WO2003082883A1 - Sels de titane, procede de preparation correspondant et procede de preparation d'epoxydes a partir de ces sels de titane - Google Patents

Sels de titane, procede de preparation correspondant et procede de preparation d'epoxydes a partir de ces sels de titane Download PDF

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WO2003082883A1
WO2003082883A1 PCT/JP2003/004154 JP0304154W WO03082883A1 WO 2003082883 A1 WO2003082883 A1 WO 2003082883A1 JP 0304154 W JP0304154 W JP 0304154W WO 03082883 A1 WO03082883 A1 WO 03082883A1
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Prior art keywords
titanium
acid
compound
formula
salt
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PCT/JP2003/004154
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English (en)
Japanese (ja)
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Yasuo Kikuzono
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Daiso Co., Ltd.
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Publication of WO2003082883A1 publication Critical patent/WO2003082883A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0257—Phosphorus acids or phosphorus acid esters
    • B01J31/0258—Phosphoric acid mono-, di- or triesters ((RO)(R'O)2P=O), i.e. R= C, R'= C, H
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
    • C07C309/30—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings of six-membered aromatic rings substituted by alkyl groups
    • C07C309/31—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings of six-membered aromatic rings substituted by alkyl groups by alkyl groups containing at least three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/095—Compounds containing the structure P(=O)-O-acyl, P(=O)-O-heteroatom, P(=O)-O-CN
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/72—Epoxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge

Definitions

  • Titanium salt its production method and its use
  • the present invention relates to a phosphate salt of a titanium salt, a titanium salt of a carboxylic acid, a titanium salt of a sulfonic acid, and an epoxide that epoxidizes an olefin with an oxidizing agent using the titanate as a catalyst. To a method of manufacturing.
  • titanium refers to tetravalent titan (IV).
  • a “production method of a titanium-containing aqueous solution” described in Japanese Patent Application Laid-Open No. 2001-322815 discloses a method of hydrolyzing a titanium alkoxide in the presence of an amine to obtain a titanium-containing aqueous solution. These are all insoluble in organic solvents.
  • Tianium alkoxy dotitanium acetylase Organic titanium compounds such as tones are known as titanium compounds soluble in organic solvents. However, since they are highly hydrophobic, insoluble in water, very unstable to water, and easily hydrolyzed, they cannot be used in systems where water is present.
  • An object of the present invention is to create a titanium salt having the property of being able to be dispersed or dissolved in both oil and water phases appropriately and stably, and to be used as a raw material for producing various titanium-containing materials.
  • a titanium salt which can be used as an effective catalyst for various reactions, and which can be used as an amphipathic substance whose amphipathic properties can be arbitrarily controlled according to the purpose. It is here. Disclosure of the invention
  • the present inventors have found that specific titanium can be appropriately and stably dispersed or dissolved in both oil and water phases, and has extremely high activity and selectivity for the selective epoxidation reaction of an olefin using a peroxide as an oxidizing agent. And completed the present invention.
  • a first aspect of the present invention is a compound represented by the general formula [I]
  • R 1 and R 2 are the same or different from each other and are a hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero element, and n is an integer of 1 to 4. ]
  • the phosphoric acid diester titanate [I] has, for example, the general formula [IV]
  • the second invention has the general formula [IX]
  • R 1 is a hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero element, and n is an integer of 1 or 2.
  • n is an integer of 1 or 2.
  • the phosphoric acid ester titanium salt [X] is, for example, represented by the general formula [X]
  • R 1 has the same meaning as described above.
  • the third invention is a compound represented by the general formula [II]
  • R 3 is a hydrocarbon group having 1 to 30 carbon atoms, and may contain a hetero element. However, R 3 does not contain a hydroxy group. n is an integer of 1 to 4. ]
  • the carboxylic acid titanium salt [II] is, for example, represented by the general formula [V]
  • the fourth invention is a compound represented by the general formula [III]
  • R 4 is a hydrocarbon group having 1 to 30 carbon atoms, and may contain a hetero element.
  • n is an integer of 1 to 4.
  • It relates to the sulfonic acid titanium salt represented by these.
  • the titanium salt of sulfonic acid [III] has the general formula [VI]
  • the titanium compound may be titanium alkoxide, titanium acetate, titanium alkoxide toner, and / or titanium chloride.
  • Aspect. 1 to 4, R!, Hydrocarbon groups represented by RR 3 and R 4 are linear, alicyclic, aromatic cyclic, fused cyclic, be of any heterocyclic And may contain a double bond or triple bond in the main chain, side chain or ring.
  • the hydrocarbon group preferably does not contain a double bond or a triple bond.
  • Hydrocarbon group oxygen in the main chain or side chain e.g.
  • the hydrocarbon group has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
  • the titanium carboxylate according to the second invention is The salt [in] does not include those obtained from hydroxycarboxylic acid as the starting carboxylic acid [V].
  • the fifth invention relates to a method for producing an epoxide which epoxidizes an olefin with a peroxide using the titanium salt according to the first to fourth inventions as a catalyst.
  • R 3 is a hydrocarbon group having 1 to 30 carbon atoms including a hydroxy group.
  • n is an integer from 1 to 4.
  • the preferred peroxide is at least one selected from the group consisting of hydrogen peroxide, which may be in solution, tertiary lipohydroxide, ethylbenzene hydroperoxide, and cumenodidropoxide. Both are one kind.
  • the peroxide may be generated in the reaction system.
  • at least one metal element selected from the group consisting of Group I, Group II and rare earth metal elements of the periodic table, and Z or ammonia are added to the reaction system. It is preferable to exist in The compound form of the metal element and Z or ammonia is preferably hydroxide and Z or a neutral salt. Carbonate is preferred as the neutral salt.
  • titanium compounds preferred Or L i, N a, K, R b, C s, M g, C a, S r, B a or L a.
  • preferred titanium compounds are titanium alkoxide and titanium alkoxide. At least one member selected from the group consisting of nickel acetate, titanium alkoxyacetonate and titanium chloride o
  • Phosphoric acid esters [IV] and [X] are, specifically, monomethylphosphoric acid, dimethylphosphoric acid, monoethylphosphoric acid, getylphosphoric acid, mono-n-propyrulinic acid, Pyrrulinic acid, monoisopropylurinic acid, diisopropylurinic acid, mono-n-butylylacid, di-n-butylphosphoric acid, mono-1-ethylhexylphosphoric acid, di-2-ethyl Hexylphosphoric acid, monododecyl monosodium phosphoric acid, monoisodecyl phosphoric acid, diisodecyl phosphoric acid, monophenyl phosphoric acid, diphenyl phosphoric acid, hydrogen phosphate-1,1 '— Binaphthyl 1,2'-diyl, monolauriluric acid, dilaurirrulinic acid, monostearinolenic acid, distearylic acid, monoeico
  • Carboxylic acids [V] are, for example, tridecanoic acid, hydroprilic acid, octanoic acid, lauric acid, heptanoic acid, myristic acid, nonanoic acid, palmitic acid , Stearic acid, azelaic acid, sebacic acid, pimelic acid, dodecandioic acid, suberic acid, tridecandioic acid, hexahydrophthalic acid, phthalic acid, 3-hydroxyhexadecane Acid, tropic acid, docosanoic acid, 2,4-dimethoxybenzoic acid, oxalic acid, polyacrylic acid, P-benzoic acid chloride, P-trifluoromethylbenzoic acid, polyacrylic acid, polymethacrylic acid, etc.
  • carboxylic acid titanium salt [II] is useful as the catalyst according to the present invention.
  • carboxylic acids represented by the chemical formula [V] include lactic acid, lingoic acid, tartaric acid, cunic acid, salicylic acid, mandelic acid, 2-hydroxybutyric acid, 2-hydroxyoctanoic acid, Using a hydroxycarboxylic acid such as 2-hydroxyhexadecanoic acid and 2-hydroxy-2-methylbutyric acid, and reacting this with a titanium compound, a titanium salt of a carboxylic acid obtained from the present invention is also available. Useful as catalysts according to the invention.
  • Sulfonic acid [VI] is, specifically, benzenesulfonic acid, P—benzenechlorosulfonic acid, p—toluenebenzenesulfonic acid, trifluoromethanesulfonic acid, 3-pyridinsulfonic acid, dodecylbenzene Sulfonic acid, poly (vinyl sulfonic acid), and Amberlist 15 DRY (MR).
  • Titanium compounds such as titanium alkoxide, titanium acetate, titanium alkoxide acetate and titanium chloride are diluted with a non-aqueous solvent as necessary. Separately, if necessary, dilute phosphate [IV] [X], carboxylic acid [V], or sulfonate [VI] with a non-aqueous solvent, and keep it at 0 to 80 ° C.
  • the above-mentioned titanium compound is added to the mixture, preferably under an inert gas or a flow of dry air while stirring, to give a phosphate [IV] [X], a carboxylic acid [V] or a sulfonate [VI]. React with titanium compound.
  • the obtained corresponding titanium salt can be isolated by evaporating the solvent under reduced pressure when it is dissolved in a solution, or by filtration or centrifugation when the titanium salt precipitates and precipitates. Can be isolated. The isolated product is dried at room temperature to 250 ° C in an inert gas, air, vacuum vessel or vacuum. Can be
  • the titanium salt according to the present invention has an affinity for both oil and water phases.
  • the following are examples of the amphipathic properties of the titanium salts according to the invention.
  • the titanium salts of carboxylic acids [II] such as those of carboxylic acids, are generally added to the aqueous phase. Although it dissolves and hardly partitions to the oil phase, titanates of 2-hydroxyhexadecanoic acid and 3-hydroxyhexadecanoic acid dissolve in the oil phase, but hardly partition to the aqueous phase.
  • carboxylic acid titanium salts [ ⁇ ] those having 6 or more carbon atoms in the group (R 3 ) are generally partially dissolved and distributed in both the oil phase and the aqueous phase.
  • the sulfonic acid titanate [III] has high solubility in the aqueous phase and hardly partitions to the oil phase.
  • Phosphate titanates [I] [IX] generally have low solubility and dispersibility in the aqueous phase and large solubility in the oil phase.
  • a phosphate salt [I] [IX], a potassium sulfonate [11], and a sulfonate titanate [III], and R 3 contains a hydroxy group
  • Each of the carboxylic acid titanate salts [II], which is a hydrocarbon group having 1 to 30 carbon atoms, has extremely high activity in the selective epoxidation reaction of orefins using peroxide as an oxidizing agent. It shows selectivity (approximately 100%) and can produce the corresponding epoxide almost quantitatively.
  • a catalyst comprising any of the salts is referred to as a titanium salt catalyst according to the present invention.
  • the titanium salt catalyst of the present invention is a titanium salt of a phosphoric acid ester, wherein the molar ratio between the phosphoric acid ester and the titanium atom satisfies the stoichiometric ratio described in claims 1 to 4. As described, it shows extremely high activity and selectivity for the olefin epoxidation reaction.However, the catalyst obtained by reacting the phosphate compound with the titanium compound disclosed in the present invention is used for the epoxidation reaction. When used, the molar ratio between the phosphoric acid ester and the titanium atom in the catalyst does not necessarily have to satisfy the stoichiometric ratio, and the ratio of P to Ti atoms (PZT i) is 0. 1 to 6, preferably 0.5 to 3, indicates that, similarly to the above, extremely high activity and selectivity can be obtained for the olefin epoxidation reaction.
  • Preferred peroxides are hydrogen peroxide, which may be in solution (aqueous solution or organic solvent solution), tertiary lipoxide, peroxyside, ethylbenzene hydroxide 0 -oxide and cumene hydroxide.
  • the peroxide may be one obtained by adding a precursor thereof to the reaction system and generating the peroxide in the reaction system.
  • the titanium salt catalyst according to the present invention is preferably added in an amount of 0.05 to 10 mol%, more preferably 0.01 to 5 mol%, based on the olefin.
  • the temperature is preferably between ⁇ 10 and 150, more preferably between 0 ° C. and 100 ° C.
  • the pressure is preferably 1 atmosphere and 50 atmospheres, more preferably Mild conditions of 1 to 20 atmospheres are sufficient. It is not necessary to use a reaction solvent, but it may be used.
  • the titanium salt catalyst according to the present invention By using the titanium salt catalyst according to the present invention, high selectivity can be achieved.
  • the reasons for converting olefins to epoxides at selectivity are known titanosilicate-based amorphous catalysts, porous catalysts having mesopores, and TS-1 having an MFI crystal structure.
  • a zeolite catalyst or the like an acid site due to a silanol group is inevitably present in the catalyst, but such an acid site does not exist in the titanium salt catalyst according to the present invention, and water coexists. This is because the epoxide generated by the oxidation reaction is not hydrated. That is, the basic structure of the titanate catalyst according to the present invention differs from that of the known titanosilicate-based compound catalyst in the presence or absence of an acid point.
  • the olefins to which the epoxidation reaction using the titanium salt catalyst according to the present invention can be applied include aliphatic monoolefins such as ethylene, propylene, butene, pentene, hexene, heptene and octene.
  • Examples include broadly defined, jS-unsaturated ketones and a, iS-unsaturated carboxylic acids having carbonyl or carboxyl groups adjacent to the double bond, such as lylic acid.
  • the concentration of hydrogen peroxide may be in a wide concentration range of 1 to 70%.
  • aqueous hydrogen peroxide exhibits a high epoxidation activity even in a low concentration region is effective, for example, when hydrogen peroxide is generated in a reaction system and an epoxidation reaction is performed.
  • the epoxidation reaction is carried out from the group consisting of metal elements of Group I, Group II and rare earth elements of the periodic table.
  • the presence of at least one selected metal element and / or ammonia in the reaction system significantly improves the catalytic activity.
  • the metal element and Z or ammonia may be in any form as long as they are hydroxides and / or neutral salts. Among them, those in the form of carbonates as neutral salts exhibit particularly excellent addition effects.
  • the metal element is preferably Li, Na, K :, Rb, Cs, Mg, Ca, Sr, Ba or La. Addition amount of metal atoms (total amount in case of plural), preferably 0.01 mol% to 6 mol%, more preferably 0.05 mol% to 3 mol% with respect to hydrogen peroxide. %.
  • the epoxidation reaction using the titanium salt catalyst according to the present invention can be carried out most simply using only the starting material olefin, the oxidizing agent and the catalyst, but a reaction solvent can be used if necessary.
  • the solvent is not particularly limited as long as it does not inhibit the reaction, and is selected from the group consisting of alkanes, cycloalkanes, nodrogenidalkans, alcohols, ethers, carboxylate esters, nitriles, aromatic hydrocarbons and the like. It may be a mixture of two or more.
  • halogenated alkenes show an epoxidation reaction-promoting effect, and particularly preferred are dichloromethane, black-mouthed form, 1,2-dichloronorethane, and 1,2-dichloropropane.
  • the amount of the solvent used is the solvent Z-offline (molar ratio), preferably 0.1 to 10 times, more preferably 0.2 to 2 times.
  • Compound 1 Five Monoisopropyl titanyl phosphate (hereinafter abbreviated as “Compound 1”) was synthesized from 2 g and 13.5 g of titanium tetraisopropoxide, and di (n-butyl) phosphate was synthesized.
  • Di (n-butyl) titanium phosphate (compound-3) was synthesized from 8 g and 7.0 g of titanium tetrasoproboxide, and mono (2-ethylhexyl) phosphate was synthesized.
  • Mono-2-ethylhexyl titanate (Compound 14) was synthesized from 4.0 g of titanium tetrasodium mouth oxide and 14.0 g, and di-2-ethylhexyl phosphate was synthesized. From 7 g and 7.0 g of titanium tetrasopropoxide, di- (2-ethylhexylhexyl) titanate (Compound 15) was synthesized, and 20.0 g of diphenyl phosphate and titanium tetrahydrate were synthesized.
  • the phosphoric acid diester portion has peaks at 53.91 (m, 4H) and (1.60-0.87 (m, 30H)), and equivalent peaks are observed in both the peak position and peak shape.
  • the peak is broadened, and no peak other than the above peak is observed in the region of (515 to -4 ppm.) From these facts, the product (compound-5) has the following structure.
  • the acid was confirmed to be di-2-ethylhexyl titan.
  • titanium lactate (hereinafter abbreviated as “compound-10”) was synthesized from 45.5 g of lactic acid and 7 2.O g of titanium tetrasopropoxide.
  • Titanium linoleate (compound 11) was synthesized from 26.8 g of the acid and 28 g of titanium tetraisopropoxide, and 15.5 lg of tartaric acid and 14 g of titanium tetrasopropoxide were used.
  • Compound-1 2 was synthesized, and titanium citrate (Compound 13) was synthesized from 12.8 g of citric acid and 14 g of titanium tetrasopropoxide, and 13.8 g of salicylic acid was synthesized.
  • g and titanium tetraisopropoxide 14 g from titanium salicylate (compound 1
  • 2-hydroxytitanium isobutyrate (compound 16) was synthesized from 20.9 g of 2-hydroxysobutyric acid and 28.5 g of titanium pentaisopropoxide.
  • Titanium 2-hydroxyoctanoate (compound 17) was synthesized from 11.6 g of 2-hydroxyoctanoic acid and 10.3 g of titanium tetrisopropoxide, and 2-hydroxyhexadeca was synthesized.
  • 2-hydroxyhexadecanoic acid (compound- 18) from 1.3 g of nitric acid 1 and 1.3 g of titanium tetraisopropoxide 6.
  • Titanium 3-hydroxydecanoate (compound 13) was synthesized from 12.1 g of hydroxydecanoic acid and 6.5 g of titanium tetraisopropoxide, and 8.3 g of tropic acid and titanium tetraethylate were synthesized. Titanium tropate (compound 24) was synthesized from 7 g of sopropoxide, and 25.5 g of cyclohexanecarboxylic acid and 14 g of titanium tetrasopropoxide were synthesized from cyclohexanecarboxylic acid.
  • titanium laurate (compound 26) was synthesized from 20.0 g of rauric acid and 7 g of titanium tetraisopropoxide, and palmitic acid 25.6 g of titanium palmitate (compound 27) was synthesized from 7 g of titanium tetraisopropoxide, and 18.2 g of 2,4-dimethoxybenzoic acid 18.2 g of titanium tetraisopropoxide 7 g, 2,4-Dimethoxybenzoic acid titanate (compound 28) was synthesized, and oxalic acid dihydrate 25.3 g and titanium tetrisopropoxide 1
  • Titanium oxalate (compound 29) was synthesized from 3.5 g, and p-chlorobenzoic acid (5.6 g) and titanium tetraisopropoxide 7 g were synthesized from p-chlorobenzoate (compound 29). — 30), and p-trifluoromethylbenzoic acid (19.0 g) and titanium tetrisopropoxide (7.5 g) were added to p—trifluoromethylbenzoic acid (compound 1 3) was synthesized, and 21.2 g of pentafluorobenzoic acid and titanium tetraisopropoxide 7
  • Example 33 Synthesis of titanium laurylbenzenesulfonate
  • 33.Og of commercially available laurylbenzenesulfonate was placed in a beaker, and 50 g of dry isopropyl alcohol was added thereto, and the former was dissolved under stirring.
  • 7 g of titanium tetraisopropoxide was put into a dropping funnel and slowly added dropwise to the solution in the beaker under vigorous stirring.
  • Polystyrene-polyacrylic acid block copolymer titan (hereinafter abbreviated as “Compound-37”) was synthesized and marketed.
  • Polystyrene-polyacrylic acid block copolymer (polystyrene average molecular weight about 66,500, polyacrylic acid average molecular weight about 4,500, Polymer Source Example 36 except that a solution of 8.0 g dissolved in 100 g of dry tetrahydrofuran was used and 0.5 g of titanium tetraisopropoxide was used. In the same manner as in the above, compound-37 was obtained.
  • Example 38 Synthesis of Titanium Salt from Sodium Polyacrylate
  • 9.4 g of commercially available sodium polyacrylate (average molecular weight: about 5,100) was added, and ion was added thereto.
  • Exchange water 200 g was added to dissolve the former.
  • Into another dropping funnel add 20.3 g of a 30% titanium sulfate solution, vigorously stir the solution in the above beaker at room temperature, and slowly drop titanium sulfate from the dropping funnel. Added down. After completion of the dropwise addition, the obtained reaction mixture was evaporated to dryness using a rotary evaporator.
  • a C conversion (number of moles of A C used / number of moles of A C in product) Number of moles of A C used X I 0 0
  • H 2 0 2 reaction rate (H 2 0 moles of H 2 0 2 2 molar number one product used) / moles X 1 0 0 of the H 2 0 2 was used
  • PD selectivity number of moles of PD in product Z number of moles of AC reacted X 100
  • Example 4 3 (-phosphate ester T i Catalyst A CZH 2 0 2 / M g C 0 3)
  • Example 4 5 (-phosphate ester T i catalysts ZAC ZH 2 0 2, L a 2 (C 0 3) 3)
  • Example 4 8 (-phosphate ester T i catalysts Z 1 - xenon emission / H 2 0 2 to)
  • Example 5 (-phosphate ester T i catalysts Z meta Li torque Rorai Dono H 2 0 2)
  • MAC 2-methyl-3-propene propene
  • the decane solution was added in an amount of 27 lg and the MAC purified by distillation was added in an amount of 16.4 g, and the autoclave was sealed. Place this in an oil bath at 100 ° C and stir for 2 hours in a light-shielded state. Was done.
  • Example 52 phosphoric acid ester Ti catalyst MA CZ t — Bu 0 HZM g C 0 3 )
  • Example 5 (-phosphate ester T i catalyst ZA CZH 2 0 2)
  • the present invention creates a titanium salt having the property that it can be dispersed or dissolved in both oil and water phases appropriately and stably, and can be used as a raw material for producing various titanium-containing materials. Further, the present invention provides a titanate salt that can be used as a catalyst effective for various reactions and can be used as an amphipathic substance whose amphipathic properties can be arbitrarily controlled according to the purpose.

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Abstract

L'invention concerne des sels de titane qui se dispersent ou se solubilisent correctement et durablement à la fois dans l'huile et dans l'eau, ainsi que des sels de titane pouvant être utilisés comme matières premières dans divers matériaux à base de titane ou comme catalyseurs dans de nombreuses réactions. Ils sont en outre utilisés comme substances amphiphiles dont le pouvoir amphiphile peut être arbitrairement régulé selon l'utilisation prévue. Par ailleurs, l'invention concerne des sels de titane de diesters phosphoriques représentés par la formule (I), dans laquelle R1 et R2 représentent indépendamment un groupe d'hydrocarbure en C1-30 pouvant contenir un hétéroatome ; n étant un nombre entier compris entre 1 et 4.
PCT/JP2003/004154 2002-04-01 2003-04-01 Sels de titane, procede de preparation correspondant et procede de preparation d'epoxydes a partir de ces sels de titane WO2003082883A1 (fr)

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JP2002098906A JP4196576B2 (ja) 2002-04-01 2002-04-01 チタン塩、その製造法、およびこれを用いるエポキシドの製造法

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US9371422B2 (en) 2011-09-07 2016-06-21 Dow Corning Corporation Titanium containing complex and condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts

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US7459572B2 (en) * 2004-08-19 2008-12-02 Rstech Corporation Process for the preparation of glycidyl derivatives
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