WO2003082883A1

WO2003082883A1 - Titanium salts, process for preparation thereof, and process for preparing epoxides with the same

Info

Publication number: WO2003082883A1
Application number: PCT/JP2003/004154
Authority: WO
Inventors: Yasuo Kikuzono
Original assignee: Daiso Co., Ltd.
Priority date: 2002-04-01
Filing date: 2003-04-01
Publication date: 2003-10-09
Also published as: JP4196576B2; JP2003292497A

Abstract

The invention aims at providing titanium salts which are properly and stably dispersible or soluble in both oil and water and titanium salts which can be used as raw material of various titanium-containing materials or as catalysts for various reactions and are useful as amphiphilic substances capable of being arbitrarily controlled in the amphiphilicity in accordance of the purpose of use. The invention provides titanium salts of phosphoric diesters as represented by the general formula [I]: [I] wherein R1 and R2 are each independently a C1-30 hydrocarbon group which may contain a heteroatom; and n is an integer of 1 to 4.

Description

Description Titanium salt, its production method and its use

Epoxide manufacturing technology

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.

Throughout this specification, titanium refers to tetravalent titan (IV). Background art

In recent years, the use of titanium materials in the field of photocatalysis has been expanding, especially in the field of titanium materials. In the production of titanium oxide thin films, the solubility of titanium precursor as a raw material in solvents and the storage stability are technical issues. It has become. As a prior art in this field, there is, for example, a “method of storing an aqueous solution of a water-soluble titanium complex” described in Japanese Patent Application Laid-Open No. 2000-35187. This technology uses hydroxycarboxylic acid as an organic ligand to form a water-soluble titanium complex, and adds a base such as ammonia to suppress hydrolysis of the formed complex. Is maintained at 2.0 to 8.0. In addition, 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. —Titanium 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.

As described above, most of the conventional technology relates to the technology related to the extremes of water-solubility or oil-solubility, and almost all titanium compounds that can be appropriately and stably dispersed or dissolved in both oil-water phases are known. Not. 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. To provide 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]

OR

0 = P- 0 Ti (0H) 4 one _n [I]

OR ²

门 [In the formula, 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. ]

And a titanium salt of a phosphoric acid diester represented by the formula:

The phosphoric acid diester titanate [I] has, for example, the general formula [IV]

Wherein R ¹ and R ² have the same meaning as described above. ]

It can be obtained by reacting a titanium compound with the phosphoric acid diester represented by

An example of the reaction between a phosphoric acid diester and a titanium alkoxide is shown in Reaction Formula [VIII].

+ 4 i-PrOH

The second invention has the general formula [IX]

[IX] [Wherein, 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. ] It is related with the titanium salt of phosphoric acid monoester represented by these.

The phosphoric acid ester titanium salt [X] is, for example, represented by the general formula [X]

[X]

[Wherein, R ¹ has the same meaning as described above. ]

It is obtained by reacting a titanium compound with a phosphoric acid monoester represented by

An example of the reaction between a phosphoric acid monoester and a titanium alkoxide is shown in Reaction Formula [VII].

RaOH

[VII]

The third invention is a compound represented by the general formula [II]

R Ti Disturbance [ _n ]

n

[In the formula, 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. ]

A carboxylic acid titanium salt represented by the formula:

The carboxylic acid titanium salt [II] is, for example, represented by the general formula [V]

R C-0H [V]

II

0

[Wherein, R ³ has the same meaning as described above]. ]

Can be obtained by reacting a titanium compound with the carboxylic acid represented by

The fourth invention is a compound represented by the general formula [III]

[In the formula, 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]

[VI]

[Wherein, R ⁴ has the same meaning as described above. And a sulfonic acid represented by the following formula:

In the first to fourth inventions, 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. However, when the titanium salt according to the first to fourth inventions is used as a catalyst, 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. - 0, = 0, One COOH, in the form of such one CHO), nitrogen (e.g., - NH _2, one N 0 _2, one N =, - NH- Etc.), silicon, and a hetero atom such as a halogen element. 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.

In the fifth invention, the general formula [Π]

[In the formula, R ³ is a hydrocarbon group having 1 to 30 carbon atoms including a hydroxy group. n is an integer from 1 to 4. ]

Epoxide epoxidation with peroxide using a carboxylic acid titanate represented by the formula (1) as a catalyst. .

In the fifth invention, 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. In the epoxidation reaction according to the fifth invention, 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. Metal elements preferred Or L i, N a, K, R b, C s, M g, C a, S r, B a or L a. In the method for producing a titanium salt in which a titanium compound is reacted with a phosphoric acid ester [IV] [X], a carboxylic acid [V], or a sulfonic acid [VI], 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, monoeicosanilyl acid, dieicosanilonic acid, etc. Ah .

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.

The carboxylic acid titanium salt [II] according to the second invention is useful as the catalyst according to the present invention. Also, 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. Regarding the dissolution and dispersibility of titanium salts in a system of aqueous hydrogen peroxide and a halogenated hydrocarbon solvent, 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. Of the carboxylic acid titanium salts [Π], 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. In addition, 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. Thus, by appropriately selecting the titanium salt according to the present invention, its properties can be arbitrarily changed from hydrophilic to hydrophobic. Therefore, it is a very useful compound for the production of titanium-containing materials and the use of high-performance catalysts that need to be distributed to both phases.

Next, the catalytic use of the titanium salt according to the present invention will be described.o

According to the present invention, 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. Hereafter, these titanium

0 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. There is at least one species selected from the group consisting of:

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. In the epoxidation reaction, the temperature is preferably between −10 and 150, more preferably between 0 ° C. and 100 ° C., and 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.

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. In 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. Arylene-substituted olefins which may have a substituent on the ring, such as styrene and getylbenzene; and aliphatic gens such as butadiene, isoprene, and chloroprene. Aryloxy chlorides, metalyl chlorides, 1,2-dichloropropene, 1,3-dichloropropene, and other non-loginated olefins; aryl alcohols, metalyl Alcohols such as alcohols having aryl alcohol skeleton; cyclopentene, cyclohexene and cyclooctene; cycloalkenes; acrylic acid; 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.

When the epoxidation reaction using the titanium salt catalyst according to the present invention is carried out using aqueous hydrogen peroxide, the concentration of hydrogen peroxide may be in a wide concentration range of 1 to 70%. The fact that 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.

Two There o

In the epoxidation reaction using a titanium salt catalyst according to the present invention, in particular, the reaction using aqueous hydrogen peroxide as an oxidizing agent, 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. Of these, 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 (in the case of a plurality of compounds, the total amount used) is the solvent Z-offline (molar ratio), preferably 0.1 to 10 times, more preferably 0.2 to 2 times.

¾).

Three BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples. In the examples, the percentages indicating the compositions are all percentages by weight.

Example 1 (Synthesis of monoisodecyl titanate phosphate)

In a nitrogen box equipped with a balance and a stirrer, put 23.9 g of commercially available monoisodecyl phosphate into a beaker, add 50 g of dry isopropyl alcohol to this, and dissolve the former under stirring. I let it. In a nitrogen box, 14.4 g of titanium tetrisopropoxide was put into a dropping funnel and slowly added dropwise to the solution in the above beaker under vigorous stirring. After completion of the dropwise addition, the obtained reaction mixture was evaporated to dryness using a rotary evaporator. The obtained dried product was washed with methanol and dried at 60 ° C. to obtain monoisodecyl titanyl phosphate (hereinafter abbreviated as “Compound 11”).

The product-phosphate Monoisodeshiru titanium ting material-phosphate Monoi Sodeshiru, pro tons nuclear magnetic resonance, respectively for structural identification was dissolved in deuterium nuclear Loloho Lum ^{(2 7 0 MH z - 1} H- NMR) spectra were measured.

As a result, in the NMR spectrum of the raw material monoisodecyl phosphate, the absorption peak due to the protons of the phosphoric acid portion was observed as a chemical shift (one peak at 8.15 ppm. In the product, this peak completely disappeared, indicating that the two H atoms in the phosphoric acid moiety were completely replaced with T i by a salt-forming reaction with T i. In addition, from the NMR chemical shift and the trapped state, the phosphoric acid ester part of the raw material and the phosphoric acid ester part of the product were both S4.05 (m, 2H) and <51.7- At 0.7 (m, 19H), the equivalent peak with the same peak position and peak shape

Four In the product, the peak at (51.7-0.7 ppm (m, 19H) is broadened. In the region of 515 to -4 ppm, no peak other than the above peak is observed. From these results, it was confirmed that the product (Compound-1) was monoisodecyl titanyl phosphate having the following structure.

material

^X H NMR (CDC1 _3> 270MHz) δ 8.15 (s, 2H) _: δ 4.05 (m, 2H) δ 1. -0.7 (m, 19H)

Compound 1 1

^{_{X H NMR (CDC1 3, 270MHz}} ) δ 4.05 (m, 2H), (51.7-0.7 (m, 19 H, broad) Example 2-7 (-phosphate Esuteruchita down the slip)

In the same manner as in Example 1, monoisopropyl phosphate 14.

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. Synthesis of diphenyl titanyl phosphate (compound-1 6) from 5.8 g of sopropoxide From 1,0.4 g of 1,1-binaphthyl acid-2,2'-diyl and 2.2 g of titanium tetrisopropoxide, 1,1-binaphthyl phosphate 1,2,2'-diylc (Compound 1-7) was synthesized.

Of these, the product di (.n-butyl) titanate (Compound-3), its raw material di (n-butyl) phosphate, and the product di (2-ethyl) phosphate to Kishiruchita emissions (compound - 5) and its raw material Li Nsanji - 2 Echiru hexyl about to the same manner as in example 1 for the structure identification pro ton nuclear magnetic resonance (2 7 0 MH z one ^r H -NMR) measurements were performed.

As a result, for the product di (n-butyl) titanium phosphate (Compound 13) and its raw material di (n-butyl), the NMR spectrum of the raw material showed that the prototype of the phosphoric acid part was The absorption peak due to the reaction is observed as a single peak at 59.39 ppm in the chemical shift, while the peak disappeared completely in the product. This indicates that one H atom in the phosphoric acid moiety is capable of forming a salt with Ti.

6 From this, it can be seen that T i was completely replaced. Also, from the NMR chemical shift and the cutting state, the phosphoric acid diester portion of the raw material has peaks at 54.07 (m, 4H) and 51.72-0.90 (m, 14H), and the product phosphorus The acid gester moiety has peaks at (54.06 (m, 4H) and <51.72-0.90 (m, 14H), and equivalent peaks are observed in both the peak position and the peak shape. In addition, no peaks other than the above peaks are observed in the range of S 15 to -4 ppm, indicating that the product (compound 13> has the following structure) It was confirmed to be di (n-butyl) titanium phosphate.

material

^{_{J H NMR (CDC1 3, 270ΜΗζ}} ) δ 9.39 (s, 1H), δ 4.07 (m, 4H), δ 1.72-0.90 (m, 14H)

Compound 1 3

JH NMR (CDC1, 270MHz) δ 4.06 (m, 4H), δ 1.72-0.90 (m, 14H, broad)

7 For the product di-2-ethylhexyl titanyl phosphate (Compound 15) and its starting material, di-2-ethylhexyl phosphate, the NMR spectrum of the starting material indicates that the phosphoric acid moiety was The absorption peak due to the compound is observed as a single peak at 58.49 ppm of the chemical shift, while the peak disappears completely in the product. This indicates that one H atom in the phosphoric acid moiety was completely replaced by T i by a salt-forming reaction with T i. From the NMR chemical shift and the cutting state, the phosphoric ester portion of the raw material had peaks at 53.93 (m, 4-H) and S 1.60-0.87 (m, 30H). 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.

material

XH NMR (CDCI3, 270MHz) «58.49 (s, 1H), δ 3.93 (m, 4H), δ 1.60-0.87 (m, 30H)

8

Compound 1 5

NMR (CDCI3, 270MHz) 63.91 (m, 4H), δ 1.60-0.87 (m, 30H, broad) Example 8 (Synthesis of mono-n-dodecyl titanate)

20.1 g of mono-n-dodecylmonosodium phosphate was placed in a viscous solution, and 506 g of 5% sulfuric acid was added thereto and stirred. To the obtained white suspension solution, 330 g of ion-exchanged water was added, and while vigorously stirring the whole, a 30% titanium sulfate solution was added dropwise from a dropping funnel. After completion of the dropwise addition, stirring was continued for about 10 minutes, and the obtained viscous white suspension solution was subjected to suction filtration. 10020 g of ion-exchanged water was added to the filtered white precipitate, and the mixture was stirred and washed at room temperature, filtered by suction, and the collected precipitate was placed in a 60 ° C. air circulation oven and dried for 15 hours. . The phosphoric acid mono-η-dodecyl titan thus synthesized is hereinafter abbreviated as Compound-8. Example 9 (Synthesis of titanium docosanoate)

In a nitrogen box equipped with a balance and a stirrer, 34.2 g of commercially available docosanoic acid was placed in a beaker, and 258 g of dry isopropyl alcohol was added thereto, and the former was dissolved with stirring. In a nitrogen box, add 7.Og of titanium tetrisopropoxide to the dropping port, and vigorously stir the solution in the beaker.

9 It was slowly added dropwise with stirring. After the completion of the dropwise addition, the obtained reaction mixture was evaporated to dryness using a single evaporator, and titan docosanoate (hereinafter abbreviated as “compound-9”) was obtained. Examples 10 to 32 (Synthesis of titanium carboxylate)

In the same manner as in Example 8, 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

4) was synthesized from 300.5 g of mandelic acid and 28 g of titanium tetrasopropoxide.

5), and 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. Of 2-hydroxyhexadecanoic acid (compound- 18) from 1.3 g of nitric acid 1 and 1.3 g of titanium tetraisopropoxide 6. Og was added to 2-hydroxy-2-methyl butyrate 1 1.8 g and Titanium tetraisopropoxide 1 5. O g to 2—Hydroxy 2-Methyl Synthesis of titanium rubutyrate (compound 19) and tridecannic acid 1

2. Synthesis of titanium tridecanedioate (Compound 10) from 2.2 g and 7 g of titanium tetraisopropoxide, 8.6 g of hexahydrophthalic acid and 7 g of titanium tetraisopropoxide Hexahydrohydrophthalate titanate (compound 121) was synthesized from phthalic acid and titanium phthalate (compound 122) was synthesized from 8.3 g of phthalic acid and 7 g of titanium tetrasopropoxide. 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. Combining titanium (compound 25) Then, 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

Two g of titanium pentafluorobenzoate (Compound 132) was synthesized. Example 33 (Synthesis of titanium laurylbenzenesulfonate) In a nitrogen box equipped with a balance and a stirrer, 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. In a nitrogen box, 7 g of titanium tetraisopropoxide was put into a dropping funnel and slowly added dropwise to the solution in the beaker under vigorous stirring. After the completion of the dropwise addition, the obtained reaction mixture was evaporated and concentrated using a rotary evaporator to obtain titanylurylbenzenesulfonate (hereinafter abbreviated as “compound 33”). Example 34 (Synthesis of titanium polyvinylsulfonate)

An Erlenmeyer flask was charged with 41.7 g of a commercially available 25% aqueous solution of sodium polyvinyl sulfonate, and 166 g of ion-exchanged water was added thereto. A solution obtained by adding 80 g of ion-exchanged water to 16.0 g of a 30% titanium sulfate solution was placed in another dropping funnel. This solution was slowly added dropwise to the solution in the Erlenmeyer flask under vigorous stirring at room temperature. After the completion of the dropwise addition, the obtained reaction mixture was evaporated to dryness using a mouth evaporator. Dry matter approx. 2

0 g was placed in a bag of regenerated cellulose dialysis membrane (molecular weight cut-off: 500, manufactured by Spectrum Lab. Inc.), transferred to a beaker containing 2 liters of ion-exchanged water, and stirred at room temperature. did. After replacing the beaker with ion-exchanged water four times to wash the dried product, the contents in the dialysis membrane bag are evaporated to dryness using a rotary evaporator, and the polyvinyl sulfonic acid titanate (hereinafter referred to as “polyvinyl sulfonate”) is removed. `` Compound 1 3 4 "). Example 35 (Synthesis of titanium polystyrenesulfonate)

In a nitrogen box equipped with a balance and a stirrer, 20.9 g of a commercially available cation exchange resin (trade name: Amberlyst 15DRY) was placed in a beaker, and 100 g of dry isopropyl alcohol was added thereto. In a nitrogen box, 14 g of titanium tetraisopropoxide was put into a dropping funnel and slowly added dropwise to the solution in the above beaker under vigorous stirring. After completion of the dropwise addition, the obtained reaction mixture was evaporated to dryness using a rotary evaporator to obtain polystyrene sulfonic acid titan (hereinafter abbreviated as “compound 135”). Example 36 (Synthesis of poly (titanium acrylate))

In a nitrogen box equipped with a balance and a stirrer, put 14.5 g of commercially available polyacrylic acid (average molecular weight: about 2,000) in a beaker, and add it to dried isopropanol. g was added, and the former was dissolved under stirring. In a nitrogen box, 14 g of titanium tetraisopropoxide was put into a dropping funnel, and slowly added dropwise to the solution in the beaker under vigorous stirring. After completion of the dropwise addition, the obtained reaction mixture was evaporated to dryness using a rotary evaporator to obtain titanium polyacrylate (hereinafter abbreviated as “compound-136”). Example 37 (Synthesis of Polystyrene-Polyacrylic Acid Block Copolymer Titanium)

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) In a beaker, 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. To about 22 g of the dried product, add 55 g of ion-exchanged water to make an aqueous solution, and put it in a bag of dialysis membrane (fraction molecular weight: 500, manufactured by Spectrum Lab. This was transferred to a beaker containing 10 liters of ion-exchanged water and stirred at room temperature. The beaker was replaced with ion-exchanged water four times. The washed water did not cloud the barium hydroxide aqueous solution. The contents in the dialysis membrane bag were evaporated to dryness using a rotary evaporator to obtain poly (acrylic acid titanate) (hereinafter abbreviated as “Compound-38”). Example 3 9 (Synthesis of titanium lactate)

In a nitrogen box equipped with a balance and a stirrer, add 18.0 g of commercially available lactic acid to a beaker, and add it to dried isopropanol alcohol. And the former was dissolved with stirring. In a nitrogen box, 47.0 g of titandiisopropyl-1,4,4-pentadionate was added to the dropping port at a dropping port, and this was slowly added dropwise to the solution in the beaker under vigorous stirring. Was. After completion of the dropwise addition, the obtained reaction mixture was evaporated to dryness using a rotary evaporator to obtain titanium lactate (hereinafter abbreviated as “compound-39”). Example 40 (Synthesis of monoisodecyl titanate phosphate)

In a nitrogen box equipped with a balance and a stirrer, 24 g of commercially available monoisodecyl phosphate was placed in a beaker, and 50 g of dry n-butyl alcohol was added thereto, and the former was dissolved with stirring. . Tetra-n-butoxytitanium (17.0 g) was added to a dropping funnel in a nitrogen box, and this was slowly added dropwise to the solution in the beaker under vigorous stirring. After completion of the dropwise addition, the obtained reaction mixture was evaporated to dryness using a rotary evaporator to obtain monoisodecyl titanyl phosphate (hereinafter, abbreviated as “compound-40”). Example 4 1 (-phosphate ester T i catalysts Noah Riruku Rorai de ZH ₂ 0 ₂₎

Glass made O with a safety valve of the pressure 1 0 kgf / cm ² - DOO click slave compound one 1 put 0. 9 7 g, to which by distillation of about 3 4% peracetic acid hydrogen water 1 0. 6 g 14.0 g of purified aryl chloride (hereinafter abbreviated as “AC”) was added thereto, and the autocrepe was sealed. This was placed in a water bath at room temperature (22 ° C.), and the reaction was carried out with stirring for 6 hours in a light-shielded state. After the reaction, the glass autoclave was cooled on ice and opened. The reaction solution After 50 g of ethanol was added and mixed well to make the liquid phase one phase, the catalyst was separated by filtration using a membrane filter. An aliquot of this filtrate was taken, and the amount of unreacted hydrogen peroxide was determined by the method of pseudometry using an aqueous NZ 10 sodium thiosulfate solution. In addition, a sample in which ethyl propionate was added as an internal standard to a part of the remaining filtrate was analyzed by gas chromatography with a flame ionization detector (FID-GC), and unreacted AC, Quantification of produced epichlorohydrin (hereinafter abbreviated as “EP”) and 3-chloro-1,2-propanediol (hereinafter abbreviated as “PD”) were performed.

The calculation formula shown below, AC reaction rate, H ₂ 0 ₂ reaction rate, EP selectivity, and was calculated PD selectivity.

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

EP selectivity-number of moles of EP in product / number of moles of reacted AC X 100

PD selectivity = number of moles of PD in product Z number of moles of AC reacted X 100

Obtained from a calculation and analysis results shown above, AC reaction rate 22. 0%, H _₂ 0 ₂ reaction rate 5 2. 6% EP selectivity 9 8. 3% PD selectivity of 1.4%, the Was. Example 4 2 (-phosphate ester T i catalyst ZA CZH ₂ 0 ₂ ZN a

₂ CO 3)

A glass-made O one preparative click slave having a safety valve of the pressure 1 0 kgf / cm ^2, compound - 1 to 0. 9 4 g and carbonate Na Application Benefits um 0.03 g was added, and 10.9 g of about 34% aqueous hydrogen peroxide and 13.9 g of AC purified by distillation were added thereto, and the autoclave was sealed. This was placed in a water bath at 10 ° C, and the reaction was stirred for 6 hours in a light-shielded state. After reaction, the anti reasonable analysis in the same manner as in Example 4 1, AC response rate _{2 6. 3%, H 2 0} 2 reaction rate 5 3. 7%, EP selectivity 1 0 0%, PD selectivity 0 %. Example 4 3 (-phosphate ester T i Catalyst _{_{A CZH 2 0 2 / M g}} C 0 3)

A glass-made O over preparative click slave having a safety valve of the pressure 1 0 kgf / cm ^2, compound - 1 to 0. 9 4 g and basic carbonate magnesite Shiumu _{(4 M g C 0 3 *} M g (OH) 2 _{* 5 H 2 0) 0. 1} lg put, AC 1 4. 0 g was added to a more purified distillation of about 3 4% hydrogen peroxide 1 8. lg thereto and sealed O Tok Leeb. This was placed in a water bath at 20 ° C., and the reaction was stirred for 4 hours in a light-shielded state. After reaction, the reaction analyzed in the same manner as in Example 4 1, AC response rate 5 9. 8% Η _₂ φ ₂ reaction rate 7 0. 6%, Ε Ρ selectivity 1 0 0%, PD selectivity 0% , Got. Example 4 4 (-phosphate ester T i catalyst _{_{ZA CZH 2 0 2 / C a}} C 0 3)

Breakdown voltage 1 0 kgf / cm Glass with ^two safety valves O - especially Loew, compound one 1 0. 9 5 g and calcium carbonate were placed 0. 0 9 5 g of about 3 4% hydrogen peroxide thereto 10.6 g of water and 14.0 g of AC purified by distillation were added, and the autoclave was sealed. This was placed in a water bath at 10 ° C, and the reaction was stirred for 6 hours in a light-shielded state. After the reaction, Example 4 1 performs anti reasonable analysis in the same manner as, AC reaction rate 2 3. 3%, H ₂ 0 ₂ reaction rate 4 2. 3%, EP selectivity 100%, PD selectivity 0% were obtained. Example 4 5 (-phosphate ester T i catalysts _{_{ZAC ZH 2 0 2, L a}} 2 (C 0 3) 3)

A glass-made O over preparative click Leeb having a safety valve of the pressure 1 0 kg ΐ / cm ^2, compound -. 1 0 9 4 g and carbon La pointer down _{_{(L a 2 (C 0 3}} ) 3 * 8 H 2 0.5 g of 0) was added thereto, and 10.7 g of about 34% aqueous hydrogen peroxide and 14.0 g of AC purified by distillation were added thereto, and the autoclave was sealed. This was placed in a water bath at 10 ° C, and a stirring reaction was performed for 6 hours in a light-shielded state. After reaction, the reaction analyzed in the same manner as the actual ¾ Example 4 1, AC response rate _{2 2. 6%, H 2 0} 2 reaction rate 4 4. 5%, EP selectivity 1 0 0%, PD election択率0%. Example 4 6 (-phosphate ester T i catalysts AC Bruno _{_{_{H 2 0 2 Z (NH 4}}} ) 2 C 0 3)

In a glass autoclave equipped with a safety valve with a pressure resistance of l O kgf Z cm ² , add 0.94 g of compound-1 and 0.087 g of ammonium carbonate, and add about 34% 11.0 g of aqueous hydrogen oxide and 14.lg of AC purified by distillation were added, and the autoclave was sealed. This was placed in a water bath at 10 ° C, and a stirring reaction was performed for 6 hours in a light-shielded state. After reaction, the reaction analyzed in the same manner as in Example 4 1, AC response rate 2 4. Ma 96, H ₂ 0 ₂ reaction rate 5 2. 0%, EP selectivity 9 9. 9%, PD selectivity 0 1%. Example 4 7 (-phosphate ester T i catalyst _{ZA C ZH O sZ C s 2} C 0 3)

Glass-made O over Tok equipped with the safety valve of the pressure-resistant 1 0 kgf / cm ² 0.96 g of compound-1 and 0.96 g of cesium carbonate in a reave.

293 g were added, and about 1.0% of a 34% aqueous hydrogen peroxide solution and 14.lg of AC purified by distillation were added thereto, and the autoclave was sealed. This was placed in a water bath at 10 ° C., and a stirring reaction was performed for 6 hours in a light-shielded state. After the reaction, the reaction was carried out analysis in the same manner as in Example 4 1, AC response rate _{2 3. 0%, H 2 0} 2 reaction rate 4 7. 5%, EP selectivity 1 0 0%, PD selectivity 0 %. Example 4 8 (-phosphate ester T i catalysts Z 1 - xenon emission / H ₂ 0 ₂ to)

To withstand 1 0 kg ΐ / cm glass O one preparative click Leeb with ^two safety valves, a compound one 1 put 0. 9 3 g, which approximately 3 to 4% hydrogen peroxide aqueous 1 0. 6 g and distilled 15.2 g of 1-hexene purified by the above procedure was added, and the autoclave was sealed. This was placed in a water bath at 20 ° C., and a stirring reaction was performed in a light-shielded state for 4 hours. After the reaction, a reaction analysis was carried out in the same manner as in Example 41. 1—Hexane reaction rate 4.6%, H ₂ O ₂ reaction rate 25.6.1% 1—Hexoxide selectivity 6 1 9%, 1; 2—Hexanediol selectivity

36.8% was obtained. EXAMPLE 4 9 (-phosphate ester T i catalysts Z 1 - xenon emission _{_{2 0 2 / M g C 0}} 3 to)

A glass-made O one preparative click slave having a safety valve of the pressure 1 0 kgf / cm ^2, the compound one 1 0. 9 5 g and basic carbonate magnesite Shiumu _{(4 M g CO 3 · M} g (OH) 2 · 0.1 lg of 5 H ₂ O), add about 18.4 lg of about 34% aqueous hydrogen peroxide and 15.5-lg of 1-hexene purified by distillation, and seal the autoclave. did. Place this in a 20 ° C water bath and The reaction was stirred for an hour. After the reaction, a reaction analysis was conducted in the same manner as in Example 41, and the reaction rate of 1-hexene was 49.4%, the reaction rate of H ₂ O ₂ was 53.2%, and the selectivity of 1-hexenoxide was 1 98.4% and 1,2-hexanediol selectivity of 1.2% were obtained. Example 5 0 (-phosphate ester T i catalysts Z meta Li torque Rorai Dono H ₂ 0 ₂₎

A glass-made O one preparative click slave having a safety valve of the pressure 1 O kgf / cm ^2, the compound one 1 0. 9 5 g and basic carbonate magnesite Shiumu _{(4 M g C 0 3 *} M g (OH) 2 -5H20) 0.12 g, and add about 34% hydrogen peroxide solution (18.0 g) and purified by distillation to 2-methyl-3-propene propene (metaryl chloride) (Hereinafter abbreviated as “MAC”). 16.2 g was added, and the autoclave was sealed. This was placed in a water bath at 20 ° C., and a stirring reaction was performed for 4 hours in a light-shielded state. After reaction, the reaction analyzed in the same manner as in Example 4 1, MA C the reaction rate _{8 3. 0%, H 2 0} 2 reaction応率8 4.9%, meta Riruku Rorai, Dokishi de selectivity 9 8 .7%, selectivity for 1,2-metyl chloridediol was 0.9%. Example 5 1 (phosphate ester Ti catalyst / MA CZ t—Bu 0 OH)

A glass-made Auto click slave having a breakdown voltage 1 0 kgf / cm ² of the safety valve, the compound one 1 put 0, 9 4 g, be referred to as the approximately 6 0% t one Puchiruhai Doropaokishi de (hereinafter "TBHP" 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. After the reaction, a reaction analysis was carried out in the same manner as in Example 41, to obtain a MAC conversion of 4.0%, a TBHP conversion of 17.6%, and a selectivity for metal chloride of 50.1%. Was. Example 52 (phosphoric acid ester Ti catalyst MA CZ t — Bu 0 HZM g C 0 ₃ )

A glass-made O over Toku Leeb having a safety valve of the pressure 1 0 kgf / cm ^2, compound - 1 to 0. 9 4 g and basic carbonate magnesite Shiumu (4 3 Ji 0 ₃ * (011) ₂ * 5 11 ₂ 0) was added to 0.11 g, 27.0 g of a decane solution of about 60% -TBHP and 16.lg of purified MAC were added thereto, and the autoclave was sealed. This was placed in a 100 ° C. oil bath, and a stirring reaction was performed for 6 hours in a light-shielded state. After the reaction, a reaction analysis was carried out in the same manner as in Example 41, and a MAC reaction rate of 12.8%, a TBHP reaction rate of 39.9%, and a selectivity of methacryloyl chloride of 27.8% were obtained. . Example 5 3 (-phosphate ester T i catalyst ZA CZH _₂ 0 ₂₎

The breakdown voltage l O kgf Z cm glass O one Toku slave with a ^second safety valve, a compound one 1 put 0. 4 7 g, which in the consequent Roeki San 7. 6 g, about 3 4% peroxide 5.2 g of hydrogen water and 7.0 g of AC purified by distillation were added, and the autoclave was closed. This was placed in a water bath at 30 ° C., and a stirring reaction was performed for 4 hours in a light-shielded state. After reaction, the reaction analyzed in the same manner as in Example 4 1, AC response rate _{2 0. 6%, H 2 0} 2 reaction rate 5 7. 3% EP selectivity 9 8.0%,? A selectivity of 1.6% was obtained. Example 5 4 (-phosphate ester T i Catalyst A CZH _₂ 0 ₂₎

Three The breakdown voltage l O kgf Bruno cm ² of having a safety valve glass-made O Toku Leeb, compound - 1 placed 0. 94 g, this 2, 3, 4-te tractor Roroeta down the 3 0. lg, about 3 4 10.6 g of an aqueous solution of hydrogen peroxide and 13.9 g of AC purified by distillation were added, and the autoclave was sealed. This was placed in a water bath at 10 ° C., and a stirring reaction was performed for 6 hours in a light-shielded state. After reaction, the reaction analyzed in the same manner as in Example 4 1, AC response rate _{2 0. 7%, H 2 0} 2 reaction rate 3 8. 1%, EP selectivity 9 9. 8%, PD selectivity 0.2% was obtained. -Example 55 (Carboxylic acid Ti catalyst ZA

The breakdown voltage l O kgf Z cm ² of glass made O Toku slave with a safety valve, a compound one 9 2. Insert 6 0 g, this approximately 3 to 4% hydrogen peroxide water 1 1. 1 g, 2 8% 0.777 g of ammonia water and 13.9 g of AC purified by distillation were added, and the autoclave was sealed. This was placed in a water bath at 50 ° C., and a stirring reaction was performed for 2 hours in a light-shielded state. After the reaction. Conducting a reaction analyzed in the same manner as in Example 4 1, AC response rates 1. 9%, H ₂ 0 ₂ reaction rate 5 7. 4%, EP selectivity 9 6. 7%, PD selectivity 2 7%. Example 5 6 (acid T i catalysts ZAC ZH _₂ 0 ₂₎

To withstand 1 0 kgf / cm ² in with a safety valve glass-made O over Toku Loew, compound one 3 4 0. 3 3 g were charged, about 3 4% aqueous hydrogen peroxide thereto 8. By 2 g and distilled 10.9 g of purified AC was added, and the autoclave was sealed. This was placed in a water bath at 50 ° C., and a stirring reaction was performed for 2 hours in a light-shielded state. After reaction, the reaction analyzed in the same manner as in Example 4 1, was obtained AC reaction rate 0. 1% H ₂ 0 ₂ reaction of 3 0.3%, the 0% EP selectivity 1 0. Examples 5 7 to 5 8

Compound 40, which is a titanium salt of phosphoric acid monoester, and compound 3, which is a titanium salt of phosphoric acid diester, were reacted in the same manner as in Example 41 under the conditions shown in Table 1. was carried out, AC reaction rate, H ₂ 0 ₂ reaction rates, to give the EP selectivity. Table 1 shows the obtained results.

Industrial applicability

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.

Claims

Claims General formula [I]

[In the formula, 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. ]

A titanium salt of a phosphoric acid diester represented by the formula:

2. General formula [IV]

OR ¹

0 = P—OH [IV]

OR ²

[In the formula, 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. ]

The phosphoric acid diester titano-¾mo according to claim 1, which is obtained by reacting a phosphoric acid diester represented by the following formula with a titanium compound.

3 General formula [IX]

[IX] [wherein, R ¹ is a hydrocarbon group having 30 carbon atoms which may contain a hetero element, and n is an integer of 1 or 2. Salt.

4. General formula [X]

0:: P—— 0H

0H

[X]

[Wherein, R ¹ is a hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero element. ]

The phosphoric acid monoester titanate salt according to claim 3, which is obtained by reacting a phosphoric acid monoester represented by the following formula with a titanium compound.

5 General formula [Π]

[In the formula, 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 from 1 to 4. ]

A carboxylic acid titanate represented by the formula:

6.

General formula [V]

Three

R-I C-0H [V]

II

0

[Wherein, R ³ is a hydrocarbon group having 1 to 3 ′ 0 carbon atoms, and may include a hetero element. However, R ³ does not contain a hydroxy group. ]

The carboxylic acid titanium salt according to claim 5, which is obtained by reacting a carboxylic acid represented by the following formula with a titanium compound.

7. —General formula [III]

[In the formula, 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. ] The sulfonic acid titanium salt represented by these.

8. —General formula [VI]

R Η [VI]

O OSHMM [wherein, R ⁴ is a hydrocarbon group having 1 to 30 carbon atoms, and may contain a hetero element. ]

The sulfonic acid titanate salt according to claim 7, which is obtained by reacting a sulfonic acid represented by the following formula with a titanium compound.

9. The method according to claim 2, 4, 6 or 8, wherein the titanium compound is at least one selected from the group consisting of titanium alkoxides, titanium acetates, titanium alkoxyacetates and titanium chloride. Titanium salt.

10. The titanium salt of a phosphoric acid diester according to claim 1 or 2, the titanium salt of a phosphoric acid monoester according to claim 3 or 4, and the titanium salt of a carboxylic acid according to claim 5 or 6. 9. The sulfonic acid according to claim 7 or 8, wherein the sulfonic acid is a titanium salt of sulfonic acid. A method for producing epoxide to be oxidized. General formula [π]

[Wherein, R ³ is a hydrocarbon group having 1 to 30 carbon atoms including a hydroxy group. n is an integer of 1 to 4. ]

A method for producing an epoxide, wherein olefin is epoxidized with peroxide using a carboxylic acid titanium salt represented by the formula (1) as a catalyst.

1 2. The peroxide is at least one selected from the group consisting of hydrogen peroxide, which may be in solution, tertiary butyl hydroperoxide, ethylbenzen hydroperoxide, and cumene hydroperoxide. 10. The method for producing the epoxide according to 10 or 11.

13. The process for producing an epoxide according to claim 12, wherein the peroxide is produced in the reaction system. , '

1 4. 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 is present in the reaction system. The method for producing an epoxide according to any one of 0 to 13.

15. The method for producing an epoxide according to claim 14, wherein the metal element and Z or ammonia are in the form of hydroxide, Z or carbonate.

1 6. The process for producing an epoxide according to claim 14 or 15, wherein the metal element is Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba or La. .