JPWO2019138989A1 - Method for producing titanium chelate compound - Google Patents
Method for producing titanium chelate compound Download PDFInfo
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- JPWO2019138989A1 JPWO2019138989A1 JP2019564685A JP2019564685A JPWO2019138989A1 JP WO2019138989 A1 JPWO2019138989 A1 JP WO2019138989A1 JP 2019564685 A JP2019564685 A JP 2019564685A JP 2019564685 A JP2019564685 A JP 2019564685A JP WO2019138989 A1 JPWO2019138989 A1 JP WO2019138989A1
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- Prior art keywords
- titanium
- chelate compound
- titanium chelate
- hydroxycarboxylic acid
- acid
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- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 123
- 239000010936 titanium Substances 0.000 title claims abstract description 116
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 150000001875 compounds Chemical class 0.000 title claims abstract description 72
- 239000013522 chelant Substances 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- -1 titanium alkoxide Chemical class 0.000 claims abstract description 53
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000002904 solvent Substances 0.000 claims abstract description 28
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 16
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000007865 diluting Methods 0.000 claims abstract description 4
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 claims abstract description 3
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims abstract 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 21
- 239000004310 lactic acid Substances 0.000 claims description 13
- 235000014655 lactic acid Nutrition 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000003085 diluting agent Substances 0.000 claims description 9
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 125000004430 oxygen atom Chemical group O* 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 125000003545 alkoxy group Chemical group 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003446 ligand Substances 0.000 description 8
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 150000003003 phosphines Chemical group 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 125000006309 butyl amino group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 125000006316 iso-butyl amino group Chemical group [H]N(*)C([H])([H])C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 2
- 125000004894 pentylamino group Chemical group C(CCCC)N* 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000006308 propyl amino group Chemical group 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- 239000004251 Ammonium lactate Substances 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- ODBLHEXUDAPZAU-ZAFYKAAXSA-N D-threo-isocitric acid Chemical compound OC(=O)[C@H](O)[C@@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-ZAFYKAAXSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- ODBLHEXUDAPZAU-FONMRSAGSA-N Isocitric acid Natural products OC(=O)[C@@H](O)[C@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-FONMRSAGSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940059265 ammonium lactate Drugs 0.000 description 1
- 235000019286 ammonium lactate Nutrition 0.000 description 1
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229940001447 lactate Drugs 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- ODBLHEXUDAPZAU-UHFFFAOYSA-N threo-D-isocitric acid Natural products OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
- C07C59/06—Glycolic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
- C07C59/08—Lactic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
- C07C59/255—Tartaric acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
- C07C59/265—Citric acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/28—Titanium compounds
Abstract
少ない工程で高い生産性により効率的にチタンキレート化合物を得ることができ、工業的に有利なチタンキレート化合物の製造方法を提供すること。本発明のチタンキレート化合物の製造方法は、チタンアルコキシドを溶媒で希釈して希釈液を得る第一工程と、前記希釈液とヒドロキシカルボン酸とを混合してチタンキレート化合物を得る第二工程と、を有する。前記チタンアルコキシドが、テトラメトキシチタン（IV）、テトラエトキシチタン（IV）、テトラ−ｎ−プロポキシチタン（IV）、テトライソプロポキシチタン（IV）、テトラ−ｎ−ブトキシチタン（IV）及びテトライソブトキシチタン（IV）から選ばれる少なくとも一種であることが好ましい。To provide an industrially advantageous method for producing a titanium chelate compound, which can efficiently obtain a titanium chelate compound with high productivity in a small number of steps. The method for producing a titanium chelate compound of the present invention includes a first step of diluting titanium alkoxide with a solvent to obtain a diluted solution, and a second step of mixing the diluted solution with a hydroxycarboxylic acid to obtain a titanium chelate compound. Has. The titanium alkoxides are tetramethoxytitanium (IV), tetraethoxytitanium (IV), tetra-n-propoxytitanium (IV), tetraisopropoxytitanium (IV), tetra-n-butoxytitanium (IV) and tetraisobutoxy. It is preferably at least one selected from titanium (IV).
Description
本発明は、チタンキレート化合物の製造方法、特にヒドロキシカルボン酸のチタンキレート化合物の製造方法に関する。 The present invention relates to a method for producing a titanium chelate compound, particularly a method for producing a titanium chelate compound of hydroxycarboxylic acid.
チタンキレート化合物は、各種の架橋剤、触媒及び分散剤等、様々な用途で使用されている。チタンキレート化合物としては、クエン酸、酒石酸、乳酸といったヒドロキシカルボン酸又はその塩と、チタンアルコキシド等のチタン化合物との反応により形成されるチタンキレート化合物が知られている。このチタンキレート化合物の生成反応として、特許文献１では、乳酸などのヒドロキシカルボン酸とチタンテトラアルコキシドを水の共存下で反応させたのちアミンアンモニア、苛性ソーダ、炭酸カリ等の塩基を加え中和造塩する方法が記載されている。
特許文献２では、テトライソプロピル・チタン酸塩を石油エーテル（エクスゾールヘプタン）中の乳酸に添加して乳酸のチタン誘導体を得たことが記載されている。特許文献３には、チタンテトライソプロポキシドにエチレングリコールを加え、その後、乳酸アンモニウムを加えて乳酸キレートチタン化合物を得たことが記載されている。また、特許文献４では、乳酸とイソプロピルアルコールを混合した後、チタンイソプロポキシドを滴下してチタンイソプロポキシ乳酸キレートの混合液を得たことが記載されている。Titanium chelate compounds are used in various applications such as various cross-linking agents, catalysts and dispersants. As the titanium chelate compound, a titanium chelate compound formed by reacting a hydroxycarboxylic acid such as citric acid, tartaric acid or lactic acid or a salt thereof with a titanium compound such as titanium alkoxide is known. As a reaction for producing this titanium chelate compound, in Patent Document 1, a hydroxycarboxylic acid such as lactic acid and titanium tetraalkoxide are reacted in the coexistence of water, and then bases such as amine ammonia, caustic soda, and potassium carbonate are added to neutralize salt formation. How to do it is described.
Patent Document 2 describes that tetraisopropyl-titanate was added to lactic acid in petroleum ether (exsol heptane) to obtain a titanium derivative of lactic acid. Patent Document 3 describes that ethylene glycol was added to titanium tetraisopropoxide, and then ammonium lactate was added to obtain a lactate chelated titanium compound. Further, Patent Document 4 describes that after mixing lactic acid and isopropyl alcohol, titanium isopropoxide was added dropwise to obtain a mixed solution of titanium isopropoxy lactic acid chelate.
特許文献1に記載の方法では、ヒドロキシカルボン酸とチタンテトラアルコキシドとを水の共存下で反応させているため、チタンテトラアルコキシドが加水分解を起こしてしまい、所望するチタンとのキレートを得難い問題がある。特許文献２及び特許文献３に記載の方法では、不純成分として石油エーテルやエチレングリコールを使用している。このためこれら文献記載の方法では、目的とするチタンキレート化合物を水含有溶媒等の石油エーテルやエチレングリコール以外の溶媒中で使用したい場合、反応液を濾別して得られた固形物を洗浄、乾燥する必要があるため工程が多くなり、工業的に不利である。特許文献４に記載の方法では、チタンイソプロポキシド１ｍｏｌに対して使用するキレート剤、すなわち乳酸の量が多く、生産性の面で改善の余地がある。また特許文献４に記載の方法では、チタンアルコキシドとヒドロキシカルボン酸とを混合した時に固形分が生じやすく均一になりにくい、イソプロパノールによる発煙が生じやすく、作業がしづらい等という問題もある。 In the method described in Patent Document 1, since the hydroxycarboxylic acid and the titanium tetraalkoxide are reacted in the coexistence of water, the titanium tetraalkoxide is hydrolyzed, and there is a problem that it is difficult to obtain a desired chelate with titanium. is there. In the methods described in Patent Document 2 and Patent Document 3, petroleum ether and ethylene glycol are used as impure components. Therefore, in the methods described in these documents, when it is desired to use the target titanium chelate compound in a solvent other than petroleum ether such as a water-containing solvent or ethylene glycol, the solid substance obtained by filtering the reaction solution is washed and dried. Since it is necessary, the number of processes increases, which is industrially disadvantageous. In the method described in Patent Document 4, the amount of the chelating agent used for 1 mol of titanium isopropoxide, that is, lactic acid is large, and there is room for improvement in terms of productivity. Further, the method described in Patent Document 4 has problems that when titanium alkoxide and hydroxycarboxylic acid are mixed, solid content is likely to be generated and is difficult to be uniform, isopropanol is likely to generate smoke, and work is difficult.
工業的に有利な方法でチタンとのキレートを形成させるためには、少ない工程で効率的な反応を促進させる必要があるが、従来技術では未だその要求を達成できていない。
したがって本発明の課題は、前述した従来技術により達成できていない点を解消し得るチタンキレート化合物の製造方法を提供することにある。In order to form a chelate with titanium by an industrially advantageous method, it is necessary to promote an efficient reaction in a small number of steps, but the conventional technique has not yet achieved the requirement.
Therefore, an object of the present invention is to provide a method for producing a titanium chelate compound, which can solve the problems that have not been achieved by the above-mentioned prior art.
本発明者は、上記実情に鑑み鋭意研究を重ねた結果、原料となるチタンアルコキシドを特定の条件を有する状態とした後にヒドロキシカルボン酸と混合することにより、工業的に有利な条件で、所望のチタンキレートを形成しうることを見出し、本発明を完成するに至った。 As a result of diligent research in view of the above circumstances, the present inventor has made titanium alkoxide, which is a raw material, into a state having specific conditions and then mixed it with hydroxycarboxylic acid, whereby it is desired under industrially advantageous conditions. We have found that a titanium chelate can be formed, and have completed the present invention.
すなわち、本発明は、チタンアルコキシドを溶媒で希釈して希釈液を得る第一工程、及び、前記希釈液とヒドロキシカルボン酸を混合して混合物を得る第二工程を有する、チタンキレート化合物の製造方法を提供するものである。 That is, the present invention comprises a first step of diluting titanium alkoxide with a solvent to obtain a diluted solution, and a second step of mixing the diluted solution with hydroxycarboxylic acid to obtain a mixture, a method for producing a titanium chelate compound. Is to provide.
以下本発明を、その好ましい実施形態に基づき説明する。本実施形態の製造方法は、チタンアルコキシドを溶媒で希釈して希釈液を得る第一工程、及び、前記希釈液とヒドロキシカルボン酸を混合して混合物を得る第二工程を有する、チタンキレート化合物の製造方法に係るものである。 Hereinafter, the present invention will be described based on its preferred embodiment. The production method of the present embodiment comprises a first step of diluting titanium alkoxide with a solvent to obtain a diluted solution, and a second step of mixing the diluted solution with hydroxycarboxylic acid to obtain a mixture of titanium chelate compounds. It relates to a manufacturing method.
本発明において、チタンアルコキシドを、予め溶媒に希釈しておくことが重要である。これにより、特許文献４等のようにヒドロキシカルボン酸を溶媒により予め希釈し、希釈したヒドロキシカルボン酸をチタンアルコキシドと混合する場合に比べて、チタンアルコキシドに対して使用するヒドロキシカルボン酸量を低減させることができる。この理由として発明者は、本発明では、希釈されたチタンアルコキシドとヒドロキシカルボン酸とを均一に混合させやすく、これにより６配位のキレート化合物へと反応が効率よく進みやすい可能性や、チタンアルコキシドの重合体等の副成分が生じにくいことなどが理由ではないかと考えている。また、本発明では、溶媒として、イソプロパノール等の溶媒を使用した場合、チタンアルコキシドと予め混合しておくことで、発煙を抑制させやすいという利点もある。 In the present invention, it is important that the titanium alkoxide is diluted with a solvent in advance. As a result, the amount of hydroxycarboxylic acid used for the titanium alkoxide is reduced as compared with the case where the hydroxycarboxylic acid is diluted in advance with a solvent and the diluted hydroxycarboxylic acid is mixed with the titanium alkoxide as in Patent Document 4 and the like. be able to. The reason for this is that in the present invention, the inventor can easily mix the diluted titanium alkoxide and the hydroxycarboxylic acid uniformly, which may facilitate the reaction to the 6-coordinate chelate compound efficiently, and the titanium alkoxide. I think that the reason is that it is difficult for auxiliary components such as the polymer of the above to be generated. Further, in the present invention, when a solvent such as isopropanol is used as the solvent, there is an advantage that smoke generation can be easily suppressed by mixing with titanium alkoxide in advance.
第一工程で使用するチタンアルコキシドとしては、チタン原子に４つのアルコキシ基が配位しているチタンテトラアルコキシドが挙げられる。チタンアルコキシドにおいて配位子であるアルコキシ基は、直鎖状であっても分岐鎖状であってもよいが、炭素数４以下であることがヒドロキシカルボン酸との反応性や水溶性キレート剤の合成しやすさの点から好ましい。チタンアルコキシドにおけるアルコキシ基の炭素数は１以上である。チタン原子に配位する４つのアルコキシ基は同一であってもよく、異なってもよいが、同一であることが、チタンアルコキシドの入手容易性の点から好ましい。これらの観点から、チタンアルコキシドは、例えば、テトラメトキシチタン（IV）、テトラエトキシチタン（IV）、テトラ−ｎ−プロポキシチタン（IV）、テトライソプロポキシチタン（IV）、テトラ−ｎ−ブトキシチタン（IV）及びテトライソブトキシチタン（IV）から選ばれる少なくとも一種であることが特に好ましい。 Examples of the titanium alkoxide used in the first step include titanium tetraalkoxide in which four alkoxy groups are coordinated with the titanium atom. The alkoxy group, which is a ligand in titanium alkoxide, may be linear or branched, but the reactivity with hydroxycarboxylic acid and the water-soluble chelating agent must have 4 or less carbon atoms. It is preferable from the viewpoint of ease of synthesis. The number of carbon atoms of the alkoxy group in the titanium alkoxide is 1 or more. The four alkoxy groups coordinated to the titanium atom may be the same or different, but the same is preferable from the viewpoint of availability of the titanium alkoxide. From these viewpoints, titanium alkoxides include, for example, tetramethoxytitanium (IV), tetraethoxytitanium (IV), tetra-n-propoxytitanium (IV), tetraisopropoxytitanium (IV), and tetra-n-butoxytitanium (IV). It is particularly preferable that it is at least one selected from IV) and tetraisobutoxytitanium (IV).
溶媒としては、有機溶媒が挙げられる。特にチタンアルコキシドを希釈液として流動性が高い状態で安定的に存在させて、ヒドロキシカルボン酸との反応性を高めることができる点や、目的物であるチタンキレート化合物を水含有溶媒中で分散又は溶解させて使用したいとき等に除去せずに使用できる等の理由から、極性有機溶媒が好ましく、特に、アルコールが好ましい。アルコールとしては、メタノール、エタノール、イソプロパノール、n−プロパノール、n−ブタノール、sec−ブタノール、tert−ブタノール、ｎ−ペンタノール等が挙げられるが、特に炭素数１以上４以下の脂肪族アルコールが、チタンアルコキシドとヒドロキシカルボン酸とを液状態で均一に混合させやすいので反応性を高めやすい点や水溶性キレート剤の合成しやすさの点で好ましい。またアルコールとして、1価のアルコールを用いることが、入手コストの点で好ましい。とりわけ、前記チタンアルコキシドが有するアルキル基の少なくとも一つと同じ炭素数のアルキル基を有する一価のアルコールを用いることがキレート生成物と溶媒との相溶性や分離回収の点で好ましく、前記チタンアルコキシドが有する４つのアルキル基と同じ炭素数のアルキル基を有する一価のアルコールが最も好ましい。これらの溶媒は、１種又は２種以上を混合して用いることができる。 Examples of the solvent include organic solvents. In particular, titanium alkoxide can be stably present as a diluent in a highly fluid state to enhance the reactivity with hydroxycarboxylic acid, and the target titanium chelate compound is dispersed or dispersed in a water-containing solvent. A polar organic solvent is preferable, and alcohol is particularly preferable, because it can be used without being removed when it is desired to be dissolved and used. Examples of the alcohol include methanol, ethanol, isopropanol, n-propanol, n-butanol, sec-butanol, tert-butanol, n-pentanol and the like. In particular, fatty alcohols having 1 or more and 4 or less carbon atoms are titanium. Since the alkoxide and the hydroxycarboxylic acid can be easily mixed uniformly in a liquid state, it is preferable in terms of easy enhancement of reactivity and ease of synthesizing a water-soluble chelating agent. Further, it is preferable to use monohydric alcohol as the alcohol in terms of acquisition cost. In particular, it is preferable to use a monohydric alcohol having an alkyl group having the same carbon number as at least one of the alkyl groups of the titanium alkoxide in terms of compatibility between the chelate product and the solvent and separation and recovery, and the titanium alkoxide is preferable. Most preferably, a monohydric alcohol having an alkyl group having the same number of carbon atoms as the four alkyl groups having. These solvents can be used alone or in admixture of two or more.
第一工程により得られる、溶媒をチタンアルコキシドと混合させた希釈液中、チタンアルコキシドの割合は、９０質量％以下であることが、チタンアルコキシドを流動化させてヒドロキシカルボン酸と混合させやすくする点で好ましい。また希釈液中におけるチタンアルコキシドの割合は、４０質量％以上であることが、溶媒及びヒドロキシカルボン酸の使用量を抑制しながら効果的に収率を高める点から好ましい。これらの点から、希釈液中のチタンアルコキシドの量は５０質量％以上８５質量％以下であることがより好ましく、６０質量％以上８０質量％以下であることが特に好ましい。また同様の観点から、希釈液中の溶媒の量はチタンアルコキシド１００質量部に対して１０質量部以上１５０質量部以下が好ましく、１５質量部以上１００質量部以下がより好ましい。 The ratio of titanium alkoxide in the diluted solution obtained in the first step obtained by mixing the solvent with titanium alkoxide is 90% by mass or less, which makes it easy to fluidize the titanium alkoxide and mix it with the hydroxycarboxylic acid. Is preferable. The proportion of titanium alkoxide in the diluted solution is preferably 40% by mass or more from the viewpoint of effectively increasing the yield while suppressing the amount of the solvent and hydroxycarboxylic acid used. From these points, the amount of titanium alkoxide in the diluent is more preferably 50% by mass or more and 85% by mass or less, and particularly preferably 60% by mass or more and 80% by mass or less. From the same viewpoint, the amount of the solvent in the diluent is preferably 10 parts by mass or more and 150 parts by mass or less, and more preferably 15 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of titanium alkoxide.
希釈液は、溶媒とチタンアルコキシド以外の成分を含有していてもよいが、得られるチタンキレート化合物の純度を高める点などから、溶媒とチタンアルコキシド以外の成分を実質的に非含有であることがより好ましい。具体的には、希釈液中、溶媒及びチタンアルコキシド以外のその他の成分の量は、１０質量％以下であることが好ましく、５質量％以下であることがより好ましい。第一工程におけるチタンアルコキシドの溶媒による希釈は、ヒドロキシカルボン酸の不存在下で行う。 The diluent may contain components other than the solvent and titanium alkoxide, but it may be substantially free of components other than the solvent and titanium alkoxide from the viewpoint of increasing the purity of the obtained titanium chelate compound. More preferred. Specifically, the amount of the solvent and other components other than the titanium alkoxide in the diluent is preferably 10% by mass or less, and more preferably 5% by mass or less. The solvent dilution of titanium alkoxide in the first step is carried out in the absence of hydroxycarboxylic acid.
溶媒は、水分含量が低いことが、チタンアルコキシドがヒドロキシカルボン酸との反応前に加水分解してしまうことを防止できる点で好ましい。この観点から、溶媒は、水分含量が１０質量％以下であることが好ましく、５質量％以下であることがより好ましい。 It is preferable that the solvent has a low water content because it can prevent the titanium alkoxide from being hydrolyzed before the reaction with the hydroxycarboxylic acid. From this point of view, the solvent preferably has a water content of 10% by mass or less, and more preferably 5% by mass or less.
第二工程で用いるヒドロキシカルボン酸としては、入手の容易性やチタンアルコキシドとの反応性、入手コストの点から、脂肪族ヒドロキシカルボン酸が好ましく挙げられる。例えば、１価のカルボン酸として、乳酸、グリコール酸、グリセリン酸、ヒドロキシ酪酸が挙げられ、２価のカルボン酸として、タルトロン酸、リンゴ酸、酒石酸が挙げられ、３価のカルボン酸としてクエン酸、イソクエン酸等が挙げられる。ヒドロキシカルボン酸は、α−ヒドロキシカルボン酸であることが、ヒドロキシカルボン酸同士が脱水反応しにくい点で好ましく、α−ヒドロキシカルボン酸の中でも、入手容易性や取扱いのし易さの点から、乳酸、グリコール酸、酒石酸、クエン酸が好ましい。特に室温で溶液となり、チタンアルコキシド希釈液と混合しやすく、容易にチタンキレート化合物が製造できる観点から、乳酸が好ましい。ここでいうヒドロキシカルボン酸としては、ヒドロキシカルボン酸のアミン塩等の塩の形態ではないことが、廃液処理のし易さや着色されにくい点で好ましい。 As the hydroxycarboxylic acid used in the second step, an aliphatic hydroxycarboxylic acid is preferably mentioned from the viewpoint of easy availability, reactivity with titanium alkoxide, and acquisition cost. For example, monovalent carboxylic acids include lactic acid, glycolic acid, glyceric acid, and hydroxybutyric acid, divalent carboxylic acids include tartronic acid, malic acid, and tartaric acid, and trivalent carboxylic acids include citric acid. Examples thereof include isocitric acid. The hydroxycarboxylic acid is preferably an α-hydroxycarboxylic acid because it is difficult for the hydroxycarboxylic acids to undergo a dehydration reaction, and among the α-hydroxycarboxylic acids, lactic acid is easy to obtain and handle. , Glycolic acid, tartrate acid, citric acid are preferable. In particular, lactic acid is preferable from the viewpoint that it becomes a solution at room temperature, is easily mixed with a titanium alkoxide diluent, and a titanium chelate compound can be easily produced. The hydroxycarboxylic acid referred to here is preferably not in the form of a salt such as an amine salt of hydroxycarboxylic acid in terms of ease of waste liquid treatment and resistance to coloring.
第二工程において、ヒドロキシカルボン酸は、希釈液に対し、該希釈液中のチタンアルコキシド１モルに対して、１モル以上混合させることが、ヒドロキシカルボン酸が配位したチタンキレート化合物を高い収量で得られる点から好ましく、３．５モル以下混合させることが、得られるチタンキレート化合物の過度なオリゴマー化を抑制しつつヒドロキシカルボン酸の使用量を抑制して、生産性を高める点で好ましい。これらの点から、ヒドロキシカルボン酸は、チタンアルコキシド１モルに対して、１．１モル以上３．３モル以下で混合させることがより好ましく、１．２モル以上３モル以下混合させることが更に一層好ましい。 In the second step, the hydroxycarboxylic acid can be mixed with the diluted solution by 1 mol or more with respect to 1 mol of the titanium alkoxide in the diluted solution to obtain a high yield of the titanium chelate compound coordinated with the hydroxycarboxylic acid. It is preferable from the viewpoint of obtaining it, and mixing 3.5 mol or less is preferable from the viewpoint of suppressing excessive oligomerization of the obtained titanium chelate compound and suppressing the amount of hydroxycarboxylic acid used to increase productivity. From these points, the hydroxycarboxylic acid is more preferably mixed in an amount of 1.1 mol or more and 3.3 mol or less, and further more preferably 1.2 mol or more and 3 mol or less, with respect to 1 mol of titanium alkoxide. preferable.
本発明においては、高い生産性により効率的にチタンキレート化合物を得るという効果を奏する範囲内において、第二工程において、ヒドロキシカルボン酸以外に、チタンに配位可能な配位子化合物を希釈液に添加してもよい。そのような配位子化合物としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子を有するハロゲン原子含有化合物、メチルアミノ基、エチルアミノ基、プロピルアミノ基、イソプロピルアミノ基、ブチルアミノ基、イソブチルアミノ基、ｔ−ブチルアミノ基、ペンチルアミノ基等の官能基を有するアミン類、トリメチルホスフィン、トリエチルホスフィン、トリブチルホスフィン、トリス−ｔ−ブチルホスフィン、トリフェニルホスフィン等のホスフィン類が挙げられる。ヒドロキシカルボン酸以外の、チタンに配位可能な配位子化合物の使用量は、ヒドロキシカルボン酸１モルに対して１モル以下であることが好ましく、０．５モル以下であることがより好ましく、０．３モル以下であることが最も好ましい。なお、第二工程における希釈液とヒドロキシカルボン酸との混合時に、溶媒に希釈されていない追加のチタンアルコキシドの添加は行わない。 In the present invention, in addition to the hydroxycarboxylic acid, a ligand compound capable of coordinating with titanium is used as a diluent in the second step within the range in which the effect of efficiently obtaining the titanium chelate compound with high productivity is obtained. It may be added. Examples of such a ligand compound include a halogen atom-containing compound having a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, and a butylamino group. Examples thereof include amines having functional groups such as isobutylamino group, t-butylamino group and pentylamino group, and phosphines such as trimethylphosphine, triethylphosphine, tributylphosphine, tris-t-butylphosphine and triphenylphosphine. The amount of the ligand compound that can be coordinated to titanium other than the hydroxycarboxylic acid is preferably 1 mol or less, more preferably 0.5 mol or less, with respect to 1 mol of the hydroxycarboxylic acid. Most preferably, it is 0.3 mol or less. When the diluent and the hydroxycarboxylic acid are mixed in the second step, no additional titanium alkoxide undiluted in the solvent is added.
溶媒とチタンアルコキシドとを混合する第一工程、及び、それにより得られる希釈液とヒドロキシカルボン酸とを混合する第二工程は、いずれも室温下（０℃以上４０℃以下）で行うことができる。第一工程及び第二工程は、連続的に行うことが好ましい。 Both the first step of mixing the solvent and the titanium alkoxide and the second step of mixing the diluted solution obtained thereby and the hydroxycarboxylic acid can be performed at room temperature (0 ° C. or higher and 40 ° C. or lower). .. It is preferable that the first step and the second step are continuously performed.
第二工程により得られるチタンキレート化合物は、チタン金属原子に、ヒドロキシカルボン酸が１分子以上配位した化合物である。このように、チタン金属原子にヒドロキシカルボン酸が配位したチタンキレート化合物は、水分と混合させた場合でもヒドロキシカルボン酸による配位状態が維持されて重合が抑制されやすい。第二工程により得られるチタンキレート化合物において、ヒドロキシカルボン酸以外の配位子としては、アルコキシ基、水酸基、ハロゲン原子、アミノ基、ホスフィン類等が挙げられ、アルコキシ基が好ましい。このようなチタンキレート化合物としては下記式（１）で示すものが挙げられる。
Ｔｉ（Ｒ１）ｍ（Ｌ）ｎ ・・・（１）
（式中、Ｒ１は、アルコキシ基、水酸基、ハロゲン原子、アミノ基又はホスフィン類を表し、複数存在する場合、同一であってもよく、異なっていてもよい。Ｌはヒドロキシカルボン酸に由来する基を表し、複数存在する場合、同一であってもよく、異なっていてもよい。ｍは０以上３以下の数を示し、ｎは１以上３以下の数を示し、ｍ＋ｎは３〜６である。）The titanium chelate compound obtained in the second step is a compound in which one or more molecules of hydroxycarboxylic acid are coordinated with a titanium metal atom. As described above, the titanium chelate compound in which the hydroxycarboxylic acid is coordinated with the titanium metal atom maintains the coordinated state by the hydroxycarboxylic acid even when mixed with water, and the polymerization is easily suppressed. In the titanium chelate compound obtained in the second step, examples of the ligand other than the hydroxycarboxylic acid include an alkoxy group, a hydroxyl group, a halogen atom, an amino group, phosphines and the like, and an alkoxy group is preferable. Examples of such a titanium chelate compound include those represented by the following formula (1).
Ti (R 1 ) m (L) n ... (1)
(In the formula, R 1 represents an alkoxy group, a hydroxyl group, a halogen atom, an amino group or phosphines, and when a plurality of them are present, they may be the same or different. L is derived from hydroxycarboxylic acid. It represents a group, and when there are a plurality of groups, they may be the same or different. M indicates a number of 0 or more and 3 or less, n indicates a number of 1 or more and 3 or less, and m + n is 3 to 6. is there.)
なお第二工程で、ヒドロキシカルボン酸とチタンアルコキシドとの反応により生じるアルコールが、ヒドロキシカルボン酸と更に反応して水が生じる場合がある。一般式（１）のＲ１で表される水酸基の由来としては、この反応により生じる水が挙げられる。一般式（１）においてチタンの配位数は、Ｌがｓ座の配位子（ｓは正の整数）である場合、ｍ＋ｓ×ｎで表され、６であることが好ましい。In the second step, the alcohol generated by the reaction between the hydroxycarboxylic acid and the titanium alkoxide may further react with the hydroxycarboxylic acid to generate water. The origin of the hydroxyl group represented by R 1 of the general formula (1) includes water produced by this reaction. In the general formula (1), the coordination number of titanium is represented by m + s × n when L is a ligand at the s locus (s is a positive integer), and is preferably 6.
Ｒ１で表されるアルコキシ基としては、チタンアルコキシドにおける配位子として挙げられたものと同様のアルコキシ基が挙げられる。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。アミノ基としては、例えばメチルアミノ基、エチルアミノ基、プロピルアミノ基、イソプロピルアミノ基、ブチルアミノ基、イソブチルアミノ基、ｔ−ブチルアミノ基、ペンチルアミノ基等が挙げられる。ホスフィン類としては、例えばトリメチルホスフィン、トリエチルホスフィン、トリブチルホスフィン、トリス−ｔ−ブチルホスフィン、トリフェニルホスフィン等が挙げられる。
Ｌで表されるヒドロキシカルボン酸に由来する基としては、ヒドロキシカルボン酸におけるヒドロキシル基の酸素原子又はヒドロキシカルボン酸におけるカルボキシル基の酸素原子が、チタン原子に配位してなる基が挙げられる。また、ヒドロキシカルボン酸におけるヒドロキシル基の酸素原子及びヒドロキシカルボン酸におけるカルボキシル基の酸素原子が、チタン原子に２座で配位してなる基が挙げられる。これらの中、ヒドロキシカルボン酸におけるヒドロキシル基の酸素原子及びヒドロキシカルボン酸におけるカルボキシル基の酸素原子が、チタン原子に２座で配位してなる基であることが好ましい。ｍが０の場合はｍ＋ｎは３であることが好ましく、ｍが１以上３以下の場合はｍ＋ｎは４又は５であることが好ましい。Examples of the alkoxy group represented by R 1 include the same alkoxy groups as those listed as ligands in titanium alkoxide. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the amino group include a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a butylamino group, an isobutylamino group, a t-butylamino group, a pentylamino group and the like. Examples of phosphines include trimethylphosphine, triethylphosphine, tributylphosphine, tris-t-butylphosphine, triphenylphosphine and the like.
Examples of the group derived from the hydroxycarboxylic acid represented by L include a group in which the oxygen atom of the hydroxyl group in the hydroxycarboxylic acid or the oxygen atom of the carboxyl group in the hydroxycarboxylic acid is coordinated with the titanium atom. In addition, there is a group in which the oxygen atom of the hydroxyl group in the hydroxycarboxylic acid and the oxygen atom of the carboxyl group in the hydroxycarboxylic acid are coordinated with the titanium atom in two positions. Among these, it is preferable that the oxygen atom of the hydroxyl group in the hydroxycarboxylic acid and the oxygen atom of the carboxyl group in the hydroxycarboxylic acid are groups coordinated with the titanium atom in two positions. When m is 0, m + n is preferably 3, and when m is 1 or more and 3 or less, m + n is preferably 4 or 5.
第二工程で得られるチタンキレート化合物は、チタン原子同士が酸素原子等を介して結合したオリゴマーなどの重合体を、水溶性を有する範囲で含有していてもよく、実質的に含有しなくてもよい。例えば、当該チタンキレート化合物のモノマーとオリゴマーが等量存在していたとしても、オリゴマーの重合度が低く水溶性を有していれば、本発明の範疇となる。例えば、第二工程で得られるチタンキレート化合物において、式（１）で表されるモノマーと上記オリゴマーとのモル比は、モノマー１モルに対してオリゴマーが１モル以下であることが好ましく、０．８モル以下であることがより好ましく、０．５モル以下であることが更に一層好ましい。 The titanium chelate compound obtained in the second step may contain a polymer such as an oligomer in which titanium atoms are bonded to each other via an oxygen atom or the like in a water-soluble range, and does not substantially contain the polymer. May be good. For example, even if the monomer and the oligomer of the titanium chelate compound are present in equal amounts, if the oligomer has a low degree of polymerization and is water-soluble, it falls under the category of the present invention. For example, in the titanium chelate compound obtained in the second step, the molar ratio of the monomer represented by the formula (1) to the above oligomer is preferably 1 mol or less of the oligomer with respect to 1 mol of the monomer. It is more preferably 8 mol or less, and even more preferably 0.5 mol or less.
前記第二工程の後、得られたチタンキレート化合物及び溶媒の混合物に水を添加してもよい。これにより、チタンキレート化合物の水含有溶媒の分散液又は溶解液を得ることができる。これは、例えば、チタンキレート化合物をその用途に適した形態とする点等から好ましい。とりわけ、本発明の方法によれば、副生物の少ない水溶性チタンキレート化合物を合成しやすく、前記第二工程の生成物と水とを混合することでチタンキレート化合物の透明な水溶液を容易に得ることができる。
第二工程により得られた混合物を、水と混合して得られる化合物としては、上記式（１）で表される化合物が挙げられる。特に式（１）において、少なくとも一つのＲ１が水酸基である化合物が容易に得やすい。
式（１）の化合物の同定には、ＮＭＲ、ＦＴ−ＩＲ、ＧＰＣ等が挙げられる。After the second step, water may be added to the resulting mixture of titanium chelate compound and solvent. As a result, a dispersion or solution of a water-containing solvent of the titanium chelate compound can be obtained. This is preferable because, for example, the titanium chelate compound is in a form suitable for the intended use. In particular, according to the method of the present invention, it is easy to synthesize a water-soluble titanium chelate compound having few by-products, and a transparent aqueous solution of the titanium chelate compound can be easily obtained by mixing the product of the second step with water. be able to.
Examples of the compound obtained by mixing the mixture obtained in the second step with water include the compound represented by the above formula (1). In particular, in the formula (1), a compound in which at least one R 1 is a hydroxyl group can be easily obtained.
Examples of the identification of the compound of the formula (1) include NMR, FT-IR, GPC and the like.
第二工程により得られた化合物及び当該化合物を水と混合して得られる化合物のいずれについても、式（１）において、Ｒ１で表される配位子としては、水酸基又はアルコキシ基が好ましい。また第二工程で得られた混合物を水と混合して得られる化合物についても、式（１）のＬの好ましい基としては上記で第二工程により得られた化合物について挙げたＬの好ましい基が挙げられる。For any of the second compound obtained by the process and compounds obtained by the compound is mixed with water, in the formula (1), as the ligand represented by R 1, hydroxyl group or an alkoxy group. As for the compound obtained by mixing the mixture obtained in the second step with water, the preferred group of L mentioned above for the compound obtained in the second step is the preferred group of L in the formula (1). Can be mentioned.
第二工程で得られた混合物に水を添加する場合、添加する水の量は、第二工程で得られた混合物１００質量部に対して、２０質量部以上であることが、Ｒ１として表されるアルコキシ基を水酸基に置換する反応を促進する点で好ましく、２００質量部以下であることがチタンの濃度を高くする点で好ましい。これらの観点から、水の添加量は前記の混合物１００質量部に対して２５質量部以上１９０質量部以下あることがより好ましい。When adding water to the mixture obtained in the second step, the amount of water to be added is, relative to the mixture 100 parts by mass obtained in the second step, it is 20 parts by mass or more, the table as R 1 It is preferable in terms of accelerating the reaction of substituting the alkoxy group to a hydroxyl group, and it is preferable that the concentration is 200 parts by mass or less in terms of increasing the concentration of titanium. From these viewpoints, the amount of water added is more preferably 25 parts by mass or more and 190 parts by mass or less with respect to 100 parts by mass of the mixture.
以上の工程により得られたチタンキレート化合物は、各種の架橋剤、触媒及び分散剤等として有用に用いることができる。 The titanium chelate compound obtained by the above steps can be usefully used as various cross-linking agents, catalysts, dispersants and the like.
以下、本発明を実施例により説明する。しかしながら本発明の範囲はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described with reference to Examples. However, the scope of the present invention is not limited to these examples.
（実施例１）
テトライソプロポキシチタン（IV）７．１２ｇにイソプロパノール３．０１ｇを混合して希釈液を得た。この希釈液にＬ−乳酸（純度９０質量％）５．０１ｇを添加して撹拌することにより乳酸チタンキレートを得た。テトライソプロポキシチタン（IV）の使用量とＬ−乳酸の使用量とのモル比は約１：２であった。その後、１２．５９ｍｌの水を添加して撹拌することにより透明な乳酸チタンキレートの水溶液を得た。水溶液にチタンの沈殿が存在しなかったことから、使用したチタンが全て式（１）で表されるキレート化合物となったものと認められる。生成した式（１）で表されるキレート化合物は、ｍ＝２、ｎ＝２、Ｒ１＝水酸基であり、Ｌが、乳酸における水酸基の酸素原子及びカルボキシル基の酸素原子がチタン原子に２座で配位してなる基である化合物を主として含んでいた。上記手順はいずれも室温（２５℃）下で行った。(Example 1)
A diluted solution was obtained by mixing 7.12 g of tetraisopropoxytitanium (IV) with 3.01 g of isopropanol. 5.01 g of L-lactic acid (purity 90% by mass) was added to this diluted solution and stirred to obtain a titanium lactate chelate. The molar ratio of the amount of tetraisopropoxytitanium (IV) used to the amount of L-lactic acid used was about 1: 2. Then, 12.59 ml of water was added and stirred to obtain a transparent aqueous solution of titanium lactate chelate. Since no titanium precipitate was present in the aqueous solution, it is recognized that all the titanium used was a chelate compound represented by the formula (1). The generated chelate compound represented by the formula (1) has m = 2, n = 2, R 1 = hydroxyl group, and L is the oxygen atom of the hydroxyl group in lactic acid and the oxygen atom of the carboxyl group at the bidentate of the titanium atom. It mainly contained a compound that was a group coordinated with. All of the above procedures were performed at room temperature (25 ° C.).
（実施例２）
テトライソプロポキシチタン（IV）７．１２ｇにイソプロパノール３．０１ｇを混合して希釈液を得た。この希釈液にＬ−乳酸（純度９０質量％）３．０１ｇを添加して撹拌することにより乳酸チタンキレートを得た。テトライソプロポキシチタン（IV）の使用量とＬ−乳酸の使用量とのモル比は約１：１．２であった。その後、１４．２４ｍｌの水を添加して撹拌することにより透明な乳酸チタンキレートの水溶液を得た。水溶液にチタンの沈殿が存在しなかったことから、使用したチタンが全て式（１）のキレート化合物となったものと認められる。生成した式（１）で表されるキレート化合物は、ｍ＝４、ｎ＝１、Ｒ１＝水酸基であり、Ｌが、乳酸における水酸基の酸素原子及びカルボキシル基の酸素原子がチタン原子に２座で配位してなる基である化合物を主として含んでいた。上記手順はいずれも室温（２５℃）下で行った。(Example 2)
A diluted solution was obtained by mixing 7.12 g of tetraisopropoxytitanium (IV) with 3.01 g of isopropanol. 3.01 g of L-lactic acid (purity 90% by mass) was added to this diluted solution and stirred to obtain a titanium lactate chelate. The molar ratio of the amount of tetraisopropoxytitanium (IV) used to the amount of L-lactic acid used was about 1: 1.2. Then, 14.24 ml of water was added and stirred to obtain a transparent aqueous solution of titanium lactate chelate. Since no titanium precipitate was present in the aqueous solution, it is recognized that all the titanium used was a chelate compound of the formula (1). The generated chelate compound represented by the formula (1) has m = 4, n = 1, R 1 = hydroxyl group, and L is the oxygen atom of the hydroxyl group in lactic acid and the oxygen atom of the carboxyl group at the bidentate of the titanium atom. It mainly contained a compound that was a group coordinated with. All of the above procedures were performed at room temperature (25 ° C.).
（実施例３）
テトライソプロポキシチタン（IV）７．１２ｇにイソプロパノール３．０１ｇを混合して希釈液を得た。この希釈液にＬ−乳酸（純度９０質量％）７．５１ｇを添加して撹拌することにより乳酸チタンキレートを得た。テトライソプロポキシチタン（IV）の使用量とＬ−乳酸の使用量とのモル比は約１：３であった。その後１０．５２ｍｌの水を添加して撹拌することにより透明な乳酸チタンキレートの水溶液を得た。水溶液にチタンの沈殿が存在しなかったことから、使用したチタンが全て式（１）のキレート化合物となったものと認められる。生成した式（１）で表されるキレート化合物は、ｍ＝０、ｎ＝３であり、Ｌが乳酸における水酸基の酸素原子及びカルボキシル基の酸素原子がチタン原子に２座で配位してなる基である化合物を主として含んでいた。上記手順はいずれも室温（２５℃）下で行った。(Example 3)
A diluted solution was obtained by mixing 7.12 g of tetraisopropoxytitanium (IV) with 3.01 g of isopropanol. 7.51 g of L-lactic acid (purity 90% by mass) was added to this diluted solution and stirred to obtain a titanium lactate chelate. The molar ratio of the amount of tetraisopropoxytitanium (IV) used to the amount of L-lactic acid used was about 1: 3. Then, 10.52 ml of water was added and stirred to obtain a transparent aqueous solution of titanium lactate chelate. Since no titanium precipitate was present in the aqueous solution, it is recognized that all the titanium used was a chelate compound of the formula (1). The generated chelate compound represented by the formula (1) has m = 0 and n = 3, and L is composed of the oxygen atom of the hydroxyl group in lactic acid and the oxygen atom of the carboxyl group coordinated to the titanium atom in two positions. It mainly contained the compound that was the group. All of the above procedures were performed at room temperature (25 ° C.).
（比較例１）
テトライソプロポキシチタン（IV）７．１２ｇにＬ−乳酸（純度９０質量％）５．０１ｇを添加したところ、粘調な塊となり、その後の操作が不能となった。(Comparative Example 1)
When 5.01 g of L-lactic acid (purity 90% by mass) was added to 7.12 g of tetraisopropoxytitanium (IV), a viscous mass was formed, and subsequent operations became impossible.
（比較例２）
本比較例は、特許文献４（特開２０１５−３６３９０号公報）と同様の手法でチタンキレート化合物を製造した例である。
Ｌ−乳酸（純度９０質量％）４．０ｇとイソプロパノール２．８ｇを混合し、撹拌しながらテトライソプロポキシチタン（IV）２．８ｇを添加した後、反応熱が無くなるまで撹拌を継続して乳酸チタンキレートを含む混合液を得た。テトライソプロポキシチタン（IV）の使用量とＬ−乳酸の使用量とのモル比は約１：４であった。得られた混合液に、１８．３ｍｌの水を添加して撹拌することにより乳酸チタンキレートを含む水溶液を得た。しかし、イソプロパノールとＬ−乳酸との混合物にテトライソプロポキシチタン（IV）を混合した際に発煙し、作業が非常に困難であるだけでなく、固形物が発生し、水を添加してもなかなか溶解せず、実施例１〜３に比べて撹拌に時間がかかった。具体的には、実施例１〜３は水添加後に、チタンキレート化合物が溶解するまでの撹拌時間が６０〜１２０分であるのに、比較例２は６時間程度であった。得られた水溶液は茶色がかっており、チタンアルコキシドの重合体等の副生物が生成している可能性が示された。(Comparative Example 2)
This comparative example is an example in which a titanium chelate compound is produced by the same method as in Patent Document 4 (Japanese Unexamined Patent Publication No. 2015-36390).
4.0 g of L-lactic acid (purity 90% by mass) and 2.8 g of isopropanol were mixed, 2.8 g of tetraisopropoxytitanium (IV) was added with stirring, and then stirring was continued until the reaction heat disappeared. A mixed solution containing a titanium chelate was obtained. The molar ratio of the amount of tetraisopropoxytitanium (IV) used to the amount of L-lactic acid used was about 1: 4. An aqueous solution containing a titanium lactate chelate was obtained by adding 18.3 ml of water to the obtained mixed solution and stirring the mixture. However, when tetraisopropoxytitanium (IV) is mixed with a mixture of isopropanol and L-lactic acid, it emits smoke, which not only makes the work very difficult, but also produces solid matter, which makes it difficult to add water. It did not dissolve and it took longer to stir as compared with Examples 1 to 3. Specifically, in Examples 1 to 3, the stirring time until the titanium chelate compound was dissolved after water addition was 60 to 120 minutes, whereas in Comparative Example 2, it was about 6 hours. The obtained aqueous solution was brownish, indicating that by-products such as a polymer of titanium alkoxide may have been produced.
本発明によれば、少ない工程で高い生産性により効率的にチタンキレート化合物を得ることができるため、工業的に有利なチタンキレート化合物の製造方法が提供される。 According to the present invention, since a titanium chelate compound can be efficiently obtained with high productivity in a small number of steps, an industrially advantageous method for producing a titanium chelate compound is provided.
Claims (7)
前記希釈液とヒドロキシカルボン酸とを混合してチタンキレート化合物を得る第二工程と、を有する、チタンキレート化合物の製造方法。The first step of diluting titanium alkoxide with a solvent to obtain a diluted solution,
A method for producing a titanium chelate compound, which comprises a second step of mixing the diluted solution with a hydroxycarboxylic acid to obtain a titanium chelate compound.
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