CN100500291C - Carrier Supported Composite Catalysts Containing Transition Metals - Google Patents

Abstract

The invention discloses a transition metal-containing composite catalyst supported by a carrier. The composite catalyst consists of component A and component B, wherein component A is represented by the following general formula: ¢-[(R ₁ ) _n0 -( OCH ₂ OCH ₂ ) _n1 -YR ₂ R ₃ R ₄ ] _m1 (Q ₁ ) _m2 X _n2 D, component B is a salt, the mass ratio of component A to component B is 1 to 100:1, the present invention The catalyst has high catalytic activity, and the structure of component A is stable and can be completely and conveniently recovered and recycled without polluting the product.

Description

Carrier Supported Composite Catalysts Containing Transition Metals

technical field

The invention relates to a carrier-supported composite catalyst, in particular to a carrier-supported composite catalyst containing transition metals.

Background technique

The effective recovery and utilization of catalysts is the focus of modern catalytic reaction research. Heteropolyacid quaternary ammonium salts are currently highly active catalysts for catalyzing the oxidation of olefins by hydrogen peroxide to prepare epoxides. This type of catalyst has good selectivity and high conversion rate, but it is difficult to obtain Separation, recovery and reuse in the reaction system, expensive catalysts cannot be effectively recovered, on the one hand will cause pollution to the product, on the other hand will cause increased production costs, making the process difficult to industrialize. The Chinese patent No. CN1401640 discloses a reaction-controlled phase transfer catalyst. The catalyst itself is a solid. Under the action of the oxidant in the reaction medium, it dissolves in the reaction system and participates in the reaction in a homogeneous phase. When the oxidant is consumed, the catalyst recovers. To the form of solid, can reclaim more conveniently, but this method all has very harsh requirement to the selection of the solvent in the reaction system and the selection of the quaternary ammonium salt in the catalyst structure corresponding to it, limits its range of application, and after the reaction finishes The catalyst can only be partially recovered, and the primary recovery rate is about 70%. The Chinese patent No. CN1765502A discloses a catalyst for oxidation reaction and its application in oxidation reaction. In this method, under the action of the reactant oxidant, the active component of the catalyst is separated from the carrier and enters the reaction medium to form Active species, so as to carry out homogeneous catalytic oxidation reaction. When the reaction ends and the oxidant is consumed, the catalyst active components in the reaction medium are combined with the carrier to form the original supported catalyst, but the supported catalyst itself has the problem of loss of catalyst active components. , this kind of reversible loading method inevitably also has this phenomenon. In the above two reactions, the catalyst can only be recovered when the oxygen source such as hydrogen peroxide and alkyl hydroperoxide is completely consumed. Therefore, in the selection of reaction conditions, in order to completely consume the oxygen source, it is necessary to add an excessive amount of substrate. In addition, because the reversible loading catalyst is also based on the principle of reaction-controlled phase transfer catalysis, in order to realize the reversible loading of the catalyst, only specific solvents and specific quaternary ammonium salt structure catalysts can be used in this catalytic system, and the catalytic systems used in the above catalysts are all It contains a large amount of solvents, and the use of a large amount of volatile, toxic and harmful solvents does not meet the requirements of green chemistry, and also increases the production cost in production.

Contents of the invention

The purpose of the present invention is to provide a transition metal-containing composite catalyst supported by a carrier with high catalytic activity, complete and convenient recovery and recycling of active components of the catalyst, and no pollution to products.

The present invention adopts the following technical solutions to achieve the above object: a carrier supports a transition metal-containing composite catalyst, the composite catalyst is composed of A component and B component, wherein A component is represented by the following general formula compound:

￠-[(R ₁ ) _n0 -(OCH ₂ OCH ₂ ) _n1 -YR ₂ R ₂ R ₄ ] _m1 (Q ₁ ) _m2 X _n2 D

Among them, ¢ in the general formula is the carrier;

或

其中R₅、R₆各自独立是甲氧基、乙氧基或Cl，R₇为—CH₂—、—CH₂CH₂—或—CH₂CH₂CH₂—，n₄＝0或1；R1 is

or

Wherein R ₅ and R ₆ are each independently methoxy, ethoxy or Cl, R ₇ is -CH ₂ -, -CH ₂ CH ₂ - or -CH ₂ CH ₂ CH ₂ -, n ₄ =0 or 1;

Y is N or P atom;

R ₂ , R ₃ , and R ₄ are independently C ₁ -C ₂₂ alkyl, cycloalkyl, benzyl, phenyl or substituted phenyl;

R ₂ , R ₃ , R ₄ are preferably each independently C ₁ -C ₂₂ alkyl, benzyl or phenyl;

Q ₁ is expressed as R ₈ R ₉ R ₁₀ R ₁₁ Y ₂ ⁺ or an alkyl pyridinium quaternary ammonium salt cation, wherein R ₈ , R ₉ , R ₁₀ , and R ₁₁ are independently C ₁ -C ₂₂ alkyl, ring Alkyl, benzyl, phenyl or substituted phenyl; R ₈ , R ₉ , R ₁₀ , R ₁₁ are preferably independently C ₁ -C ₂₂ alkyl, benzyl or phenyl; Y ₂ is N or P atom ;

X is H, Na, K, NH ₄ or Ca;

D is heteropolyacid, isopolyacid or hypervalent metal oxyacid, wherein heteropolyacid is represented by A _a B _c O _4a+3c , isopolyacid is represented by B _c O _4c-r , and A is P, Si or As atom; B is W, Mo or V atom, O is oxygen atom; A is preferably P or Si atom; B is preferably W or Mo atom;

The hypervalent metal oxyacid radical is a hypervalent metal acid radical of W, Mo or V; preferably WO ₄ ^2- or MoO ₄ ^2- ;

n ₀ =0 or 1, n ₁ =0-15, m ₁ =1-2, m ₂ =0-7, n ₂ =0-7, a=1-2, c=1-18, r=0 -6;

Wherein preferred a=1, c=1-12,

A component is again preferably the following general formula compound:

或

or

Among them, PS represents polystyrene resin skeleton, PVC represents polyvinyl chloride resin skeleton, Wang represents Wang resin skeleton, PN represents polyaniline resin skeleton, and CI represents inorganic carrier skeleton;

Y is N or P atom;

R ₂ , R ₃ , and R ₄ are each independently C ₁ -C ₂₂ alkyl, benzyl or phenyl;

wherein R ₅ and R ₆ are each independently methoxy, ethoxy or Cl, and R ₇ is —CH ₂ —, —CH ₂ CH ₂ — or —CH ₂ CH ₂ CH ₂ —;

Q ₁ is represented by R ₈ R ₉ R ₁₀ R ₁₁ Y ₂ ⁺ or alkyl pyridinium quaternary ammonium salt cation, wherein R ₈ , R ₉ , R ₁₀ , and R ₁₁ are each independently C ₁ -C ₂₂ alkyl, benzyl Base or phenyl, Y ₂ is N or P atom;

X is H, Na, K, NH ₄ or Ca;

D is a heteropolyacid radical, an isopolyacid radical or a transition metal hypervalent oxyacid radical;

Among them, the heteropoly acid radical is represented by A _a B _c O _4a+3c , and the isopoly acid radical can be expressed as B _c O _4c-r , A is a P or Si atom; B is a W or Mo atom, and O is an oxygen atom;

High-valent metal oxyacids are WO ₄ ^2- or MoO ₄ ^2- ;

n ₀ =0 or 1, n ₁ =0-15, m ₁ =1-2, m ₂ =0-7, n ₂ =0-7, a=1, c=1-12, r=0-6 .

The A component is most preferably represented by a compound of the general formula:

or

Among them, PS means polystyrene resin skeleton, PVC means polyvinyl chloride resin skeleton, Wang means Wang resin skeleton, PN means polyaniline resin skeleton, CI means inorganic carrier;

R ₂ and R ₃ are most preferably independently methyl;

R ₄ is most preferably C ₁₀ -C ₁₈ linear alkyl or benzyl;

wherein R ₅ and R ₆ are each independently methoxy, ethoxy or Cl, and R ₇ is —CH ₂ —, —CH ₂ CH ₂ — or —CH ₂ CH ₂ CH ₂ —;

Q ₁ is represented by R ₈ R ₉ R ₁₀ R ₁₁ Y ₂ ⁺ or an alkyl pyridinium quaternary ammonium salt cation, wherein R ₈ , R ₉ , R ₁₀ , and R ₁₁ are most preferably independently C ₁ -C ₂₂ alkyl groups , benzyl or phenyl, Y ₂ is N or P atom;

X is H or Na, K, NH ₄ or Ca;

n ₁ =0-10, m ₁ =1-2, m ₂ =0-2, n ₂ =0-2, p=1-12;

Group B is salt.

The B component is preferably Na salt, K salt, Ca salt, Mg salt, NH ₄ salt or any mixture of the above salts.

The B component is preferably HCO ₃ , CO ₃ , halogen, SO ₄ , HSO ₄ , PO ₄ , HPO ₄ , H ₂ PO ₄ , CH ₃ COO, HCOO, acid ion of benzoic acid and Na, K, Ca, Salt formed by Mg, NH ₄ ions or any mixture of the above salts.

Component B is most preferably a salt formed by HCO ₃ , halogen, SO ₄ , HSO ₄ acid ions and Na, K, Ca, NH ₄ ions or any mixture of the above salts.

The mass ratio of component A to component B is 1-100:1.

The mass ratio of component A to component B is most preferably 50˜1:1.

The carrier ¢ is an organic material containing halogen atoms, quaternary ammonium salts or quaternary phosphonium salts or an inorganic material containing active hydroxyl groups, halogen atoms, quaternary ammonium salts or quaternary phosphonium salts.

Organic materials are preferably polystyrene polymer modified materials, polyvinyl chloride modified resins, Wang resin modified resins or polyaniline modified resins; inorganic carriers are preferably silica gel containing halogen atoms, quaternary ammonium salts or quaternary phosphonium salts , titanium dioxide containing halogen atoms, quaternary ammonium salts or quaternary phosphonium salts, molecular sieves containing halogen atoms, quaternary ammonium salts or quaternary phosphonium salts, diatomaceous earth containing halogen atoms, quaternary ammonium salts or quaternary phosphonium salts, containing halogen atoms, quaternary phosphonium salts, Aluminum oxide of ammonium salt or quaternary phosphonium salt or silicon aluminum hydrated solid material containing halogen atoms, quaternary ammonium salt or quaternary phosphonium salt.

The preparation method of the carrier-supported composite catalyst containing transition metal comprises the following steps: (1), quaternization or quaternary phosphonium treatment of the carrier; (2), the carrier is swollen with a solvent, and the active component contains a transition metal-containing heteropolyacid , isopolyacids, high-valent oxyacids or their salts are added to the swollen carrier, reacted at 10-80°C for 6-14 hours, filtered, washed, and dried to directly obtain the carrier-supported transition metal-containing composite catalyst A Components, or use weakly basic salts, quaternary ammonium salts or quaternary phosphonium salt solutions to process and dry the supported phase transfer multi-acid composite catalyst A component; (3), A component and B component according to the above ratio Mixed to obtain a composite catalyst.

The preparation method of composite catalyst is specifically the following steps:

1. Quaternary ammonium (phosphonium) treatment of the carrier

The quaternary ammonium (phosphonium) treatment of the carrier is a prior art, and the treatment method is briefly described below:

1. The treatment process of polystyrene resin (PS) is:

(1) For polystyrene resin: polystyrene resin reacts with chloromethyl ether for chloromethylation reaction, then reacts with chloroethanol to introduce (OCH ₂ CH ₂ ) _n1 (called interarm), and then reacts with tertiary Amine (triphenylphosphine or derivatives thereof) undergoes a quaternary ammonium (phosphonium) reaction to obtain a quaternary ammonium (phosphonium) resin;

(2), p-chloromethylation resin: chloromethylation resin reacts with chloroethanol to introduce interarm, reacts with tertiary amine (or triphenylphosphine or its derivatives) to carry out quaternary ammonium (phosphonium) conversion to obtain quaternary ammonium ( Phosphonium) resin;

(3) For the quaternized ammonium (phosphonium) resin, it can be directly used to support the active components.

2. The treatment process of polyvinyl chloride resin (PVC) is: PVC reacts with chloroethanol to introduce (OCH ₂ CH ₂ ) _n1 (called interarm), and then reacts with tertiary amine (or triphenylphosphine or its derivatives) Quaternary ammonium (phosphonium) reaction to obtain quaternary ammonium (phosphonium) resin; or direct quaternization of PVC and tertiary amine (or triphenylphosphine or its derivatives) to obtain quaternary ammonium (phosphonium) resin;

3. The treatment process of Wang resin is as follows: Wang resin reacts with thionyl chloride to introduce active benzyl chloride, then reacts with chloroethanol to introduce interarm (OCH ₂ CH ₂ ) _n , and reacts with tertiary amine (or triphenylphosphine or its derivatives) quaternary ammonium (phosphonium) reaction to obtain quaternary ammonium (phosphonium) resin; or Wang resin reacts with thionyl chloride to introduce active benzyl chloride and directly reacts with tertiary amine (or triphenylphosphine or its derivatives) Quaternary ammonium (phosphonium) to give quaternary ammonium (phosphonium) resin.

4. The treatment process of benzylamine resin is as follows: the benzylamine resin is swollen with solvent, amine methylated with formaldehyde to obtain tertiary aminated resin, and then reacted with chloroalkane for quaternization.

中，R₂、R₃、R₄各自独立为C₁-C₂₂的烷基、苄基、苯基或者取代苯基，Y是N或P原子；Tertiary amine or triphenylphosphine and its derivatives for carrier quaternization

wherein, R ₂ , R ₃ , and R ₄ are independently C ₁ -C ₂₂ alkyl, benzyl, phenyl or substituted phenyl, and Y is an N or P atom;

5. Treatment of inorganic carrier:

For the modification of inorganic carriers containing active hydroxyl groups: use chlorosiloxane as a coupling agent to chemically bond and introduce active chlorine atoms or react with thionyl chloride to introduce active chlorine atoms, then introduce interarms, and then combine with tertiary amines ( Triphenylphosphine or its derivatives) react with quaternary ammonium (phosphonium) to obtain quaternary ammonium (phosphorus) inorganic carrier; another method is to use aminosiloxane as coupling agent to carry out chemical bonding to introduce active amine, and then carry out Tertiary amination, and then react with chloroalkane for quaternization to obtain a quaternary ammonium inorganic carrier;

表示，M为Cl或NH₂，R₅、R₆、R₁₂各自独立为甲氧基、乙氧基或Cl；R₇为—CH₂—、—CH₂CH₂—或—CH₂CH₂CH₂—，n₄＝0或1，硅氧烷偶联剂优选3-氯丙基-三乙氧基硅烷、3-氯丙基-三甲氧基硅烷、等3-胺丙基-三乙氧基硅烷、3-胺丙基-三甲氧基硅烷或二氯二甲基硅烷。The modified siloxane coupling agent consists of

Indicates that M is Cl or NH ₂ , R ₅ , R ₆ , and R ₁₂ are each independently methoxy, ethoxy or Cl; R ₇ is —CH ₂ —, —CH ₂ CH ₂ — or —CH ₂ CH ₂ CH ₂ —, n ₄ =0 or 1, the siloxane coupling agent is preferably 3-chloropropyl-triethoxysilane, 3-chloropropyl-trimethoxysilane, etc. 3-aminopropyl-triethyl oxysilane, 3-aminopropyl-trimethoxysilane or dichlorodimethylsilane.

2. Support of active components

Swell the modified carrier with an alcohol solvent, add transition metal-containing heteropolyacids, isopolyacids, high-valent metal oxyacids or their salts and react at 10-80°C for 6-14 hours to obtain carrier support Phase-transfer heteropolyacids, isopolyacids or hypervalent metal oxoacids.

The alcohol solvent is preferably ethanol or a mixed solution of ethanol and water.

3. Catalyst post-treatment

The active components of the above-prepared catalysts are ion-exchanged with dilute solutions of weakly basic salts, quaternary ammonium salts or quaternary phosphonium salts to treat part or all of the unreacted hydrogen in the phosphotungstic acid in the catalyst, and then dried to obtain A component.

The weakly basic salts used to treat catalysts are NaHCO ₃ , Na ₂ CO ₃ , NH ₄ HCO ₃ , (NH ₄ ) ₂ CO ₃ , KCO ₃ or KHCO ₃ , with a concentration of 0.5%-10% by mass; Ammonium salt or quaternary phosphonium salt is R ₈ R ₉ R ₁₀ R ₁₁ Y ₂ Cl, wherein R ₈ , R ₉ , R ₁₀ , and R ₁₁ are each independently C ₁ -C ₂₂ alkyl, benzylphenyl or substituted benzene base, _Y2 represents N or P, and the mass percentage concentration is 0.5%-10%.

4. Combination of catalysts

The above-prepared component A and component B salts are mixed according to the proportions in the above technical scheme to obtain a carrier-supported composite catalyst containing transition metals. But it is also possible to add component A and component B respectively according to the above ratio during the reaction.

The carrier-supported transition metal-containing composite catalyst of the present invention includes two components A and B. The two components act synergistically, and the catalytic activity of the catalyst is high. Salt or high-valent metal oxo acid salt is the active component of the catalyst, and this part of the catalyst can be recovered conveniently; component B is a cheap salt, which improves the activity and selectivity of the catalyst, and component A is used alone It has certain catalytic activity and selectivity, but the catalytic activity is low and the selectivity is also poor, while component B alone has no activity at all. The component A and component B of the composite catalyst are interdependent and indispensable . Component A of the composite catalyst of the present invention is to branch the active component of the catalyst on the carrier through chemical bonding, the catalyst structure is stable, the catalyst active component is not easy to fall off, and the active component does not break away from the catalyst carrier during the reaction; It is carried out in the micropores of the catalyst, so the active components of the catalyst do not enter the reaction organic phase, do not pollute the product, and the recovery is very convenient. It can be used for re-reaction only after the reaction is completed, and other steps such as centrifugation can be omitted. , the separation of the catalyst will not cause loss of active components when the hydrogen peroxide is not fully reacted, so it can avoid adding a large amount of substrate olefins in order to complete the reaction of hydrogen peroxide, and can be separated when needed, which can be convenient In-situ characterization of the catalyst is achieved. The composite catalyst also has quite high stability, and the active component (A component) can still maintain activity and selectivity after being reused 15 times. The active component (A component) not only has the function of catalyzing hydrogen peroxide oxidation of olefins, It also has the function of phase transfer, and can also conveniently regulate its acidity and alkalinity. The composite catalyst of the present invention can not only be used in the reaction of preparing epoxides by the solvent-free method of hydrogen peroxide oxidizing olefins, and realize the greening of epoxides preparation, but also can be used in a wide range of It is used in the reaction of preparing α, α'-diol, the reaction of oxidizing olefin to prepare carboxylic acid or diacid, etc.

Nicolet 10 DX-FTIR infrared spectrometer was used for infrared spectrum analysis, with a spectral range of 4000-400 cm ^-1 and a resolution of 0.5-4 cm ^-1 , and KBr was used for tableting.

Detailed ways

1. Preparation of active component phosphotungstic heteropolyacid or isopolytungstic acid:

Embodiment 1, the preparation of peroxyphosphotungstic acid

Weigh 3.3g of sodium tungstate, dissolve it in 30mL of water, add 30mL of 6mol/L hydrochloric acid dropwise, filter with suction, wash with distilled water, dissolve the obtained solid in 30mL of 27.5% hydrogen peroxide, add 0.29g of 85% H ₃ PO ₄ , and then Add 40mL of water to dilute to obtain peroxyphosphotungstic acid.

Embodiment 2, the preparation of peroxypolytungstic acid

Weigh 3.3g of potassium tungstate, dissolve it in 20mL of water, add 30mL of 5mol/L hydrochloric acid dropwise, filter with suction, wash with distilled water, and dissolve the obtained solid in 30mL of 30% hydrogen peroxide to obtain peroxytungstic acid.

2. Preparation of component A:

Example 3, preparation of chloromethylated polystyrene resin supported N,N-dimethyloctadecylammonium phosphotungstic heteropolyacid

Place 4 g of dry chloromethylated polystyrene divinylbenzene cross-linked resin (chlorine balls for short, the same below) in a three-necked flask, and swell overnight with a mixed solvent of 50 mL 1,2-dichloroethane and 20 mL ethanol. n(Cl):n(tertiary amine)=1:3 Add N,N-dimethyloctadecylamine, reflux reaction for 12h, filter with suction, wash, dry in the air, extract for 12h, vacuum dry at room temperature to constant weight . N,N-dimethyloctadecylammonium supported on light yellow chloromethylated polystyrene can be obtained, and the infrared spectrum results are as follows: 2924cm ^-1 (CH antisymmetric stretching vibration peak of CH ₂ ), 2853cm ^-1 (CH symmetric stretching vibration peak of CH ₂ ), 3024cm ^-1 (υ(-CH ₃ ) stretching vibration absorption), 1376cm ^-1 (δ(-CH ₃ ) bending vibration), 670cm ^-1 (C-Cl bond absorption peak ) and 1268cm ^-1 (the characteristic absorption peak of benzyl CH) almost disappear, indicating that there is almost no -CH ₂ Cl structure in the structure, and υ(CN) at 1117cm ^-1 further indicates that the quaternization has been completed.

Add chloromethylated polystyrene-supported N,N-dimethyloctadecylammonium to 50mL absolute ethanol as the swelling agent to swell overnight, adding according to n(N):n(P):n(W)= 1:1:4 peroxyphosphotungstic acid, react at room temperature for 12 hours, filter with suction, wash with water, and dry to obtain light yellow-green chloromethylated polystyrene supported N,N-dimethyloctadecyl Ammonium Phosphotungstic Heteropoly Acid. The infrared spectrum results are as follows: 2922cm ^-1 , 2851cm ^-1 , 3025cm ^-1 , 1377cm ^-1 , 1079cm ^-1 (υ(PO) vibration of PO ₄ ^3- ), 940cm ^-1 (belonging to υ(W=O)), 883cm ^-1 (υ(W-Ob-W)(common angle)), 811cm ^-1 (υ(W-Oc-W)(common side)).

Example 4, preparation of chloromethylated polystyrene resin supported polyethylene glycol N, N-dimethyl dodecyl ammonium phosphotungstic heteropolyacid

3g of chloromethylated macroporous polystyrene resin was placed in a three-necked flask, and 30mL of toluene was added to swell overnight. Add 70mL of 2-chloroethanol, an appropriate amount of anhydrous K ₂ CO ₃ and a quaternary ammonium salt catalyst, then add 20mL of toluene, control the temperature at 90°C, and react for 14h. After vacuum filtration, washing and drying, PS-(OCH ₂ CH ₂ ) ₁₅ Cl can be obtained. Put the dry PS-(OCH ₂ CH ₂ ) ₁₅ Cl 4g in a three-necked flask, and swell with a mixed solvent of 50mL 1,2-dichloroethane and 20mL ethanol overnight, according to n(Cl):n(tertiary amine )=1:3 Add N,N-dimethyldodecylamine, reflux for 12 hours, filter with suction, wash, dry in the air, and extract for 12 hours. Dry under vacuum at room temperature to constant weight. N, N-polyethylene glycol dimethyl dodecyl ammonium supported by light yellow chloromethylated polystyrene can be obtained. Swell the above resin overnight with 50mL absolute ethanol as swelling agent, add peroxyphosphotungstic acid according to n(N):n(P):n(W)=1:1:4, react at room temperature for 12h, pump Filter, wash with water, and dry to obtain light yellow-green chloromethylated polystyrene-supported N,N-polyethylene glycol dimethyl dodecyl ammonium phosphotungstic heteropolyacid.

Example 5, preparation of chloromethylated polystyrene resin supported N,N-dimethyltetradecammonium phosphotungstic heteropolyacid

Place 4g of dry chlorine balls in a three-necked flask, swell overnight with a mixed solvent of 40mL 1,2-dichloroethane and 30mL ethanol, and add N,N- Dimethyltetradecylamine, after reflux reaction for 12 hours, suction filtered, washed, and dried in the air. Extraction 12h. Dry in vacuo to constant weight. N,N-dimethyltetradecyl ammonium supported by light yellow chloromethylated polystyrene can be obtained. The infrared spectrum results are as follows: 2923cm ^-1 , 2852cm ^-1 , 3026cm ^-1 , 1374cm ^-1 , 1119cm ^-1 . Add chloromethylated polystyrene-supported N,N-dimethyltetradecylammonium to 50mL absolute ethanol as the swelling agent to swell overnight, adding according to n(N):n(P):n(W)= 1:2:10 phosphotungstic acid peroxide, react at room temperature for 12 hours, filter with suction, wash with water, and dry to obtain N,N-dimethyltetradecylammonium phosphotungsten supported on chloromethylated polystyrene Heteropoly acid quaternary ammonium salt catalyst. The infrared spectrum data are as follows: 2921cm ^-1 , 2854cm ^-1 , 3027cm ^-1 , 1376cm ^-1 , 1077cm ^-1 , 943cm ^-1 , 885cm ^-1 , 814cm ^-1 .

Example 6, Preparation of Triphenylphosphopolytungstic Acid Supported by Chloromethylated Polystyrene Resin

Put 4 g of dry chlorine balls in a three-necked flask, swell overnight with a mixed solvent of 40 mL 1,2-dichloroethane and 30 mL ethanol, and add triphenyl Phosphorus, after reflux reaction for 12h, filter with suction, wash and dry in air. Extract for 12 hours, and vacuum dry to constant weight to obtain chloromethylated polystyrene supported triphenyl quaternary phosphonium salt. The above-mentioned chloromethylated polystyrene supported triphenyl quaternary phosphonium salt was added to 50mL of absolute ethanol as a swelling agent to swell overnight, and peroxypolytungstic acid was added according to n(P):n(W)=1:2, After reacting at room temperature for 12 hours, filter with suction, wash with water, and dry to obtain triphenyl quaternary phosphonium salt polytungstic acid supported by chloromethylated polystyrene.

Example 7, preparation of chloromethylated polystyrene resin supported N,N-dimethylbenzyl ammonium phosphotungstic heteropolyacid

Put 4 g of dry chlorine balls in a three-necked flask, swell overnight with a mixed solvent of 20 mL 1,2-dichloroethane and 50 mL ethanol, according to n(Cl):n(tertiary amine)=1:2.5 N,N-di Methylbenzylamine, after 12 hours of reflux reaction, suction filtration, washing, drying, extraction for 12 hours, vacuum drying at room temperature to constant weight to obtain chloromethylated polystyrene resin supported N,N-dimethylbenzyl Ammonium. Add 50mL of absolute ethanol to chloromethylated polystyrene resin supported N,N-dimethylbenzyl ammonium as swelling agent to swell overnight, add according to n(N):n(P):n(W)=1 : 3:12 peroxyphosphotungstic acid, after reacting at 80°C for 6 hours, suction filtration, washing with water, treatment with 0.5% NaHCO ₃ , and vacuum drying to obtain light brown chloromethylated polystyrene resin supported N,N-di Methylbenzylammonium Phosphotungstic Heteropoly Acid.

Example 8, Preparation of polyvinyl chloride resin supported N,N-dimethylbenzyl ammonium phosphotungstic heteropoly acid

Put 4 g of dry polyvinyl chloride resin in a three-necked flask, swell overnight with a mixed solvent of 40 mL 1,2-dichloroethane and 40 mL ethanol, add N according to n(Cl):n(tertiary amine)=1:1.5, N-dimethylbenzylamine, after 12 hours of reflux reaction, suction filtration, washing, air drying, extraction for 12 hours, vacuum drying at room temperature to constant weight. N, N-dimethyl benzyl ammonium chloride supported by polyvinyl chloride can be obtained. Add 50mL absolute ethanol to the above resin to swell overnight as a swelling agent, add phosphotungstic heteropoly acid H ₃ PW ₁₂ O ₄₀ aqueous solution according to n(N):n(H ₃ PW ₁₂ O ₄₀ )=1:1, 60°C After reacting for 8 hours, filter with suction, wash with water, dry, and treat with 5% NH ₄ HCO ₃ aqueous solution to obtain polyvinyl chloride-supported N,N-dimethylbenzylammonium phosphotungstic heteropolyacid.

Embodiment 9, preparation of Wang-resin supported N, N-dimethyl behenyl ammonium phosphotungstic heteropoly acid

Swell 4g of Wang resin with 20mL tetrahydrofuran overnight, add thionyl chloride to reflux for 6h, filter, wash with tetrahydrofuran, and dry; add 30mL 1,2-dichloroethane and 50mL ethanol mixed solvent to swell the above resin overnight, according to n (Cl): n (tertiary amine) = 1:2 Add N,N-dimethylbehenylbehenylamine, reflux for 12 hours, filter with suction, wash, dry in the air, and extract for 12 hours. Vacuum drying at room temperature to constant weight can prepare Wang-resin supported N,N-dimethylbehenyl ammonium chloride. Add the above resin to 50mL of absolute ethanol as a swelling agent to swell overnight, add (NH ₄ ) ₆ P ₂ W ₁₈ O ₆₂ according to n(N):n[(NH ₄ )P ₂ W ₁₈ O ₆₂ ]=2:1 After reacting at room temperature for 12 hours, suction filter, wash with water, dry, and use 10% cetyl quaternary ammonium chloride for treatment to obtain Wang-resin supported N, N-dimethyl behenyl ammonium Phosphotungstic heteropolyacid catalyst.

Example 10, preparation of benzylamine-resin-supported N, N-dimethyldodecammonium arsenovanadate heteropolyacid

Benzylamine resin 5g, 5mL formaldehyde and 10mL formic acid were reacted at 100°C for 10h. The reaction product was washed with water and methanol, filtered with suction and dried. Put the above resin into the reaction device, add 12mL dodecane chloride, and react the mixture under stirring at 42°C for 24h, wash with petroleum ether and acetone, filter with suction, and dry. That is, benzylamine supported N, N-dimethyl dodecyl ammonium resin. Add 50mL of absolute ethanol to the above resin as a swelling agent to swell overnight, add H ₃ AsV ₁₂ O ₄₀ according to n(N):n(H ₃ AsV ₁₂ O ₄₀ )=1:1, react at 10°C for 14 hours, and then filter with suction , washed with water, and dried to obtain benzylamine-supported N, N-dimethyldodecylammonium arsenovanadate heteropolyacid.

Example 11, Preparation of N,N-Dimethyloctadecylammonium Phosphotungstic Heteropoly Acid Supported by Chlorinated Silica

Weigh 5g of silica gel, add 40mL of xylene as a solvent, soak overnight, slowly add 1.4ml of distilled water with a burette, stir and mix at room temperature for 15min, then add 7ml of 3-chloropropyl-trimethoxysilane to it, Reflux reaction at 80°C for 6h, filter, extract, and dry under reduced pressure to obtain pale yellow chlorinated silicon dioxide. Swell the chlorinated silica with 50mL of 1,2-dichloroethane and 20mL of ethanol overnight, and add N,N-dimethyloctadecylamine according to n(Cl):n(tertiary amine)=1:3 the next day , after 12 hours of reflux reaction, suction filtration, washing and extraction with absolute ethanol for 12 hours to obtain N,N-dimethyloctadecyl ammonium chloride supported on silica, the infrared spectrum data are as follows: 2927cm ^-1 , 2855cm ^{- 1} . Add 50mL of absolute ethanol to chlorinated silicon dioxide supported N,N-dimethyloctadecylammonium as the swelling agent to swell overnight, adding according to n(N):n(P):n(W)=1: 3:12 peroxyphosphotungstic acid, after reflux reaction for 12h, suction filtration, washing with water, drying to obtain N,N-dimethyloctadecylammonium phosphotungstic heteropolyacid supported on light brown silica chloride . The infrared spectrum data are as follows: 2927cm ^-1 , 2855cm ^-1 , 979cm ^-1 (W=O), 894cm ^-1 (υ _as (WOW)).

Example 12, preparation of titanium dioxide chloride supported N,N-dimethyloctadecylammonium phosphotungstic heteropolyacid

Weigh 5g of titanium dioxide, add 40mL of toluene as solvent, soak overnight, slowly add 1.4ml of distilled water with a burette, stir and mix at room temperature for 15min, then add 7ml of 3-chloropropyl-triethoxysilane, Reflux at 80°C for 6 hours, filter, extract, and dry under reduced pressure to obtain titanium dioxide chloride. Swell titanium dioxide chloride with a mixed solvent of 50 mL of 1,2-dichloroethane and 20 mL of ethanol as a swelling agent overnight, and add N, N-dimethyl N, N-dimethyl octadecyl ammonium supported on titanium dioxide chloride, after 12 hours of reflux reaction, suction filtration, washing, and extraction for 12 hours, to obtain N, N-dimethyl octadecyl ammonium supported on titanium dioxide. The infrared spectrum data are as follows: 2921cm ^-1 , 2952cm ^{- 1} , 1466cm ^-1 . Titanium dioxide chloride is supported with N,N-dimethyloctadecyl ammonium, and 50mL of absolute ethanol is added as a swelling agent to swell overnight, and the addition is based on n(N):n(P):n(W)=1:3 : 12 peroxyphosphotungstic acid, after reflux reaction for 12h, suction filtration, washing with water, and vacuum drying to obtain light brown titanium dioxide chloride supported N, N-dimethyloctadecylammonium phosphotungstic heteropolyacid, infrared Spectral data are as follows: 2921cm ^-1 , 2952cm ^-1 , 1466cm ^-1 , 1077cm ^-1 , 977cm ^-1 , 820cm ^-1 .

Example 13, preparation of titanium dioxide chloride supported N, N-dimethylhexadecyl ammonium tungstate

Weigh 5g of titanium dioxide that has been processed, add 40mL of toluene as a solvent, soak overnight, slowly add 1.4ml of distilled water with a burette, stir and mix at room temperature for 15min, and then add 7ml of 3-chloropropyltrimethoxysilane , Reflux at 80°C for 6h, filter, extract for 12h, and dry under reduced pressure for 12h. Titanium dioxide chloride. Swell titanium dioxide chloride with a mixed solvent of 50 mL of 1,2-dichloroethane and 20 mL of ethanol as a swelling agent overnight, and add N, N-dimethyl Hexadecylamine, after 12 hours of reflux reaction, suction filtration, washing and extraction with absolute ethanol for 12 hours. White titanium dioxide chloride was prepared supporting N,N-dimethylhexadecyl ammonium, and the infrared spectrum data were as follows: 2921cm ^-1 , 2952cm ^-1 , 1466cm ^-1 . Titanium dioxide chloride is supported with N,N-dimethylhexadecyl ammonium, and 50mL of absolute ethanol is added as a swelling agent to swell overnight, and sodium tungstate is added according to n(N):n(W)=1:2. Ion exchange reaction for 12 hours, suction filtration, washing with water, and vacuum drying to obtain N,N-dimethylhexadecylammonium tungstate supported on titanium dioxide chloride.

3. Compounding of catalysts:

Example 14, preparation of chloromethylated polystyrene resin supported N,N-dimethyltetradecylammonium phosphotungstic heteropolyacid composite catalyst

The chloromethylated polystyrene resin in Example 5 was supported by N,N-dimethyltetradecylammonium phosphotungstic heteropolyacid and sodium bicarbonate in a mass ratio of 1:1 to obtain chloromethylated polystyrene Styrene resin supported N,N-dimethyltetradecylammonium phosphotungstic heteropolyacid composite catalyst.

Example 15, Preparation of Chloromethylated Polystyrene Resin Supported Triphenylphosphopolytungstic Acid Composite Catalyst

Composite the chloromethylated polystyrene resin-supported triphenylphosphorous polytungstic acid catalyst in Example 6 with calcium sulfate and ammonium acetate in a mass ratio of 40:1 to obtain chloromethylated polystyrene resin-supported triphenylphosphorous polytungstic acid catalyst Phenylphosphopolytungstic acid composite catalyst.

Example 16, preparation of Wang-resin-supported N, N-dimethyl behenyl ammonium phosphotungstic heteropolyacid composite catalyst

The Wang-resin supported N,N-dimethyl behenyl ammonium phosphotungstic heteropoly acid and sodium chloride in Example 9 were compounded according to the mass ratio of 100:1 to obtain Wang-resin supported N,N-dimethyl Docosammonium phosphotungstic acid composite catalyst.

Four, the embodiment that catalyst is used for reaction:

Embodiment 17, preparation of cyclohexene epoxy by solvent-free hydrogen peroxide oxidation of cyclohexene

Cyclohexene 40mL, 30% hydrogen peroxide 10mL, chloromethylated polystyrene supported N,N-dimethyloctadecyl phosphotungstic heteropolyacid CaCl ₂ composite catalyst (50:1) 2g, react at 55°C for 5h , filter the catalyst, carry out gas chromatography analysis in the organic phase, measure the hydrogen peroxide content in the water phase, the conversion rate of hydrogen peroxide reaches 90.3%, the selectivity of epoxy cyclohexane can reach 95.6%, and the yield of epoxy cyclohexane can reach 86.3% .

Catalyst A component was filtered out, 40 mg of CaCl ₂ was added, and used again for the reaction. The above procedure was repeated five times, and the yield of epoxycyclohexane was 85.4%.

Example 18, preparation of adipic acid by oxidizing cyclohexene with hydrogen peroxide

Add 6 mL of cyclohexene and 2 g of chloromethylated polystyrene supported N,N-dimethyloctadecyl ammonium into a 100 mL three-necked flask, add 30 mL of H ₂ O ₂ , stir, and heat to reflux for 3 hours. The temperature was raised to 95°C within 1.5 hours, and the temperature was kept for 6 hours. After the reaction was completed, the catalyst was filtered out while it was hot, and the filtrate was cooled to crystallize, filtered and dried, and then weighed. The yield of adipic acid was 63%.

The recovered catalyst was simply washed and reused for the reaction without adding a new catalyst, and the average yield of adipic acid was 60% after five repeated reactions.

Claims (6)

1, a kind of carrier props up and carries the composite catalyst that contains transition metal, it is characterized in that this composite catalyst is made up of A component and B component, and wherein the A component is represented by following general formula compound:

￠-[(R ₁) _n0-(OCH ₂OCH ₂) _n1-YR ₂R ₃R ₄] _m1(Q ₁) _m2X _n2D

Wherein, ￠ is a carrier in the general formula, is organic material that contains halogen atom, quaternary ammonium salt Huo quaternary alkylphosphonium salt or the inorganic material that contains halogen atom, quaternary ammonium salt Huo quaternary alkylphosphonium salt; Described organic material is selected the modified resin or the polyaniline-modified resin of the macromolecule modified material of polystyrene, polyvinyl chloride modified resin, Wang resin for use; Inorganic material is selected silica gel, titanium dioxide, molecular sieve, diatomite, aluminium oxide or sial hydration solid material for use;

R ₁For -CH ₂-,

Or

R wherein ₅, R ₆Independently be methoxyl group, ethyoxyl or Cl separately, R ₇For-CH ₂-,-CH ₂CH ₂-or-CH ₂CH ₂CH ₂-, n ₄=0 or 1;

Y is N or P atom;

R ₂, R ₃, R ₄Independently be C separately ₁-C ₂₂Alkyl, cycloalkyl, benzyl, phenyl or substituted-phenyl;

Q ₁Be expressed as R ₈R ₉R ₁₀R ₁₁Y ₂ ⁺Or alkyl pyridine quaternary ammonium salt cation, wherein R ₈, R ₉, R ₁₀, R ₁₁Independently be C separately ₁-C ₂₂Alkyl, cycloalkyl, benzyl, phenyl or substituted-phenyl; Y ₂Be N or P atom;

X is H, Na, K, NH ₄Or Ca;

D is heteropoly acid root, isopolyacid root or high-valency metal oxyacid root, and wherein, the heteropoly acid root is by A _aB _cO _4a+3cExpression, the isopolyacid root is by B _cO _4c-rExpression, A is P, Si or As atom, and B is W, Mo or V atom, and O is an oxygen atom;

High-valency metal oxyacid root is the highest price metallate of W, Mo or V;

n ₀=0 or 1, n ₁=0-15, m ₁=1-2, m ₂=0-7, n ₂=0-7, a=1-2, c=1-18, r=0-6;

The B component is Na salt, K salt, Ca salt, Mg salt, NH ₄Any mixture of salt or above salt; The mass ratio of A component and B component is 1～100:1.

2, carrier as claimed in claim 1 props up and carries the composite catalyst that contains transition metal, it is characterized in that,

R ₂, R ₃, R ₄Independently be C separately ₁-C ₂₂Alkyl, benzyl or phenyl;

Q ₁Be R ₈R ₉R ₁₀R ₁₁Y ₂ ⁺Or alkyl pyridine quaternary ammonium salt cation, wherein R ₈, R ₉, R ₁₀, R ₁₁Independently be C separately ₁-C ₂₂Alkyl, benzyl or phenyl, Y ₂Be N or P atom;

D is heteropoly acid root, isopolyacid root or high-valency metal oxyacid root;

Wherein, the heteropoly acid root is by A _aB _cO _4a+3cExpression, the isopolyacid root is by B _cO _4c-rExpression, A is P or Si atom, and B is W or Mo atom, and O is an oxygen atom;

High-valency metal oxyacid root is WO ₄ ^2-Or MoO ₄ ^2-

n ₀=0 or 1, n ₁=0-15, m ₁=1-2, m ₂=0-7, n ₂=0-7, a=1, c=1-12, r=0-6.

3, carrier as claimed in claim 1 or 2 props up and carries the composite catalyst that contains transition metal, it is characterized in that the A component is following general formula compound:

Or

Wherein PS represents the polystyrene resin skeleton, and PVC represents the Corvic skeleton, and Wang represents the Wang resin matrix, and PN represents the polyaniline resin skeleton, and CI represents the inorganic carrier skeleton;

Y is N or P atom;

R ₂, R ₃, R ₄Independently be C separately ₁-C ₂₂Alkyl, benzyl or phenyl;

R wherein ₅, R ₆Independently be methoxyl group, ethyoxyl or Cl separately, R ₇For-CH ₂-,-CH ₂CH ₂---or-CH ₂CH ₂CH ₂-;

Q ₁By R ₈R ₉R ₁₀R ₁₁Y ₂ ⁺Or alkyl pyridine quaternary ammonium salt cation represents, wherein R ₈, R ₉, R ₁₀, R ₁₁Independently be C separately ₁-C ₂₂Alkyl, benzyl or phenyl, Y ₂Be N or P atom;

X is H, Na, K, NH ₄Or Ca;

D is heteropoly acid root, isopolyacid root or transition metal high price oxyacid root;

Wherein, the heteropoly acid root is by A _aB _cO _4a+3cExpression, the isopolyacid root is by B _cO _4c-rExpression, A is P or Si atom, and B is W or Mo atom, and O is an oxygen atom;

High-valency metal oxyacid root is WO ₄ ^2-Or MoO ₄ ^2-

n ₀=0 or 1, n ₁=0-15, m ₁=1-2, m ₂=0-7, n ₂=0-7, a=1, c=1-12, r=0-6.

4, carrier as claimed in claim 1 or 2 props up and carries the composite catalyst that contains transition metal, it is characterized in that the B component is HCO ₃, CO ₃, halogen, SO ₄, HSO ₄, PO ₄, HPO ₄, H ₂PO ₄, CH ₃COO, HCOO, benzoic acid ion respectively with Na, K, Ca, Mg, NH ₄The salt that ion forms or any mixture of above salt.

5, carrier as claimed in claim 4 props up and carries the composite catalyst that contains transition metal, it is characterized in that the A component is represented by following general formula compound:

Or

Wherein, PS represents the polystyrene resin skeleton, and PVC represents the Corvic skeleton, and Wang represents the Wang resin matrix, and PN represents the polyaniline resin skeleton, and CI represents inorganic carrier;

R ₂, R ₃Independently be methyl separately;

R ₄Be C ₁₀-C ₁₈Straight chained alkyl or benzyl;

R wherein ₅, R ₆Independently be methoxyl group, ethyoxyl or Cl separately, R ₇For-CH ₂-,-CH ₂CH ₂-or-CH ₂CH ₂CH ₂-;

Q ₁By R ₈R ₉R ₁₀R ₁₁Y ₂ ⁺Or alkyl pyridine quaternary ammonium salt cation represents, wherein R ₈, R ₉, R ₁₀, R ₁₁Independently be C separately ₁-C ₂₂Alkyl, benzyl or phenyl, Y ₂Be N or P atom;

X is H or Na, K, NH ₄Or Ca;

n ₁＝0-10，m ₁＝1-2，m ₂＝0-2，n ₂＝0-2，p＝1-12；

The B component is HCO ₃, halogen, SO ₄, HSO ₄Acid ion and Na, K, Ca, NH ₄The salt that ion forms or any mixture of above salt, the mass ratio of A component and B component is at 50～1:1.

6, carrier as claimed in claim 1 props up the preparation method of carrying the composite catalyst that contains transition metal, it is characterized in that, may further comprise the steps: the quaternized Huo quaternary phosphine processing of (1), carrier; (2), carrier solvent swell, heteropoly acid, isopolyacid, highest price oxyacid or their salt that active component contains transition metal adds in the carrier of swelling, reacted 6～14 hours down at 10～80 ℃, filter, washing, dry direct carrier prop up and carry the composite catalyst A component that contains transition metal, perhaps use must prop up after alkalescent salt material, the quaternary ammonium salt Huo quaternary alkylphosphonium salt solution-treated drying to carry a phase transfer polyacid composite catalyst A component; (3), A component and B component according to aforementioned proportion mix composite catalyst.