JPH01316389A - Method for removing organotin compound - Google Patents
Method for removing organotin compoundInfo
- Publication number
- JPH01316389A JPH01316389A JP6715689A JP6715689A JPH01316389A JP H01316389 A JPH01316389 A JP H01316389A JP 6715689 A JP6715689 A JP 6715689A JP 6715689 A JP6715689 A JP 6715689A JP H01316389 A JPH01316389 A JP H01316389A
- Authority
- JP
- Japan
- Prior art keywords
- organotin
- compound
- organotin compound
- acid
- carboxylic 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
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims description 16
- -1 carboxylic acid compound Chemical class 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000005809 transesterification reaction Methods 0.000 claims description 12
- 238000010992 reflux Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 150000002148 esters Chemical class 0.000 abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 abstract description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000005711 Benzoic acid Substances 0.000 abstract description 2
- 239000005909 Kieselgur Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 abstract description 2
- 235000010233 benzoic acid Nutrition 0.000 abstract description 2
- 239000004310 lactic acid Substances 0.000 abstract description 2
- 239000010451 perlite Substances 0.000 abstract description 2
- 235000019362 perlite Nutrition 0.000 abstract description 2
- 239000011541 reaction mixture Substances 0.000 abstract description 2
- HFVMEOPYDLEHBR-UHFFFAOYSA-N (2-fluorophenyl)-phenylmethanol Chemical compound C=1C=CC=C(F)C=1C(O)C1=CC=CC=C1 HFVMEOPYDLEHBR-UHFFFAOYSA-N 0.000 abstract 1
- 239000001384 succinic acid Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000002253 acid Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 150000003606 tin compounds Chemical class 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- MACVNMKPAKPZQG-UHFFFAOYSA-N dioctyltin(2+);methanolate Chemical compound CCCCCCCC[Sn](OC)(OC)CCCCCCCC MACVNMKPAKPZQG-UHFFFAOYSA-N 0.000 description 2
- WDQNIWFZKXZFAY-UHFFFAOYSA-M fentin acetate Chemical compound CC([O-])=O.C1=CC=CC=C1[Sn+](C=1C=CC=CC=1)C1=CC=CC=C1 WDQNIWFZKXZFAY-UHFFFAOYSA-M 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 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
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle 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
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [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
- 238000005406 washing Methods 0.000 description 2
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- BEOSQUOYHDCDNU-UHFFFAOYSA-L 4,4-dibutyl-1,3,2,4-dioxathiastannetane 2,2-dioxide Chemical compound CCCC[Sn]1(CCCC)OS(=O)(=O)O1 BEOSQUOYHDCDNU-UHFFFAOYSA-L 0.000 description 1
- MOZDKDIOPSPTBH-UHFFFAOYSA-N Benzyl parahydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 MOZDKDIOPSPTBH-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- CYBDMPYGULOWLP-UHFFFAOYSA-N S1SCC=C1.C(CCC)[Sn]CCCC Chemical compound S1SCC=C1.C(CCC)[Sn]CCCC CYBDMPYGULOWLP-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 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
- YLFRJROMPGNJRP-UHFFFAOYSA-L [dibutyl(3-sulfanylpropanoyloxy)stannyl] 3-sulfanylpropanoate Chemical compound [O-]C(=O)CCS.[O-]C(=O)CCS.CCCC[Sn+2]CCCC YLFRJROMPGNJRP-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
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- WFLLPKDDXLHZLQ-UHFFFAOYSA-N dibutoxy(dioctyl)stannane Chemical compound CCCCCCCC[Sn](OCCCC)(OCCCC)CCCCCCCC WFLLPKDDXLHZLQ-UHFFFAOYSA-N 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- UROKUKHYYXBCQE-UHFFFAOYSA-L dibutyl(diphenoxy)stannane Chemical compound C=1C=CC=CC=1O[Sn](CCCC)(CCCC)OC1=CC=CC=C1 UROKUKHYYXBCQE-UHFFFAOYSA-L 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- JJPZOIJCDNHCJP-UHFFFAOYSA-N dibutyl(sulfanylidene)tin Chemical compound CCCC[Sn](=S)CCCC JJPZOIJCDNHCJP-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- QSHZUFRQHSINTB-UHFFFAOYSA-L dibutyltin(2+);dibromide Chemical compound CCCC[Sn](Br)(Br)CCCC QSHZUFRQHSINTB-UHFFFAOYSA-L 0.000 description 1
- WNVQCJNZEDLILP-UHFFFAOYSA-N dimethyl(oxo)tin Chemical compound C[Sn](C)=O WNVQCJNZEDLILP-UHFFFAOYSA-N 0.000 description 1
- YAHBZWSDRFSFOO-UHFFFAOYSA-L dimethyltin(2+);2-(2-ethylhexoxy)-2-oxoethanethiolate Chemical compound CCCCC(CC)COC(=O)CS[Sn](C)(C)SCC(=O)OCC(CC)CCCC YAHBZWSDRFSFOO-UHFFFAOYSA-L 0.000 description 1
- SDTDHTCWRNVNAJ-UHFFFAOYSA-L dimethyltin(2+);diacetate Chemical compound CC(=O)O[Sn](C)(C)OC(C)=O SDTDHTCWRNVNAJ-UHFFFAOYSA-L 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 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
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 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
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([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
- 235000014655 lactic acid Nutrition 0.000 description 1
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 1
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 1
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 1
- 229960002216 methylparaben Drugs 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- ODOPKAJVFRHHGM-UHFFFAOYSA-N phenyltin Chemical compound [Sn]C1=CC=CC=C1 ODOPKAJVFRHHGM-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 1
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は有機錫化合物の工業上有用な除去法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to an industrially useful method for removing organotin compounds.
〔従来の技術と発明が解決しようとする課題〕モノおよ
びジ有機錫化合物は工業的に価値が高く、ポリ塩化ビニ
ル樹脂用安定剤、有機合成触媒、カチオン電着塗装触媒
またはそれらの合成中間体などとして多用され、また、
トリ有機錫化合物は農薬などの分野で重要な位置をしめ
ている。特に、近年、有機錫オキサイドはエステル交換
法などの有機合成反応において、触媒として電波されて
いる。[Prior art and problems to be solved by the invention] Mono- and diorganotin compounds have high industrial value, and can be used as stabilizers for polyvinyl chloride resins, organic synthesis catalysts, cationic electrodeposition coating catalysts, or synthetic intermediates thereof. It is often used as,
Tri-organotin compounds play an important role in fields such as agricultural chemicals. In particular, in recent years, organic tin oxides have been used as catalysts in organic synthesis reactions such as transesterification.
ところで、エステル交換反応において、有機錫化合物を
触媒として使用する場合、生成した反応混合物から除去
することが必要である。しかしながら、有機錫化合物を
洗浄、濾過、蒸留、再結晶などの通常の方法により除去
することには種々の難点があった。By the way, when an organotin compound is used as a catalyst in the transesterification reaction, it is necessary to remove it from the generated reaction mixture. However, there are various difficulties in removing organotin compounds by conventional methods such as washing, filtration, distillation, and recrystallization.
すなわち、有機錫化合物は通常、水不溶性または水ｌｄ
溶性のため有機層に溶解しており、水洗浄のみによって
反応系から除去することはほとんど不可能である。また
、アルカリ水溶液を用いて対応する水酸化物にするなど
して、溶媒に不溶性の化合物に変えて濾過する方法もあ
るが、水酸化物の粒子形が微細であり、ｉｌ！過効率が
悪く、濾過に長時間を要し、工業上問題である。このよ
うなことから、蒸留操作により目的物を分取して、有機
錫化合物を残香として得る方法、吸着剤を用いて有機錫
化合物を吸着させる方法、または再結晶などの手段によ
り母液中に残す方法などが採られてきていた。ところが
、これらの方法はいずれも特殊な装置を要することなど
の設備上の問題があり、また、有機錫化合物の除去率、
目的物の収率などの点で工業的に満足できる結果が得ら
れていないのが実状である。That is, organotin compounds are typically water-insoluble or water-soluble.
Due to its solubility, it is dissolved in the organic layer, and it is almost impossible to remove it from the reaction system only by washing with water. There is also a method of converting the corresponding hydroxide into a compound insoluble in the solvent using an alkaline aqueous solution and filtering it, but the particle shape of the hydroxide is fine and il! The filtration efficiency is poor and filtration takes a long time, which is an industrial problem. For this reason, it is possible to obtain the organic tin compound as a residual aroma by separating the target substance by distillation, by adsorbing the organic tin compound using an adsorbent, or by leaving it in the mother liquor by means such as recrystallization. methods have been adopted. However, all of these methods have equipment problems such as the need for special equipment, and the removal rate of organotin compounds is low.
The reality is that industrially satisfactory results have not been obtained in terms of the yield of the target product.
一般に、有機錫化合物を触媒とする反応では目的物が好
収率、好品質で得られることから、特別な精製手段を用
いることなく、この触媒を除去することができれば、目
的物はそのまま製品として使用しうるのである。したが
って、本発明は有機錫化合物含有エステル交換反応液か
ら簡便かつ効率よく、有機錫化合物を除去する方法を提
供することを目的としている。In general, reactions using organotin compounds as catalysts yield the target product in good yield and quality, so if this catalyst can be removed without using special purification methods, the target product can be used as a product as it is. It can be used. Therefore, an object of the present invention is to provide a method for easily and efficiently removing an organotin compound from an organotin compound-containing transesterification reaction solution.
上記目的を達成するために、本発明者らは鋭意検討した
結果、カルボン酸化合物水溶液を用いて有機溶媒に不溶
性の有Ｖ／ｍ錫化合物とすることによって、容易に有機
錫化合物を除去しうろことを見出し、本発明を完成させ
るに至った。In order to achieve the above object, the present inventors have made extensive studies and found that by using an aqueous solution of a carboxylic acid compound to form a tin compound with V/m that is insoluble in an organic solvent, the organotin compound can be easily removed and the scales removed. They discovered this and completed the present invention.
ところで、カルボン酸化合物のみの使用によっても、有
機溶媒に不溶性の有機錫化合物は、生成するが、除去時
、濾過時間が長くかかることもあり、工業生産上困難な
こともある。しかし、本発明のようにカルボン酸化合物
水溶液として使用することにより、非常に濾過の容易な
有機錫化合物として生成することが判明した。この方法
によれば、工業的にも十分操作が可能であり、満足のい
く結果が得られる。Incidentally, even if only a carboxylic acid compound is used, an organic tin compound insoluble in an organic solvent is produced, but it may take a long time to filter during removal, which may be difficult in industrial production. However, it has been found that when used as an aqueous solution of a carboxylic acid compound as in the present invention, it is produced as an organic tin compound that is very easily filterable. This method is industrially operable and provides satisfactory results.
本発明は、有機錫化合物含有エステル交換反応液へカル
ボン酸化合物水溶液を加え、還流脱水することにより生
成する濾過性の良好な不溶性有機錫化合物を除去するこ
とを特徴とする有機錫化合物の除去法に関する。The present invention is a method for removing an organotin compound, which is characterized by adding an aqueous solution of a carboxylic acid compound to an organotin compound-containing transesterification reaction solution and removing an insoluble organotin compound with good filterability produced by reflux dehydration. Regarding.
本発明方法に適用しうる有機錫化合物としては、有機錫
ハライド（有機錫クロライド、有機錫ブロマイド、有機
錫アイオダイドなど）、有機錫オキサイド、有機錫酸、
有機錫ハイドロオキサイド、有機錫スルフイソド、有機
錫メルカプタン、有機錫硫酸塩、有機錫アルコキサイド
（アルコキサイド部は炭素数１〜８個のアルキル基を含
む）、有機錫カルボン酸、その塩（アルカリ金属、アル
カリ土類金属、銅、亜鉛、アルミニウムなどの塩）もし
くはそのエステル（エステル部は炭素数１〜８個のアル
キル、アリール、アラルキルを含む）または有機錫チオ
アルカン酸エステル（エステル部は炭素数１〜８個のア
ルキル基を含む）などがあげられ、それぞれモノ−、ジ
ーおよびトリ有機錫化合物が含まれる。置換基である有
ａ基としては炭素数１〜８個のアルキル基（メチル、エ
チル、プロピル、イソプロピル、ブチル、イソブチル、
第３級ブチル、ペンチル、イソペンチル、ネオペンチル
、ヘキシル、オクチル、２−エチルヘキシル、１．１，
３．３−テトラメチルブチルなどがあげられ、特にブチ
ル、オクチルが好ましい。）、炭素数３〜７個のシクロ
アルキル（シクロプロピル、シクロペンチル、シクロヘ
キシル、シクロヘプチルなどがあげられ、特にシクロヘ
キシルが好ましい。）、フェニル、置換フェニル（置換
基としては、好ましくは炭素数１〜８個のアルキル基が
あげられる。）、アラルキル（ベンジル、ベンズヒドリ
ル、トリチル、２−フェニルエチル、ネオフィルなど）
などの炭素数１〜１８個の炭化水素基を意味する。Organotin compounds that can be applied to the method of the present invention include organotin halides (organotin chloride, organotin bromide, organotin iodide, etc.), organotin oxide, organotin acid,
Organotin hydroxide, organotin sulfisode, organotin mercaptan, organotin sulfate, organotin alkoxide (the alkoxide part contains an alkyl group having 1 to 8 carbon atoms), organotin carboxylic acid, its salt (alkali metal, alkali salts of earth metals, copper, zinc, aluminum, etc.) or their esters (ester part includes alkyl, aryl, aralkyl having 1 to 8 carbon atoms) or organotin thioalkanoic acid ester (ester part contains 1 to 8 carbon atoms) alkyl groups), including mono-, di-, and tri-organotin compounds, respectively. Examples of a substituent groups include alkyl groups having 1 to 8 carbon atoms (methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Tertiary butyl, pentyl, isopentyl, neopentyl, hexyl, octyl, 2-ethylhexyl, 1.1,
Examples include 3,3-tetramethylbutyl, and butyl and octyl are particularly preferred. ), cycloalkyl having 3 to 7 carbon atoms (including cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, etc., with cyclohexyl being particularly preferred), phenyl, substituted phenyl (the substituent preferably has 1 to 8 carbon atoms) ), aralkyl (benzyl, benzhydryl, trityl, 2-phenylethyl, neophyll, etc.)
means a hydrocarbon group having 1 to 18 carbon atoms.
これら有機錫化合物としては、具体的には、たとえば、
ジメチル錫オキシド、ジブチル錫オキシド、ジオクチル
錫オキシド、ビストリブチル錫オキシド、モツプチル錫
オキシド、モノブチル錫酸、モノメチル錫酸、モノオク
チル錫酸、モノフェニル錫酸などの有機錫酸化物、ジブ
チル錫スルフィド、ジフェニル錫スルフィドなどの有機
錫硫化物、モツプチル錫トリクロリド、ジブチル錫ジブ
ロミド、モノフェニル錫トリプロミドなどの有機錫ハロ
ゲン化物、ジブチル錫サルフェートなどの有機錫硫酸塩
、ジメチル錫ジアセテート、ジブチル錫ジアセテート、
ジオクチル錫ジアセテート、トリフェニル錫アセテート
、ジブチル錫ジラウレート、ジオクチル錫ジラウレート
、ジブチル錫マレエートなどの有機錫カルボン酸エステ
ル、ジブチル錫チオグレコレート、ジブチル錫β−メル
カプトプロピオネートなどの有機錫チオアルカン酸エス
テル、ジブチル錫ジチオールなどの有機錫メルカプタン
、ジオクチル錫ジメトキシド、ジオクチル錫ジブトキシ
ド、ジブチル錫ジフェノキシドなどの有ａｔｕｙｔアル
コキシドやフェノキシト、テトラブチル錫、テトラフェ
ニル錫などのテトラアルキルまたはアリール錫があげら
れるが、勿論これらに限定されるものではない。Specifically, these organic tin compounds include, for example,
Organic tin oxides such as dimethyltin oxide, dibutyltin oxide, dioctyltin oxide, bistributyltin oxide, motuputyltin oxide, monobutyltin oxide, monomethylstannic acid, monooctyltinnic acid, monophenyltinnic acid, dibutyltin sulfide, diphenyl Organotin sulfides such as tin sulfide, organotin halides such as motuputyltin trichloride, dibutyltin dibromide, monophenyltin tripromide, organotin sulfates such as dibutyltin sulfate, dimethyltin diacetate, dibutyltin diacetate,
Organic tin carboxylic acid esters such as dioctyltin diacetate, triphenyltin acetate, dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin maleate; organic tin thioalkanoic acid esters such as dibutyltin thiogrecolate and dibutyltin β-mercaptopropionate; , organic tin mercaptans such as dibutyltin dithiol, atuyt alkoxides and phenoxides such as dioctyltin dimethoxide, dioctyltin dibutoxide, and dibutyltin diphenoxide, and tetraalkyl or aryltins such as tetrabutyltin and tetraphenyltin. It is not limited to these.
これら有機錫化合物含有エステル交換反応液は、通常、
有機溶媒（ベンゼン、トルエン、キシレンなどの芳香族
炭化水素類、ヘキサン、ヘプタン、アイソパーＥ（エク
ソン化学型、炭素数８〜１０の混合溶媒）などの脂肪族
炭化水素類、クロロメタン、ジクロロエタン、クロロホ
ルム、四塩化炭素、クロロベンゼンなどのハロゲン化炭
化水素などがあげられる。）に熔解している。These organotin compound-containing transesterification reaction solutions are usually
Organic solvents (aromatic hydrocarbons such as benzene, toluene, xylene, etc., aliphatic hydrocarbons such as hexane, heptane, Isopar E (exon chemical type, mixed solvent with 8 to 10 carbon atoms), chloromethane, dichloroethane, chloroform , carbon tetrachloride, halogenated hydrocarbons such as chlorobenzene, etc.).
有機錫化合物と反応して不溶性化合物を生成するために
用いられるカルボン酸化合物とは脂肪族、芳香族または
複素芳香族カルボン酸で、モノ、ジまたはトリカルボン
酸が含まれる。たとえば酢酸、プロピオン酸、乳酸、シ
ュウ酸、コハク酸、クエン酸、フマール酸、マレイン酸
、マロン酸、アジピン酸、グルタル酸、安息香酸、フク
ル酸、テレフタル酸、サリチル酸、ニコチン酸などがあ
げられる。The carboxylic acid compound used to react with the organotin compound to form the insoluble compound is an aliphatic, aromatic or heteroaromatic carboxylic acid, including mono-, di- or tricarboxylic acids. Examples include acetic acid, propionic acid, lactic acid, oxalic acid, succinic acid, citric acid, fumaric acid, maleic acid, malonic acid, adipic acid, glutaric acid, benzoic acid, fucuric acid, terephthalic acid, salicylic acid, and nicotinic acid.
不溶性有機錫化合物は有機錫化合物含有エステル交換反
応液に有機酸水溶液を添加し、約１０分から数時間還流
させ、その後数時間、脱水を行なうことにより生成され
る。なお、必要により濾過助剤（ケイソウ土、パーライ
ト、セルロース、アスベスト、プラスチック粒、鋸屑、
マグネシア、セラコラ、活性炭、酸性白土、ツルカフロ
ックなど）が使用される。カルボン酸化合物の使用量は
有機錫化合物に対して、約０．３〜約ｌＯモル、好まし
くは０．５〜５モルでよく適当量の水に溶解し、水溶液
として使用する。また、濾過助剤の有機錫化合物に対す
る使用量は約１０〜約１０００モル、好ましくは１００
〜５００モルがよい。The insoluble organotin compound is produced by adding an organic acid aqueous solution to an organotin compound-containing transesterification reaction solution, refluxing the mixture for about 10 minutes to several hours, and then dehydrating it for several hours. In addition, filter aids (diatomaceous earth, perlite, cellulose, asbestos, plastic particles, sawdust,
(magnesia, ceracola, activated carbon, acid clay, turca floc, etc.) are used. The amount of the carboxylic acid compound to be used is about 0.3 to about 10 mol, preferably 0.5 to 5 mol, based on the organotin compound, and the carboxylic acid compound is dissolved in an appropriate amount of water and used as an aqueous solution. The amount of the filter aid to be used relative to the organic tin compound is about 10 to about 1000 mol, preferably 100 mol.
-500 mol is good.
このようにして生成した不溶性有機錫化合物は有機溶媒
に対し、不溶性ないし難溶性を示すものであって、水溶
性であっても差支えないし、また水および有機溶媒に不
溶性ないし難溶性のミセル化合物を形成していてもよい
。この不溶性有機錫化合物は濾過などの簡便な方法によ
りほぼ完全に分離することができる。また、必要に応じ
、遠心沈降操作などにより得た上澄液を濾過すると、よ
り効率的である。The insoluble organotin compound thus produced is insoluble or poorly soluble in organic solvents, and may be water-soluble. It may be formed. This insoluble organotin compound can be almost completely separated by a simple method such as filtration. Furthermore, if necessary, it is more efficient to filter the supernatant obtained by centrifugal sedimentation.
このようにして得た濾液は必要に応じ、本発明方法を反
復実施することにより、有機錫化合物の濃度を低減させ
ることができる。The concentration of the organotin compound in the filtrate thus obtained can be reduced by repeatedly carrying out the method of the present invention, if necessary.
本発明方法により、有機錫化合物が除去されたエステル
交換反応液は、そのまま目的物どして使用できるし、ま
た、再結晶、蒸留、カラムクロマトグラフィーなどの常
法により目的物を単離、精製することができる。The transesterification reaction solution from which organotin compounds have been removed by the method of the present invention can be used as it is as the target product, or the target product can be isolated and purified by conventional methods such as recrystallization, distillation, and column chromatography. can do.
本発明方法を実施することにより、反応系から不要な有
機錫化合物を１０ｐｐｍ以下の濃度にまでほぼ完全に除
去することができ、また特別な装置も不要であることか
ら操作も極めて簡便であり、さらに、目的物はほとんど
吸着除去されないことから、工業的にすぐれた方法であ
る。By carrying out the method of the present invention, unnecessary organotin compounds can be almost completely removed from the reaction system to a concentration of 10 ppm or less, and since no special equipment is required, the operation is extremely simple. Furthermore, since the target substance is hardly removed by adsorption, it is an industrially excellent method.
以下に実施例を挙げて、本発明を具体的に説明するが、
本発明はこれらにより限定されるものではない。The present invention will be specifically explained with reference to Examples below.
The present invention is not limited to these.
実施例１
モノブチル錫オキサイドを触媒として用い３−（３，５
−ジ第３級ブチルー４−ヒドロキシフェニル）プロピオ
ン酸メチルとペンタエリスリトールとのエステル交換反
応により生成したテトラキス（３−（３，５−ジ第３級
ブチル−４−ヒドロキシフェニル）プロピオニルオキシ
メチルコメタンのトルエン溶液３００ｄ（絡合量７００
ｐｐｍ）にシュウ酸・２水和物０．５ｇを水６ｇに溶解
した水溶液を加え、還流下３０分間撹拌し、その後、還
流脱水を２時間行なう。そして約１００℃まで冷却し、
合成ケイ酸マグネシウム０．６ｇを加えて３０分間ｔ
ｏ ｏ ’ｃで撹拌する。その後１００℃で濾過して透
明なトルエン溶液を得る。原子吸光光度法により錫残存
量を測定したところ３ｐｐｍであった。（除去率９９．
６％）
実施例２
溶媒をトルエンからアイソパーＥに変えて実施例１と同
様な操作を行なったところ、錫残存量は５ｐｐｍであっ
た。（除去率９９．３％）実施例３
モノブチル錫オキサイドを触媒として用いて３−（３，
５−ジ第３級ブチルー４−ヒドロキシフェニル）プロピ
オン酸メチルとオクタデシルアルコールとのエステル交
換反応により生成した３〜（３，５−ジ第３級ブチルー
４−ヒドロキシフェニル）プロピオン酸オクタデシルの
トルエン溶液３００Ｍ１（絡合、１２００ｐｐｍ）にシ
ュウ酸・２水和吻０．１ｇを水２ｇに溶解した水溶液を
加え、還流下３０分間撹拌し、その後、還流脱水を２時
間行なう。そして約１００℃まで冷却し、ツルカフロッ
ク０．２ｇを加えて３０分間１００℃で撹拌する。その
後１００°Ｃで濾過して透明なトルエン溶液を得る。原
子吸光光度法により錫残存量を測定したところ、ｌｐｐ
ｍであった。（除去率９９．５％）
実施例４
実施例１においてモノブチル錫オキサイドの代りに、ト
リフェニル錫アセテートまたはジオクチル錫メトキサイ
ドを用いて同様のエステル交換反応を行ない、ついで処
理したところ、錫残存量はそれぞれ５または６ｐｐｍで
あった。Example 1 3-(3,5
- Tetrakis(3-(3,5-ditert-butyl-4-hydroxyphenyl)propionyloxymethylcomethane) produced by transesterification reaction between methyl ditert-butyl-4-hydroxyphenyl)propionate and pentaerythritol 300 d of toluene solution (amount of entanglement 700
An aqueous solution of 0.5 g of oxalic acid dihydrate dissolved in 6 g of water was added to the mixture (ppm), stirred under reflux for 30 minutes, and then dehydrated under reflux for 2 hours. Then, cool it to about 100℃,
Add 0.6g of synthetic magnesium silicate and leave for 30 minutes.
Stir at o o'c. It is then filtered at 100°C to obtain a clear toluene solution. The residual amount of tin was measured by atomic absorption spectrophotometry and was found to be 3 ppm. (Removal rate 99.
6%) Example 2 The same operation as in Example 1 was carried out by changing the solvent from toluene to Isopar E, and the residual amount of tin was 5 ppm. (Removal rate 99.3%) Example 3 Using monobutyltin oxide as a catalyst, 3-(3,
Toluene solution of octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate produced by transesterification reaction between methyl 5-ditert-butyl-4-hydroxyphenyl)propionate and octadecyl alcohol 300M1 (entanglement, 1200 ppm) was added with an aqueous solution of 0.1 g of oxalic acid dihydrate dissolved in 2 g of water, stirred under reflux for 30 minutes, and then dehydrated under reflux for 2 hours. Then, the mixture is cooled to about 100°C, 0.2 g of Tulka floc is added, and the mixture is stirred at 100°C for 30 minutes. It is then filtered at 100°C to obtain a clear toluene solution. When the residual amount of tin was measured by atomic absorption spectrophotometry, lpp
It was m. (Removal rate 99.5%) Example 4 A similar transesterification reaction was carried out in Example 1 using triphenyltin acetate or dioctyltin methoxide instead of monobutyltin oxide, and then the remaining amount of tin was They were 5 or 6 ppm, respectively.
実施例５
実施例２においてモノブチル錫オキサイドの代りに、ジ
ブチル錫ジクロライド、ジメチル錫ビス（２−エチルへ
キシルチオグリコレート）、テトラメチル錫またはジオ
クチル錫ジブ・ロマイドを用いて同様の反応、処理を行
なったところ、錫残存量はそれぞれ７．４．６または３
ｐｐｍであった。Example 5 The same reaction and treatment as in Example 2 was carried out using dibutyltin dichloride, dimethyltin bis(2-ethylhexylthioglycolate), tetramethyltin or dioctyltin dibu-romide instead of monobutyltin oxide. As a result, the residual amount of tin was 7, 4, 6 or 3, respectively.
It was ppm.
実施例６
パラヒドロキシ安息香酸メチル、ベンジルアルコールお
よびジプチル錫オキサイドを用いてエステル交換反応を
行ない、生成したバラヒドロキシ安息香酸ベンジルのト
ルエン溶？＆３００ｍｌ （絡合量４００ｐｐｍ）にク
エン酸０．２ｇを水４ｇに溶解した水溶液を加え、還流
下３０分間撹拌し、その後、還流脱水を２時間行なう。Example 6 Transesterification was carried out using methyl para-hydroxybenzoate, benzyl alcohol and diptyltin oxide, and benzyl para-hydroxybenzoate was dissolved in toluene. An aqueous solution of 0.2 g of citric acid dissolved in 4 g of water was added to 300 ml (entanglement amount: 400 ppm), stirred under reflux for 30 minutes, and then dehydrated under reflux for 2 hours.
約１００℃まで冷却しツルカフロック０．４ｇを加えて
３０分間１００℃で撹拌する。その後１００℃で濾過す
ると、絡合量が３ｐｐｍであった。（除去率９９．３％
）Cool to about 100°C, add 0.4 g of Tulka floc, and stir at 100°C for 30 minutes. Thereafter, when it was filtered at 100°C, the amount of entanglement was 3 ppm. (Removal rate 99.3%
)
Claims (1)
カルボン酸化合物水溶液を加え、生成する不溶性有機錫
化合物を除去することを特徴とする有機錫化合物の除去
法。(1) A method for removing an organotin compound, which comprises adding an aqueous solution of a carboxylic acid compound to a transesterification reaction solution using an organotin compound as a catalyst, and removing the generated insoluble organotin compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6715689A JPH078878B2 (en) | 1988-03-25 | 1989-03-17 | Method for removing organotin compounds |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7281488 | 1988-03-25 | ||
| JP63-72814 | 1988-03-25 | ||
| JP6715689A JPH078878B2 (en) | 1988-03-25 | 1989-03-17 | Method for removing organotin compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01316389A true JPH01316389A (en) | 1989-12-21 |
| JPH078878B2 JPH078878B2 (en) | 1995-02-01 |
Family
ID=26408333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6715689A Expired - Lifetime JPH078878B2 (en) | 1988-03-25 | 1989-03-17 | Method for removing organotin compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH078878B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6184411B1 (en) | 1998-02-02 | 2001-02-06 | Ciba Specialty Chemicals Corporation | Process for the preparation of substituted hydroxyhydrocinnamate esters by removal of tin catalysts |
| WO2018199203A1 (en) * | 2017-04-26 | 2018-11-01 | 大阪有機化学工業株式会社 | Method for producing polyfunctional acrylate |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102018131625B4 (en) * | 2018-12-10 | 2020-10-08 | Schaeffler Technologies AG & Co. KG | Planetary gear for a robot gear assembly |
-
1989
- 1989-03-17 JP JP6715689A patent/JPH078878B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6184411B1 (en) | 1998-02-02 | 2001-02-06 | Ciba Specialty Chemicals Corporation | Process for the preparation of substituted hydroxyhydrocinnamate esters by removal of tin catalysts |
| WO2018199203A1 (en) * | 2017-04-26 | 2018-11-01 | 大阪有機化学工業株式会社 | Method for producing polyfunctional acrylate |
| CN110573489A (en) * | 2017-04-26 | 2019-12-13 | 大阪有机化学工业株式会社 | Method for producing multifunctional acrylate |
| US10774025B2 (en) | 2017-04-26 | 2020-09-15 | Osaka Organic Chemical Industry Ltd. | Method for producing polyfunctional acrylate |
| EP3617184A4 (en) * | 2017-04-26 | 2021-01-20 | Osaka Organic Chemical Industry Ltd. | Method for producing polyfunctional acrylate |
| TWI757476B (en) * | 2017-04-26 | 2022-03-11 | 日商大阪有機化學工業股份有限公司 | Production method of polyfunctional acrylate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH078878B2 (en) | 1995-02-01 |
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