン、テトラメチレン、ペンタメチレン
、ヘキシレン、ヘキサメチレン、オクチレン基などのジ
アルキレングリコール、トリアル、キレングリコール、
テトラアルキレングリコール、ペンタアルキレングリコ
ール、ｍが６以上のポリアルキレングリコールなどが挙
げられる。Examples of the polyalkylene glycols represented by formula (I) include dialkylene glycols in which the alkylene group of R1 is ethylene, propylene, butylene, tetramethylene, pentamethylene, hexylene, hexamethylene, octylene, etc.; Killen glycol,
Examples include tetraalkylene glycol, pentaalkylene glycol, and polyalkylene glycol in which m is 6 or more.
一方、前記−数式（ＩＩ）で表されるアルキレングリコ
ールモノアルキルエーテル類としては、例えばＲ２がエ
チレン、プロピレン、ブチレン、テトラメチレン、ペン
タメチレン、ヘキシレン、ヘキサメチレン、オクチレン
基などで、かつＲ３がメチル、エチル、プロピル、ブチ
ル、ペンチル、ヘキンル、ヘプチル、オクチル、ノニル
、デシル、ウンデシル、ドデシル、トリデシル、テトラ
デシル、ペンタデシル、ヘキサデシル、オクタデシルな
どのアルキル基、ベンジル、フェニル、アルキルベンジ
ル、アルキルフェニル基などのアリール基（置換基のア
ルキル基としては前記に例示したものが挙げられる）で
ある、アルキレングリコールモノアルキルエーテル、ジ
アルキレングリコールモノアルキルエーテル、トリアル
キレングリコールモノアルキルエーテル、テトラアルキ
レングリコールモノアルキルエーテル
レングリフールモノアルキルエーテル、ｎが６以上のポ
リアルキレングリコールモノアルキルエーテルなどが挙
げられる。On the other hand, as the alkylene glycol monoalkyl ethers represented by formula (II), for example, R2 is ethylene, propylene, butylene, tetramethylene, pentamethylene, hexylene, hexamethylene, octylene group, etc., and R3 is methyl , ethyl, propyl, butyl, pentyl, hequinyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, alkyl groups, benzyl, phenyl, alkylbenzyl, alkylphenyl groups, etc. alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, trialkylene glycol monoalkyl ether, tetraalkylene glycol monoalkyl ether lene glycol, which is a group (the alkyl group of the substituent includes those exemplified above) Monoalkyl ethers, polyalkylene glycol monoalkyl ethers in which n is 6 or more, and the like.
窒素原子を有するヒドロキシ化合物としては、例えば−
数式
％式％（）
（式中のＲ４は炭素数２〜８のアルキレン基、ｐはｌ，
２又は３である）
で表されるヒドロキシル基１〜３個を有するヒドロキシ
アルキルアミン類、−数式
（式中のＲ４及びｐは前記と同じ意味をもつ）で表され
るヒドロキシル基１〜３個を有するヒドロキシアルキル
ピリジン類、−数式
（式中のＲ６は前記と同じ意味をもつ）で表されるヒド
ロキシル基１個を有するＮ−（ヒドロキシアルキル）ピ
ペリジン類、−数式（式中のＲ４は前記と同じ意味をも
つ）で表されるヒドロキシル基１個を有するＮ−（ヒド
ロキシアルキル）ピロリジン類、−数式（式中のＲ４は
前記と同じ意味をもつ）で表されるヒドロキシル基１個
を有するＮ−（ヒドロキシアルキル）へキサメチレンイ
ミン類、数式
（式中のＲ４は前記と同じ意味をもつ）で表されるヒド
ロキシル基１個を有するＮ−（ヒドロキシアルキル）ピ
ペラジン類、−数式（式中のＲ４は前記と同じ意味をも
つ）で表されるヒドロキシル基２個を有するＮ、Ｎ’ジ
（ヒドロキシアルキル）ピペラジン類などが挙げられる
。Examples of hydroxy compounds having a nitrogen atom include -
Formula % Formula % () (R4 in the formula is an alkylene group having 2 to 8 carbon atoms, p is l,
2 or 3) Hydroxyalkylamines having 1 to 3 hydroxyl groups represented by -1 to 3 hydroxyl groups represented by the formula (R4 and p in the formula have the same meanings as above) hydroxyalkylpyridines having one hydroxyl group represented by the formula (R6 in the formula has the same meaning as above); N-(hydroxyalkyl)piperidines having one hydroxyl group represented by the formula (R4 in the formula has the same meaning as above); - N-(hydroxyalkyl)pyrrolidines having one hydroxyl group represented by the formula (having the same meaning as above), - having one hydroxyl group represented by the formula (in which R4 has the same meaning as above) N-(hydroxyalkyl)hexamethyleneimines, N-(hydroxyalkyl)piperazines having one hydroxyl group represented by the formula (R4 in the formula has the same meaning as above), -(hydroxyalkyl)piperazines having one hydroxyl group represented by the formula (in the formula Examples include N,N' di(hydroxyalkyl)piperazines having two hydroxyl groups represented by (R4 has the same meaning as above).
これらの窒素原子を有するヒドロキシ化合物におけるＲ
１としては、例えばエチレン基、プロピレン基、ブチレ
ン基、ペンチレン基、ヘキシレン基、オクチレン基など
が挙げられ、まＩ；、複素環式アミン類については、そ
の環状の炭素原子に炭素数１〜１８のアルキル基、例え
ばメチル、エチル、プロピル、ブチル、ペンチル、ヘキ
シル、ヘプチル、オクチル、ノニル、デシル、ウンデシ
ル、ドデシル、トリデシル、テトラデシル、ペンタデシ
ル、ヘキサデシル、オクタデシル基などが置換していて
もよい。R in these hydroxy compounds having nitrogen atoms
Examples of 1 include ethylene group, propylene group, butylene group, pentylene group, hexylene group, and octylene group; may be substituted with an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl group, etc.
前記−数式（■）で表されるヒドロキシアルキルアミン
類には、モノ（ヒドロキシアルキル）アミン、ジ（ヒド
ロキシアルキル）アミン、トリ（ヒドロキシアルキル
記−数式（ＩＶ）で表されるヒドロキシアルキルピリジ
ン類には、モノ（ヒドロキシアルキル）ピリジン、ジ（
ヒドロキシアルキル）ピリジン、トリ（ヒドロキシアル
キル）ピリジンがある。The hydroxyalkylamines represented by formula (■) include mono(hydroxyalkyl)amine, di(hydroxyalkyl)amine, tri(hydroxyalkyl) and hydroxyalkylpyridine represented by formula (IV). is mono(hydroxyalkyl)pyridine, di(
There are hydroxyalkyl)pyridine and tri(hydroxyalkyl)pyridine.
窒素原子及び酸素原子の両方を有するヒドロキシ化合物
としては、例えば−数式
（式中のＲ′は炭素数２〜８のアルキレン基である）で
表されるヒドロキシル基１個を有するＮ−（ヒドロキシ
アルキル）モルホリン類、具体的に１：ｉ，Ｎ−（ヒド
ロキシエチル）モルホリン、Ｎ−（ヒドロキシプロピル
）モルホリン、Ｎ−（ヒドロキシブチル）モルホリン、
Ｎ−（ヒドロキシペンチル）モルホリン、Ｎ−（ヒドロ
キシヘキシル）モルホリン、Ｎ−（ヒドロキシオクチル
）モルホリンなどが挙げられる。Examples of hydroxy compounds having both a nitrogen atom and an oxygen atom include N-(hydroxyalkyl ) Morpholines, specifically 1:i, N-(hydroxyethyl)morpholine, N-(hydroxypropyl)morpholine, N-(hydroxybutyl)morpholine,
Examples include N-(hydroxypentyl)morpholine, N-(hydroxyhexyl)morpholine, N-(hydroxyoctyl)morpholine, and the like.
以上、本発明方法において、（Ｂ）［Ｎ成分として用い
られるヒドロキシ化合物の具体例を示したが、もちろん
これらに限定されるものではない。Although specific examples of the hydroxy compound used as component (B) [N] have been shown above in the method of the present invention, it is of course not limited to these.
本発明方法においては、エステル化反応の触媒として、
金属スズ、金属鉛、スズ化合物及び鉛化合物の中から選
ばれた少なくとも１種が用いられる。In the method of the present invention, as a catalyst for the esterification reaction,
At least one selected from metal tin, metal lead, tin compounds, and lead compounds is used.
触媒として金属スズや金属鉛を用いる場合、その形状、
形態及び純度については特に制限はなく、金属単体はも
ちろん、粗製物、合金、混合物など金属スズや金属鉛を
含有するものであればよく、任意の形状のものを使用す
ることができるし、まＩ；スズと鉛の混合物であっても
よい。形状の具体例としては、粒状、砂状、粉末状、金
属箔、伸線状、棒状、網状、板状、塊状などが挙げられ
、まｔ；形態の具体例としては、地金、金属単体、他の
金属との合金・混合物、スズ化合物及び／又は鉛化合物
との混合物、他の金属化合物との混合物、その他の物質
との混合物などが挙げられるが、反尾液中での分散が良
好な形状のものが好ましく、例えば１００メノシユの金
網を通過する粒径を有する粉末状の金属単体のものが使
いやすく有利である。When using metallic tin or metallic lead as a catalyst, its shape,
There are no particular restrictions on the form and purity, and any metal can be used, as long as it contains metal tin or metal lead, such as simple metals, crude materials, alloys, and mixtures. I; May be a mixture of tin and lead. Specific examples of shapes include granules, sand, powder, metal foil, drawn wire, rods, nets, plates, lumps, etc. Specific examples of shapes include bare metal, single metal , alloys/mixtures with other metals, mixtures with tin compounds and/or lead compounds, mixtures with other metal compounds, mixtures with other substances, etc., but they disperse well in the tailing liquid. For example, a powdered metal having a particle size that can pass through a 100-mesh wire mesh is advantageous because it is easy to use.
触媒として用いるスズ化合物については特に制限はなく
、第一スズ化合物、第二スズ化合物のいずれであっても
よいし、無機化合物の形態であっても、有機スズ化合物
の形態であってもよい。第一スズ化合物としては、例え
ば酸化第一スズ、水酸化第一スズ、塩化第一スズ、臭化
第一スズ、ギ酸第一スズ、酢酸第一スズ、プロピオン酸
第−スズ、酪酸第一スズ、吉草酸第一スズ、カプロン酸
第−スズ、カプリル酸第−スズ、カプリン酸第−スズ、
ラウリン酸第−スズ、安息香酸第一スズ、シュウ酸第−
スズ、サリチル酸第−スズ、マレインａ第一スズ、７マ
ル酸第−スズ、メトキシ第一スズ、エトキシ第一スズ、
プロポキシ第一スズ、ブトキシ第一スズ、ペンタオキシ
第一スズ、ヘキサオキン第一スズ、フェノキシ第一スズ
、ベンジルオキシ第一スズなどが挙げられ、第二スズ化
合物としては、例えば酸化第二スズ、水酸化第二スズ、
塩化第二スズ、臭化第二スズ、ジメチル酸化第二スズ、
ジブチル酸化第二スズ、ジオクチル酸化第二スズ、ジオ
クチル酸化第二スズ、トリブチル水酸化第二スズ、トリ
オクチル水酸化第二スズ、ジブチル水酸化第二スズ、ジ
オクチル水酸化第二スズ、トリブチル塩化第二スズ、ト
リオクチル塩化第二スズ、ジブチル塩化第二スズ、ジオ
クチル塩化第二スズ、酢酸ジブチルスズ、酢酸ジオクチ
ルスズ、酪酸ジブチルスズ、酪酸ジオクチルスズ、ラウ
リン酸ジブチルスズ、ラウリン酸ジオクチルスズ、安息
香酸ジブチルスズ、安息香酸ジオクチルスズ、サリチル
酸ジブチルスズ、マレイン酸ジオクチルスズ、メトキシ
ジブチルスズ、メトキシジオクチルスズ、エトキシジブ
チルスズ、プロポキシジオクチルスズ、ブトキシジブチ
ルスズ、ブトキシジオクチルスズ、フェノキシジブチル
スズ、ベンジルオキシジオクチルスズなどが挙げられる
。The tin compound used as a catalyst is not particularly limited and may be either a stannous compound or a stannic compound, or may be in the form of an inorganic compound or an organic tin compound. Examples of stannous compounds include stannous oxide, stannous hydroxide, stannous chloride, stannous bromide, stannous formate, stannous acetate, stannous propionate, and stannous butyrate. , stannous valerate, stannous caproate, stannous caprylate, stannous caprate,
stannous laurate, stannous benzoate, stannous oxalate
tin, stannous salicylate, stannous maleate, stannous heptimalate, stannous methoxy, stannous ethoxy,
Examples of stannous compounds include stannous propoxy, stannous butoxy, stannous pentaoxy, stannous hexaoquine, stannous phenoxy, and stannous benzyloxy. stannic,
stannic chloride, stannic bromide, dimethyl stannic oxide,
Dibutyl stannic oxide, dioctyl stannic oxide, dioctyl stannic oxide, tributyl stannic hydroxide, trioctyl stannic hydroxide, dibutyl stannic hydroxide, dioctyl stannic hydroxide, tributyl stannic chloride Tin, trioctyl stannic chloride, dibutyl stannic chloride, dioctyl stannic chloride, dibutyl tin acetate, dioctyl tin acetate, dibutyl tin butyrate, dioctyl tin butyrate, dibutyl tin laurate, dioctyl tin laurate, dibutyl tin benzoate, dioctyl tin benzoate Examples include tin, dibutyltin salicylate, dioctyltin maleate, methoxydibutyltin, methoxydioctyltin, ethoxydibutyltin, propoxydioctyltin, butoxydibutyltin, butoxydioctyltin, phenoxydibutyltin, benzyloxydioctyltin, and the like.
また、触媒として用いる鉛化合物については特に制限は
なく、酸化物、水酸化物、塩などの無機鉛化合物、有機
酸塩、アルコキシド、キレートなどの有機鉛化合物など
広範囲な鉛化合物が使用できる。Further, there is no particular restriction on the lead compound used as a catalyst, and a wide range of lead compounds can be used, including inorganic lead compounds such as oxides, hydroxides, and salts, and organic lead compounds such as organic acid salts, alkoxides, and chelates.
無機船化合物としては、例えば、−酸化鉛、二酸化鉛、
四三酸化船、水酸化鉛、塩基性水酸化鉛、硝酸鉛、硫酸
鉛、硫化鉛、炭酸鉛、塩基性炭酸鉛、リン酸鉛、ホウ酸
鉛、クロム酸鉛、チオシアン酸鉛、塩化鉛、臭化鉛、ス
ズ酸鉛などが挙げられ、有機鉛化合物としては、例えば
、ギ酸鉛、酢酸鉛、塩基性酢酸鉛、プロピオン酸鉛、酢
酸鉛、古草酸鉛、カプロン酸鉛、カプリル酸鉛、カプリ
ン酸鉛、酒石酸鉛、クエン酸鉛、オレイン酸鉛、ステア
リン酸鉛、安息香酸鉛、シュウ酸鉛、サリチル酸鉛、マ
レイン酸鉛、フマル酸鉛、メトキシ鉛、エトキシ船、プ
ロポキシ鉛、ブトキシ鉛、ペンタオキシ鉛、ヘキサオキ
シ鉛、フェノキシ鉛、ベンジルオキシ鉛、アセト酢酸鉛
などが挙げられる。Examples of inorganic ship compounds include -lead oxide, lead dioxide,
Trioxide, lead hydroxide, basic lead hydroxide, lead nitrate, lead sulfate, lead sulfide, lead carbonate, basic lead carbonate, lead phosphate, lead borate, lead chromate, lead thiocyanate, lead chloride Examples of organic lead compounds include lead formate, lead acetate, basic lead acetate, lead propionate, lead acetate, lead archaic acid, lead caproate, and lead caprylate. , lead caprate, lead tartrate, lead citrate, lead oleate, lead stearate, lead benzoate, lead oxalate, lead salicylate, lead maleate, lead fumarate, lead methoxy, lead ethoxy, lead propoxy, lead butoxy. , pentaoxylead, hexaoxylead, phenoxylead, benzyloxylead, lead acetoacetate, and the like.
本発明方法においては、前記触媒は１種用いてもよいし
、２種以上を組み合わせて用いてもよく、また、分散を
良好にするために、撹拌を強力に行うことや、活性炭の
ような分散剤を併用することもできる。In the method of the present invention, one type of the catalyst may be used, or two or more types may be used in combination, and in order to improve dispersion, strong stirring or activated carbon or other catalysts may be used. A dispersant can also be used in combination.
本発明において、触媒として金属スズ及び／又は金属鉛
を使用する場合には、スズ及び／又は鉛とアクリル酸又
はメタクリル酸が反応して生皮するアクリル酸又はメタ
クリル酸のスズ及び／又は鉛塩が触媒活性種として機能
しているものと推定される。In the present invention, when metallic tin and/or metallic lead is used as a catalyst, the tin and/or lead salt of acrylic acid or methacrylic acid is formed by the reaction of tin and/or lead with acrylic acid or methacrylic acid. It is presumed that it functions as a catalytically active species.
本発明方法においては、アクリル酸又はメタクリル酸と
ヒドロキシ化合物との使用割合は、用いるヒドロキシ化
合物のヒドロキシル基の数及び沸点により適宜選ぶこと
が望ましい。In the method of the present invention, the ratio of acrylic acid or methacrylic acid and hydroxy compound to be used is desirably selected as appropriate depending on the number of hydroxyl groups and boiling point of the hydroxy compound used.
例えば分子中にヒドロキシル基１個を有するヒドロキシ
化合物の使用においては、一般に常圧での沸点が概略２
００ ’Ｏ以上のヒドロキシ化合物を用いてエステル化
反応を行う場合には、ヒドロキシ化合物の沸点が高いた
めに、反応後の蒸留操作において、原料のヒドロキシ化
合物の分離除去が困難であることから、通常アクリル酸
又はメタクリル酸に対するヒドロキシ化合物のモル比が
小さい、すなわちアクリル酸又はメタクリル酸が過剰な
反応系でエステル化反応が行われる。For example, when using a hydroxy compound having one hydroxyl group in the molecule, the boiling point at normal pressure is generally about 2.
When carrying out an esterification reaction using a hydroxy compound of 00'O or more, it is difficult to separate and remove the raw material hydroxy compound in the distillation operation after the reaction due to the high boiling point of the hydroxy compound. The esterification reaction is carried out in a reaction system in which the molar ratio of hydroxy compound to acrylic acid or methacrylic acid is small, that is, acrylic acid or methacrylic acid is in excess.
一方、常圧での沸点が概略２００℃以下のヒドロキシ化
合物を用いてエステルを製造する場合には、前記のよう
にアクリル酸又はメタクリル酸が過剰な反応系でエステ
ル化反応を行ってもよいし、逆にヒドロキシ化合物が過
剰な反応系で該反応を行ってもよい。On the other hand, when producing an ester using a hydroxy compound with a boiling point of approximately 200°C or less at normal pressure, the esterification reaction may be carried out in a reaction system containing an excess of acrylic acid or methacrylic acid as described above. Conversely, the reaction may be carried out in a reaction system in which the hydroxy compound is present in excess.
両者の具体的な使用割合については、アクリル酸又はメ
タクリル酸が過剰な反応系では、ヒドロキシ化合物１モ
ルに対し、アクリル酸又はメタクリル酸が通常１〜７モ
ル、好ましくは１〜４モルの割合で用いられ、一方ヒド
ロキシ化合物が過剰な反応系では、アクリル酸又はメタ
クリル酸１モルに対し、ヒドロキシ化合物が通常１〜５
０モル、好ましくは１〜２０モルの割合で用いられる。Regarding the specific proportion of both, in a reaction system in which acrylic acid or methacrylic acid is in excess, acrylic acid or methacrylic acid is usually used at a ratio of 1 to 7 mol, preferably 1 to 4 mol, per 1 mol of the hydroxy compound. On the other hand, in a reaction system in which the hydroxy compound is used in excess, the hydroxy compound is usually 1 to 5 mol per 1 mole of acrylic acid or methacrylic acid.
It is used in a proportion of 0 mol, preferably 1 to 20 mol.
さらに、触媒の使用量は、アクリル酸又はメタクリル酸
が過剰な反応系ではヒドロキシ化合物に対し、また、ヒ
ドロキシ化合物が過剰な反応系ではアクリル酸又はメタ
クリル酸に対し、通常０．０５〜５０モル％、好ましく
は０．１〜１０モル％の範囲で選ばれる。Furthermore, the amount of the catalyst used is usually 0.05 to 50 mol % based on the hydroxy compound in a reaction system containing an excess of acrylic acid or methacrylic acid, and based on the acrylic acid or methacrylic acid in a reaction system containing an excess of a hydroxy compound. , preferably in the range of 0.1 to 10 mol%.
一方、分子中にヒドロキシル基２個以上を有するヒドロ
キシ化合物の使用においては、該ヒドロキシ化合物のす
べてのヒドロキシル基をエステル化する場合、ヒドロキ
シ化合物１．０／（１分子中のヒドロキシル基の数）モ
ルに対し、アクリル酸又はメタクリル酸が通常１〜７モ
ル、好ましくは１〜４モルの割合で用いられ、また、咳
ヒドロキシ化合物の一部のヒドロキシル基をエステル化
する場合には、ヒドロキシ化合物１．０／（１分子当た
りのエステル化すべき数）モルに対し、通常１．０〜１
．６モル、好ましくは１．０−１．２モルの割合で用い
られる。On the other hand, when using a hydroxy compound having two or more hydroxyl groups in the molecule, if all the hydroxyl groups in the hydroxy compound are esterified, the hydroxy compound is 1.0/(number of hydroxyl groups in one molecule) mole. On the other hand, acrylic acid or methacrylic acid is usually used in a proportion of 1 to 7 moles, preferably 1 to 4 moles, and when some hydroxyl groups of the cough hydroxy compound are esterified, the hydroxy compound 1. 0/(number to be esterified per molecule) mole, usually 1.0 to 1
．． It is used in a proportion of 6 mol, preferably 1.0-1.2 mol.
また、触媒の使用量はヒドロキシ化合物に対し、通常０
．０５〜５０モル％、好ましくは０．１〜１０モル％の
範囲で選ばれる。In addition, the amount of catalyst used is usually 0 relative to the hydroxy compound.
．． 05 to 50 mol%, preferably 0.1 to 10 mol%.
本発明方法においては、所望に応じ、反応系に重合禁止
剤を添加することができる。該重合禁止剤としては、例
えばハイドロキノン、メトキシハイドロキノン、ハイド
ロキノン七ノメチルエーテル、フェノチアジン、ｔ−ブ
チルクレゾール、ジメチル−ｔ−ブチルフェノール、ｔ
−ブチルカテコールなどが挙げられ、これらは１種用い
てもよいし、２種以上を組み合わせて用いてもよく、ま
Ｉ；、その添加量は、反応系に対し、通常５〜５０００
ｗ ｔ ｐｐｍ ｓ好ましくは２０〜２０００ｗｔｐ
ｐｍの範囲で選ばれる。In the method of the present invention, a polymerization inhibitor can be added to the reaction system if desired. Examples of the polymerization inhibitor include hydroquinone, methoxyhydroquinone, hydroquinone heptamethyl ether, phenothiazine, t-butyl cresol, dimethyl-t-butylphenol, t-
-butylcatechol, etc. These may be used alone or in combination of two or more, and the amount added is usually 5 to 5,000 to the reaction system.
wtppm spreferably 20-2000wtp
Selected within the pm range.
本発明においては、反応溶媒を特に必要としないが、所
望に応じ、副生ずる水を共沸除去しうるような溶媒、例
えば水と共沸混合組成を形成して、沸点が水の沸点より
低くなるような溶媒を用いてもよい。このような溶媒と
しては、例えばペンタン、ヘキサン、ヘゲタン、オクタ
ン、ノナン、石油エーテル、石油ベンジン、ナフサ、ガ
ソリン、灯油、リグロイン、シクロヘキサン、メチルシ
クロヘキサンなどの炭化水素化合物、あるいはベンゼン
、トルエン、キシレン、エチルベンゼン、トリメチルベ
ンゼン、メチルエチルベンゼン、キュメン、その他炭素
数９〜１１の芳香族炭化水素や、クロロベンゼンのよう
な塩素化芳香族炭化水素などの芳香族化合物、ジエチル
エーテル、ジイソプロピルエーテル、メチルプロピルエ
ーテル、メチルブチルエーテルなどの水不溶性エーテル
などが挙げられ、これらは１種用いてもよいし、２種以
上を組み合わせて用いてもよい。In the present invention, a reaction solvent is not particularly required, but if desired, a solvent capable of azeotropically removing water as a by-product, for example, forms an azeotropic mixture composition with water, so that the boiling point is lower than that of water. You may use the following solvents. Such solvents include, for example, hydrocarbon compounds such as pentane, hexane, hegetane, octane, nonane, petroleum ether, petroleum benzine, naphtha, gasoline, kerosene, ligroin, cyclohexane, methylcyclohexane, or benzene, toluene, xylene, and ethylbenzene. , trimethylbenzene, methylethylbenzene, cumene, other aromatic hydrocarbons having 9 to 11 carbon atoms, and aromatic compounds such as chlorinated aromatic hydrocarbons such as chlorobenzene, diethyl ether, diisopropyl ether, methylpropyl ether, methyl butyl ether Examples include water-insoluble ethers such as, and these may be used alone or in combination of two or more.
また、反応温度は、通常８０〜２５０°Ｃ１好ましくは
１２０〜２２０°Ｃの範囲で選ばれ、一方反応時間は通
常０．５〜２０時間、好ましくは１〜１０時間程度であ
る。反応は大気圧下で行ってもよいし、生皮した水を容
易に除去するために、減圧下で行ってもよい。また、留
出した水のみを分離し、溶媒や原料を還流させるための
分水器を反応装置に設置して、反応を行ってもよい。さ
らに、重合禁止効果を高めるために、空気の気流下で反
応を行ってもよいし、空気を反応系に導入してバブリン
グしながら反応を行ってもよい。Further, the reaction temperature is usually selected in the range of 80 to 250°C, preferably 120 to 220°C, and the reaction time is usually about 0.5 to 20 hours, preferably about 1 to 10 hours. The reaction may be carried out under atmospheric pressure, or in order to easily remove the raw water, it may be carried out under reduced pressure. Alternatively, the reaction may be carried out by installing a water separator in the reaction apparatus to separate only the distilled water and reflux the solvent and raw materials. Furthermore, in order to enhance the polymerization inhibition effect, the reaction may be carried out under a stream of air, or the reaction may be carried out while introducing air into the reaction system and bubbling it.
本発明方法においては、原料、触媒及び所望に応じて用
いられる溶媒などの添加順序については特に制限はなく
、全部最初に仕込んでから反応させてもよいし、触媒を
逐次的に添加しながら反応を行ってもよいが、原料、触
媒及び所望に応じて用いられる溶媒などを全部最初に仕
込んでから反応させる方法が効率的である。In the method of the present invention, there are no particular restrictions on the order of addition of raw materials, catalysts, and solvents used as desired; all may be charged first and then reacted, or the catalyst may be added sequentially while reacting. However, it is more efficient to first charge all the raw materials, catalyst, and optionally used solvent, and then carry out the reaction.
本発明方法におけるエステル化反応終了後の生成物の後
処理としては、まず、反応混合液中には、触媒の残液や
触媒に由来する生成物が完全に溶解せず残存しているた
め、ろ過によって分離する。As for the post-treatment of the product after the completion of the esterification reaction in the method of the present invention, first, since the residual liquid of the catalyst and the products derived from the catalyst are not completely dissolved and remain in the reaction mixture, Separate by filtration.
この回収触媒は、循環再使用することもできる。This recovered catalyst can also be recycled and reused.
次いで、残存する未反応のアクリル酸又はメタクリル酸
を、アルカリ水溶液で中和洗浄する。この際分離生成す
る水層のｐＨが８以上（好ましくは、ｐＨ９以上）にな
るようにアルカリ水溶液を添加する。Next, remaining unreacted acrylic acid or methacrylic acid is neutralized and washed with an alkaline aqueous solution. At this time, an alkaline aqueous solution is added so that the pH of the aqueous layer to be separated and produced becomes 8 or more (preferably pH 9 or more).
この中和洗浄する際には、水不溶性の有機溶媒を添加し
て反応生成物であるエステルと水層の分離を容易にする
こともできる。このために添加する溶媒としては、反応
溶媒として使用できる溶媒と同じものを用いるのが有利
である。During this neutralization and washing, a water-insoluble organic solvent may be added to facilitate separation of the ester, which is a reaction product, and the aqueous layer. As the solvent added for this purpose, it is advantageous to use the same solvent that can be used as the reaction solvent.
中和した際に白色の沈澱物が析出するが、これはスズ及
び／又は鉛の水酸化物であり、これも触媒としての能力
を有しているため、ろ別して循環再使用することもでき
る。When neutralized, a white precipitate is deposited, but this is tin and/or lead hydroxide, which also has the ability as a catalyst, so it can be filtered out and recycled for reuse. .
最後に、蒸留（常圧又は減圧）にて分離精製できる比較
的低沸点のエステルは、蒸留にて精製する。Finally, esters with relatively low boiling points that can be separated and purified by distillation (normal pressure or reduced pressure) are purified by distillation.
ここで、分離精製できるものは、常圧での沸点が約２５
０℃以下のエステルである。Here, those that can be separated and purified have a boiling point of about 25 at normal pressure.
It is an ester with a temperature below 0°C.
高沸点のエステルは、常圧若しくは減圧下にて溶媒や軽
質の副生成物を蒸留除去し、その蒸留残液として得るこ
とができる。The high-boiling ester can be obtained as a distillation residue by removing the solvent and light by-products by distillation under normal pressure or reduced pressure.
このようにして、得られた精製アクリル酸エステル又は
メタクリル酸エステルは、重合しやすい性質を有するた
めに、ただちに次の重合工程で使用するか、あるいは保
存する場合には重合禁止剤を新たに添加する必要がある
。この場合、該重合禁止剤の添加量は、アクリル酸エス
テル又はメタクリル酸エステルに対し、通常５〜２００
０ｗｔｐｐｍ、好ましくは１０〜８００ｗｔｐｐｍの範
囲で選ばれる。Since the purified acrylic ester or methacrylic ester obtained in this way has the property of being easily polymerized, it can be used immediately in the next polymerization step, or if stored, a polymerization inhibitor must be added to it. There is a need to. In this case, the amount of the polymerization inhibitor added is usually 5 to 200% based on the acrylic ester or methacrylic ester.
It is selected in the range of 0 wtppm, preferably 10 to 800 wtppm.
次に、実施例により本発明をさらに詳細に説明するが、
本発明はこれらの例によってなんら限定されるものでは
ない。Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these examples.
実施例１〜１０、比較例１〜４
撹拌装置、空気導入管、冷却管、分水器（デイーンスタ
ークトラップ）及び温度計を取り付けた１Ｌの四つロフ
ラスコに、第１〜第３表に示す種類と量のヒドロキシ化
合物、アクリル酸又はメタクリル酸、触媒、重合禁止剤
及び溶媒を仕込んだ。Examples 1 to 10, Comparative Examples 1 to 4 In a 1L four-loaf flask equipped with a stirring device, an air introduction tube, a cooling tube, a water separator (Dean Stark trap), and a thermometer, the ingredients shown in Tables 1 to 3 were added. The indicated types and amounts of hydroxy compound, acrylic acid or methacrylic acid, catalyst, polymerization inhibitor, and solvent were charged.
次に、フラスコ内に空気を導入し、空気雰囲気下で油浴
を使用して加熱し、内容液を撹拌しながら、溶媒と副生
ずる水が共沸し始めてから、数表に示した反応時間の間
、大気圧下で分水器で水を共沸除去しながら、溶媒のみ
還流して反応させた。Next, air is introduced into the flask and heated using an oil bath in an air atmosphere, and the content is stirred until the solvent and by-produced water begin to azeotrope, and then the reaction time shown in the table is shown. During this time, while water was azeotropically removed using a water separator under atmospheric pressure, only the solvent was refluxed and reacted.
反応中の温度は、数表に示すとおりである。The temperature during the reaction is as shown in the table.
反応終了後、反応生成物を高速液体クロマトグラフィー
及びガスクロマトグラフィーにて分析し、ヒドロキシ化
合物基準の転化率及びアクリル酸エステル又はメタクリ
ル酸エステルの収率を求めた。After the reaction was completed, the reaction product was analyzed by high performance liquid chromatography and gas chromatography to determine the conversion rate and the yield of acrylic ester or methacrylic ester based on hydroxy compounds.
その結果を数表に示す。The results are shown in the numerical table.
生成物は、赤外分光光度計及びガスクロマトグラフィー
質量分析計により同定を行って、いずれも原料ヒドロキ
シ化合物に対応するアクリル酸エステル又はメタクリル
酸エステルを確認した。The product was identified using an infrared spectrophotometer and a gas chromatography mass spectrometer, and both were confirmed to be acrylic ester or methacrylic ester corresponding to the raw material hydroxy compound.
（以下余白）
実施例１１〜１９、比較例５〜８
第４〜第６表に示す種類と量のヒドロキシ化合物、アク
リル酸又はメタクリル酸、触媒、重合禁止剤及び溶媒を
用いて反応を行った以外は、実施例１〜１０と同様に実
施した。その結果を数表に示す。(Left below) Examples 11 to 19, Comparative Examples 5 to 8 Reactions were carried out using hydroxy compounds, acrylic acid or methacrylic acid, catalysts, polymerization inhibitors, and solvents of the types and amounts shown in Tables 4 to 6. Except for this, it was carried out in the same manner as in Examples 1 to 10. The results are shown in the numerical table.
生成物は、赤外分光光度計及びガスクロマトグラフィー
質量分析計により同定を行って、いずれも原料ヒドロキ
シ化合物に対応するアクリル酸エステル又はメタクリル
酸エステルを確認した。The product was identified using an infrared spectrophotometer and a gas chromatography mass spectrometer, and both were confirmed to be acrylic ester or methacrylic ester corresponding to the raw material hydroxy compound.
（以下余白）
〔発明の効果〕
本発明方法によると、アクリル酸又はメタクリル酸と、
ヒドロキシル基を少なくとも２個有するヒドロキシ化合
物、あるいはヒドロキシル基の酸素原子以外の酸素原子
及び／又は窒素原子を少なくとも１個有するヒドロキシ
化合物とを反応させて、そのエステルを製造する際に、
特定の触媒を用いることにより、着色及び副反応がほと
んどなく、容易に高収率でアクリル酸エステル又はメタ
クリル酸エステルを製造することができる。(The following is a blank space) [Effect of the invention] According to the method of the present invention, acrylic acid or methacrylic acid,
When producing an ester by reacting a hydroxy compound having at least two hydroxyl groups, or a hydroxy compound having at least one oxygen atom and/or nitrogen atom other than the oxygen atom of the hydroxyl group,
By using a specific catalyst, acrylic esters or methacrylic esters can be easily produced in high yields with almost no coloration or side reactions.
Claims (1)
ロキシル基を少なくとも２個有するか、あるいはヒドロ
キシル基の酸素原子以外の酸素原子及び／又は窒素原子
を少なくとも１個有するヒドロキシ化合物とを反応させ
てアクリル酸エステル又はメタクリル酸エステルを製造
するに当たり、触媒として金属スズ、金属鉛、スズ化合
物及び鉛化合物の中から選ばれた少なくとも１種を用い
ることを特徴とするアクリル酸エステル又はメタクリル
酸エステルの製造方法。1. Reacting (A) acrylic acid or methacrylic acid with (B) a hydroxy compound having at least two hydroxyl groups or having at least one oxygen atom and/or nitrogen atom other than the oxygen atom of the hydroxyl group. Production of acrylic ester or methacrylic ester, characterized in that at least one selected from metal tin, metallic lead, tin compounds, and lead compounds is used as a catalyst in producing acrylic ester or methacrylic ester. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1173931A JPH0341051A (en) | 1989-07-07 | 1989-07-07 | Preparation of acrylate or methacrylate ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1173931A JPH0341051A (en) | 1989-07-07 | 1989-07-07 | Preparation of acrylate or methacrylate ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0341051A true JPH0341051A (en) | 1991-02-21 |
Family
ID=15969726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1173931A Pending JPH0341051A (en) | 1989-07-07 | 1989-07-07 | Preparation of acrylate or methacrylate ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0341051A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05310654A (en) * | 1991-09-02 | 1993-11-22 | Yoshinori Hayashi | Esterification by new catalytic method |
| EP0646567A2 (en) * | 1993-09-03 | 1995-04-05 | CPS CHEMICAL COMPANY, Inc. | Organotin catalyzed transesterification |
| EP0663386A1 (en) * | 1994-01-17 | 1995-07-19 | Röhm GmbH | Process for the transesterification of (meth-)acrylic esters |
| US5606103A (en) * | 1993-09-03 | 1997-02-25 | Cps Chemical Company, Inc. | Organotin catalyzed transesterification |
| JP2006028172A (en) * | 2004-06-16 | 2006-02-02 | Central Glass Co Ltd | 2-trifluoromethylacrylic acid 3-hydroxypropyl ester and method for producing the same |
| US7199262B2 (en) | 2004-06-16 | 2007-04-03 | Central Glass Company, Limited | 3-Hydroxypropyl ester of 2-trifluoromethylacrylic acid and process for producing same |
| JP2016520096A (en) * | 2013-05-20 | 2016-07-11 | サウディ ベーシック インダストリーズ コーポレイション | Method for purifying acetic acid and acrylic acid |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5461294A (en) * | 1977-10-26 | 1979-05-17 | Ube Ind Ltd | Production of oligoestr acrylate |
| JPS55130937A (en) * | 1979-03-29 | 1980-10-11 | Sekisui Chem Co Ltd | Preparation of ester |
| JPS55139339A (en) * | 1979-04-13 | 1980-10-31 | Ube Ind Ltd | Preparation of oligoester acrylate |
| JPS56133033A (en) * | 1980-03-01 | 1981-10-17 | Bp Chem Int Ltd | Nonhomogeneous esterifying catalyst, its manufacture and use in manufacture of residual ester of its catalyst |
| JPS62106051A (en) * | 1985-11-01 | 1987-05-16 | Sanyo Chem Ind Ltd | Production of acrylic acid ester |
| JPS62106057A (en) * | 1985-11-01 | 1987-05-16 | Sanyo Chem Ind Ltd | Production of acrylic acid ester |
-
1989
- 1989-07-07 JP JP1173931A patent/JPH0341051A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5461294A (en) * | 1977-10-26 | 1979-05-17 | Ube Ind Ltd | Production of oligoestr acrylate |
| JPS55130937A (en) * | 1979-03-29 | 1980-10-11 | Sekisui Chem Co Ltd | Preparation of ester |
| JPS55139339A (en) * | 1979-04-13 | 1980-10-31 | Ube Ind Ltd | Preparation of oligoester acrylate |
| JPS56133033A (en) * | 1980-03-01 | 1981-10-17 | Bp Chem Int Ltd | Nonhomogeneous esterifying catalyst, its manufacture and use in manufacture of residual ester of its catalyst |
| JPS62106051A (en) * | 1985-11-01 | 1987-05-16 | Sanyo Chem Ind Ltd | Production of acrylic acid ester |
| JPS62106057A (en) * | 1985-11-01 | 1987-05-16 | Sanyo Chem Ind Ltd | Production of acrylic acid ester |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05310654A (en) * | 1991-09-02 | 1993-11-22 | Yoshinori Hayashi | Esterification by new catalytic method |
| EP0930290A1 (en) * | 1993-09-03 | 1999-07-21 | CPS CHEMICAL COMPANY, Inc. | Organotin catalysed transesterification |
| EP0646567A2 (en) * | 1993-09-03 | 1995-04-05 | CPS CHEMICAL COMPANY, Inc. | Organotin catalyzed transesterification |
| EP0646567A3 (en) * | 1993-09-03 | 1995-06-21 | Cps Chem Co Inc | Organotin catalyzed transesterification. |
| US5498751A (en) * | 1993-09-03 | 1996-03-12 | Cps Chemical Company, Inc. | Organotin catalyzed transesterification |
| US5554785A (en) * | 1993-09-03 | 1996-09-10 | Cps Chemical Company, Inc. | Organotin catalyzed transesterification products |
| US5606103A (en) * | 1993-09-03 | 1997-02-25 | Cps Chemical Company, Inc. | Organotin catalyzed transesterification |
| EP0799816A1 (en) * | 1993-09-03 | 1997-10-08 | CPS CHEMICAL COMPANY, Inc. | Organotin catalyzed transesterification |
| EP0663386A1 (en) * | 1994-01-17 | 1995-07-19 | Röhm GmbH | Process for the transesterification of (meth-)acrylic esters |
| JP2006028172A (en) * | 2004-06-16 | 2006-02-02 | Central Glass Co Ltd | 2-trifluoromethylacrylic acid 3-hydroxypropyl ester and method for producing the same |
| US7199262B2 (en) | 2004-06-16 | 2007-04-03 | Central Glass Company, Limited | 3-Hydroxypropyl ester of 2-trifluoromethylacrylic acid and process for producing same |
| JP2016520096A (en) * | 2013-05-20 | 2016-07-11 | サウディ ベーシック インダストリーズ コーポレイション | Method for purifying acetic acid and acrylic acid |
| US9944582B2 (en) | 2013-05-20 | 2018-04-17 | Saudi Basic Industries Corporation | Method for the purification of acetic acid and acrylic acid |
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