CN100500291C - Composite catalyst containing transient metal loaded by carrier - Google Patents
Composite catalyst containing transient metal loaded by carrier Download PDFInfo
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- CN100500291C CN100500291C CNB2007100539479A CN200710053947A CN100500291C CN 100500291 C CN100500291 C CN 100500291C CN B2007100539479 A CNB2007100539479 A CN B2007100539479A CN 200710053947 A CN200710053947 A CN 200710053947A CN 100500291 C CN100500291 C CN 100500291C
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Abstract
The invention discloses a composite catalyst of transition metal, which consists of component A and component B, wherein the component A is displayed by phi-[(R1) n0-(OCH2OCH2) n1-YR2R3R4] m1 (Q1) m2Xn2D; the component B is salt; the weight rate of component A and component B is 1-100: 1.
Description
Technical field
The present invention relates to a kind of carrier and prop up and carry a composite catalyst, especially relate to a kind of carrier and prop up and carry the composite catalyst that contains transition metal.
Background technology
The effective recycling of catalyst is the emphasis of modern catalytic reaction research, heteropoly acid quaternary ammonium salt material is the high activated catalyst of current catalysis hydrogen peroxide oxidation olefin production epoxides, this class catalyst selectivity is good, conversion ratio is high, reclaim and reuse but be difficult to from reaction system, separate, expensive catalysts can not effectively reclaim, can pollute product on the one hand, can cause production cost to improve on the other hand, make technology be difficult to industrialization.The patent No. is that the Chinese patent of CN1401640 discloses a kind of reaction control phase transfer catalyst, this catalyst itself is a solid, in reaction medium under the effect of oxidant, be dissolved in the reaction system, homogeneous phase participates in reaction, when oxidant consumption is finished, catalyst returns to the form of solid again, can more conveniently reclaim, but this method all has very harsh requirement to the selection of the quaternary ammonium salt in choice of Solvent in the reaction system and the catalyst structure correspondingly, limit its range of application, and reaction to finish with rear catalyst also only be can be partially recycled, primary recovery is about 70%.The patent No. is the Chinese patent of CN1765502A, a kind of catalyst that is used for oxidation reaction is disclosed and in the application of oxidation reaction, catalyst is under the effect of reactant oxidant in this method, the activity of such catalysts component is separated with carrier to enter and is formed active specy in the reaction medium, thereby carry out the homogeneous catalysis oxidation reaction, after reaction end oxidant consumption is intact, catalyst activity component in the reaction medium is combined into original supported catalyst with carrier again, but the problem of supported catalyst with regard to existing the catalyst activity component to run off itself, inevitably also there is this phenomenon in the method for this reversible load.At two kinds of above-mentioned reacting middle catalysts at oxidant such as hydrogen peroxide, oxygen sources such as alkyl peroxide consume completely, and situation could realize reclaiming, so choosing at reaction condition in order to make oxygen source consumption complete, need to add excessive substrate, in addition, also be based on the principle of reaction-controlled phase transfer catalysis because of reversible supported catalyst, in order to realize the reversible load of catalyst, can only use specific solvent and specific quaternary ammonium salt structure catalyst in this catalyst system and catalyzing, and the catalyst system and catalyzing that above catalyst uses all includes a large amount of solvents, a large amount of is volatile, poisonous, the use of harmful solvent, do not meet the requirement of Green Chemistry, on producing, improved production cost yet.
Summary of the invention
The purpose of this invention is to provide that a kind of catalytic activity height, activity of such catalysts component conveniently fully reclaim and recycle, the carrier of pollution products does not prop up and carries the composite catalyst that contains transition metal.
The present invention realizes above-mentioned purpose by the following technical solutions: a kind of carrier props up and carries the composite catalyst that contains transition metal, and 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
2R
4]
m1(Q
1)
m2X
n2D
Wherein, ￠ is a carrier in the general formula;
R1 is
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;
R
2, R
3, R
4Preferably independently be C separately
1-C
22Alkyl, benzyl or 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; R
8, R
9, R
10, R
11Preferably independently 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 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; B is W, Mo or V atom, and O is an oxygen atom; A is preferably P or Si atom; B is preferably W or Mo atom;
High-valency metal oxyacid root is the high-valency metal acid group of W, Mo or V; Be 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,
The A component is preferably following general formula compound again:
Wherein PS represents the polystyrene resins skeleton, and PVC represents the polyvinyl chloride resin skeleton, and Wang represents the Wang resin matrix, and PN represents the polyaniline compound resin matrix, 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 can be expressed as B
cO
4c-r, A is P or Si atom; 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.
The A component is most preferably represented by following general formula compound:
Or
Wherein, PS represents the polystyrene resins skeleton, and PVC represents the polyvinyl chloride resin skeleton, and Wang represents the Wang resin matrix, and PN represents the polyaniline compound resin matrix, and CI represents inorganic carrier;
R
2, R
3Most preferably independently be methyl separately;
R
4Most preferably be 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
11Most preferably independently 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 a salt.
The B component is preferably Na salt, K salt, Ca salt, Mg salt, NH
4Any mixture of salt or above salt.
The B component is preferably HCO again
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.
The B component most preferably 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 1～100:1.
The mass ratio of A component and B component most preferably is 50～1:1.
Carrier ￠ is the inorganic material that contains the organic material of halogen atom, quaternary ammonium salt Huo quaternary alkylphosphonium salt or contain active hydroxyl, halogen atom, quaternary ammonium salt Huo quaternary alkylphosphonium salt.
The modified resin or the polyaniline-modified resin of the macromolecule modified material of the preferred polystyrene type of organic material, polyvinyl chloride modified resin, Wang resin; Inorganic carrier preferably contains the silica gel of halogen atom, quaternary ammonium salt Huo quaternary alkylphosphonium salt, the titanium dioxide that contains halogen atom, quaternary ammonium salt Huo quaternary alkylphosphonium salt, the molecular sieve that contains halogen atom, quaternary ammonium salt Huo quaternary alkylphosphonium salt, the diatomite that contains halogen atom, quaternary ammonium salt Huo quaternary alkylphosphonium salt contains the aluminium oxide of halogen atom, quaternary ammonium salt Huo quaternary alkylphosphonium salt or contains the sial hydration solid material of halogen atom, quaternary ammonium salt Huo quaternary alkylphosphonium salt.
Carrier props up the preparation method of carrying the composite catalyst that contains transition metal and may further comprise the steps: the quaternized Huo quaternary phosphine processing of (1), carrier; (2), carrier solvent swell, heteropoly acid, isopolyacid, high 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, wash, dry direct carrier props up and carries the composite catalyst A component that contains transition metal, perhaps uses must prop up after alkalescent salts substances, 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.
The preparation method of composite catalyst is specially following steps:
One, the quaternary ammonium (Phosphonium of carrier) changes processing
The quaternary ammonium (Phosphonium of carrier) change is treated to prior art, below sketches processing method:
1, the processing procedure of p-poly-phenyl vinyl resins (PS) is:
(1), p-poly-phenyl vinyl: polystyrene resin carries out chloromethylation through reacting with chloromethyl ether, introduces (OCH with the chlorethanol reaction then
2CH
2)
N1(being called an arm), carry out quaternary ammonium (Phosphonium with tertiary amine (triphenyl phosphorus or derivatives thereof) again) change reaction and obtain quaternary ammonium (Phosphonium) change resin;
(2), to chloromethyl resin: arm between chloromethyl resin and chlorethanol reaction are introduced, with tertiary amine (or triphenyl phosphorus or derivatives thereof) reaction carrying out quaternary ammonium (Phosphonium) change obtain quaternary ammonium (Phosphonium) change resin;
(3), for quaternary ammonium (Phosphonium) resin changed then can be directly used in carrying of active component.
2, the processing procedure of Corvic (PVC) is: (OCH is introduced in PVC and chlorethanol reaction
2CH
2)
N1(being called an arm), carry out quaternary ammonium (Phosphonium with tertiary amine (or triphenyl phosphorus or derivatives thereof) again) change reaction and obtain quaternary ammonium (Phosphonium) change resin; Or PVC and tertiary amine (or triphenyl phosphorus or derivatives thereof) directly carry out quaternary ammonium (Phosphonium) change obtain quaternary ammonium (Phosphonium) change resin;
3, the processing procedure to the Wang resin is: active benzyl chlorine is introduced in Wang resin and thionyl chloride reaction, arm (OCH between the chlorethanol reaction is introduced then
2CH
2)
n, carry out quaternary ammonium (Phosphonium with tertiary amine (or triphenyl phosphorus or derivatives thereof)) change reaction and obtain quaternary ammonium (Phosphonium) change resin; Or the reaction of Wang resin and thionyl chloride is directly directly carried out quaternary ammonium (Phosphonium with tertiary amine (or triphenyl phosphorus or derivatives thereof) after introducing active benzyl chlorine) change obtain quaternary ammonium (Phosphonium) the change resin.
4, the processing procedure to the benzylamine resin is: benzylamine resin solvent swelling, and carry out Mannich reaction with formaldehyde and obtain the tertiary amine resin, carry out quaternized with the alkyl chloride reaction again.
Carry out the quaternised tertiary amine of carrier or triphenyl phosphorus and derivative thereof
In, R
2, R
3, R
4Independent separately is C
1-C
22Alkyl, benzyl, phenyl or substituted-phenyl, Y is N or P atom;
5, the processing of inorganic carrier:
Modification for the inorganic carrier that contains active hydroxyl is handled: carry out chemical bonding with chlorosiloxanes as coupling agent and introduce active chlorine atom or introduce active chlorine atom with the thionyl chloride reaction, arm between introducing again is again with tertiary amine (triphenyl phosphorus or derivatives thereof) reaction carrying out quaternary ammonium (Phosphonium) change quaternary ammonium (phosphorus) inorganic carrier; Another kind method is introduced reactive amines for carrying out chemical bonding for siloxanes as coupling agent with amine, carry out tertiary amineization again, carries out the quaternized quaternary ammonium inorganic carrier that gets with the alkyl chloride reaction again;
The siloxanes coupling agent of modifying by
Expression, M is Cl or NH
2, R
5, R
6, R
12Independent separately is methoxyl group, ethyoxyl or Cl; R
7For-CH
2-,-CH
2CH
2-or-CH
2CH
2CH
2-, n
4=0 or 1, the preferred 3-chloropropyl-triethoxysilane of siloxanes coupling agent, 3-chloropropyl-trimethoxy silane, etc. 3-amine propyl group-triethoxysilane, 3-amine propyl group-trimethoxy silane or dichlorodimethylsilane.
Two, propping up of active component carried
The carrier alcohols solvent swelling that modification is handled well, add the heteropoly acid, isopolyacid, high-valency metal oxyacid or their salt that contain transition metal and reacted 6-14 hour down, obtain carrier and prop up phase transfer heteropolyacid salt, isopolyacid salt or the high-valency metal oxysalt that carries at 10-80 ℃.
The mixed liquor of alcohols solvent preferred alcohol or ethanol and water.
Three, the post processing of catalyst
Use alkalescent salt weak solution, quaternary ammonium salt or quaternary alkylphosphonium salt weak solution to carry out ion-exchange above preparation activity of such catalysts component,, get the A component then after the drying with part or all of unreacted hydrogen in the phosphotungstic acid in the processing catalyst.
The alkalescent salt that is used to handle catalyst is NaHCO
3, Na
2CO
3, NH
4HCO
3, (NH
4)
2CO
3, KCO
3Or KHCO
3, mass percentage concentration is 0.5%-10%; Quaternary ammonium salt Huo quaternary alkylphosphonium salt is R
8R
9R
10R
11Y
2Cl, wherein R
8, R
9, R
10, R
11Independent separately is C
1-C
22Alkyl, benzyl phenyl or substituted-phenyl, Y
2Expression N or P, mass percentage concentration is 0.5%-10%.
Four, catalyst is compound
The A component of above preparation and B component salt are mixed composite according to ratio in the technique scheme, promptly obtain carrier and prop up and carry the composite catalyst that contains transition metal.But also can when reaction, add A component and B component respectively according to above ratio.
Carrier of the present invention props up and carries the composite catalyst contain transition metal and comprise two kinds of A, B component, two kinds of component synergies, the catalytic activity height of catalyst, the A component is that carrier props up year phase transfer heteropolyacid salt, isopolyacid salt or a high-valency metal oxysalt, be the activity of such catalysts component, this part catalyst can reclaim easily; The B component is cheap salt, this component has improved activity of such catalysts and selectivity, use the A component that certain catalytic activity and selectivity are arranged separately, but catalytic activity is lower, selectivity is also relatively poor, use the B component then not have activity fully separately, the A component and the B component of this composite catalyst are complementary, and be indispensable.Composite catalyst A component of the present invention is by chemical bonding the activity of such catalysts group of branches to be stated from the carrier, and catalyst structure is stable, catalyst activity component difficult drop-off, and active component does not break away from catalyst carrier in course of reaction; Catalytic reaction is carried out in the microchannel of catalyst, therefore the catalyst activity component does not enter the reaction organic facies, pollution products not, and reclaim very convenient, only needing to finish simple filtration washing later in reaction promptly can be used for reacting again, can omit centrifugal other step that waits, in addition, catalyst does not have complete reaction to separate under the situation completely at hydrogen peroxide can not cause damage to active component, therefore just can avoid adding a large amount of substrate alkene for hydrogen peroxide has been reacted, can in needs, carry out separating treatment, can realize easily that the scene (in-situ) to catalyst characterizes.This composite catalyst also has quite high stability, active component (A component) is reused 15 times, still can keep activity and selectivity, active component (A component) had both had the function of catalysis hydrogen peroxide oxidation alkene, the function that also has phase transfer simultaneously, can also regulate and control its Acidity of Aikalinity easily, composite catalyst of the present invention not only can be used for the reaction of solventless method hydrogen peroxide oxidation olefin production epoxides, realize the greenization of preparation of epoxides, and can be widely used in the preparation α, the reaction of α '-glycol, oxyalkylene prepare the reaction of carboxylic acid or diacid etc.
Nicolet 10 DX-FTIR type infrared spectrometers, spectral region: 4000～400cm are adopted in infrared spectrum analysis
-1, resolution ratio 0.5～4cm
-1, compressing tablet adopts KBr.
The specific embodiment
One, active component phosphorus heteropoly tungstic acid or with the preparation of many wolframic acids:
Embodiment 1, the preparation of peroxide phosphotungstic acid
Take by weighing the 3.3g sodium tungstate, separate with 30mL is water-soluble, drip 6mol/L hydrochloric acid 30mL, suction filtration with the distilled water washing, with the dissolving of 30mL 27.5% hydrogen peroxide, adds 85% H with 0.29g with the gained solid
3PO
4, add the dilution of 40mL water again, promptly make the peroxide phosphotungstic acid.
Embodiment 2, the preparation of the many wolframic acids of peroxide
Take by weighing the 3.3g potassium tungstate, separate with 20mL is water-soluble, Dropwise 5 mol/L hydrochloric acid 30mL, suction filtration with the distilled water washing, with the dissolving of 30mL 30% hydrogen peroxide, promptly makes the peroxide wolframic acid with the gained solid.
Two, the preparation of A component:
Embodiment 3, and the chloromethylated polystyrene resin props up and carries N, the preparation of N-dimethyl stearyl ammonium phosphorus heteropoly tungstic acid
Dry chloromethylated polystyrene divinylbenzene crosslink resin (is called for short the chlorine ball, down together) 4g places there-necked flask, and with 50mL 1,2-dichloroethanes and 20mL ethanol mixed solvent swelling are spent the night, according to n (Cl): n (tertiary amine)=1: 3 adding N, Dymanthine, behind the back flow reaction 12h, suction filtration, washing, dry, extracting 12h, vacuum drying is to constant weight under the room temperature.Can make little yellow chloromethylated polystyrene and prop up a year N, N-dimethyl stearyl ammonium, The results of FT-IR is as follows: 2924cm
-1(CH
2C-H antisymmetric stretching vibration peak), 2853cm
-1(CH
2C-H symmetrical stretching vibration peak), 3024cm
-1(υ (CH
3) the stretching vibration absorption), 1376cm
-1(δ (CH
3) flexural vibrations), 670cm
-1(C-Cl key absworption peak) almost disappears, 1268cm
-1(characteristic absorption peak of benzyl C-H) almost disappears, and existence-CH hardly is described in this structure
2The Cl structure, 1117cm
-1The υ of place (C-N) further specifies and quaternizedly finishes.
Chloromethylated polystyrene is propped up a year N, N-dimethyl stearyl ammonium adds the 50mL absolute ethyl alcohol and spends the night for the sweller swelling, adding is according to the peroxide phosphotungstic acid of n (N): n (P): n (W)=1:1:4, after normal temperature reacts 12h down, suction filtration, washing, drying, promptly get the yellowish green chloromethylated polystyrene and prop up a year N, N-dimethyl stearyl ammonium phosphorus heteropoly tungstic acid.The results of FT-IR is as follows: 2922cm
-1, 2851cm
-1, 3025cm
-1, 1377cm
-1, 1079cm
-1(PO
4 3-υ (P-O) vibration), 940cm
-1(belonging to υ (W=O)), 883cm
-1(υ (W-Ob-W) (angle altogether)), 811cm
-1(υ (W-Oc-W) (limit altogether)).
Embodiment 4, and the chloromethylated polystyrene resin props up and carries polyethylene glycol N, the preparation of N-dimethyl dodecyl ammonium phosphorus heteropoly tungstic acid
3g chloromethylation macropore polystyrene resin (ps) is positioned over there-necked flask, adds the 30mL toluene swell and spends the night.Add the 70mL ethylene chlorhydrin, an amount of anhydrous K
2CO
3And the quaternary ammonium salt catalyst, add 20mL toluene again, 90 ℃ of temperature controls, reaction 14h.Vacuum filtration washing, drying can get PS-(OCH
2CH
2)
15Cl.PS-(OCH with above-mentioned drying
2CH
2)
15Cl 4g places there-necked flask, and with 50mL 1,2-dichloroethanes and 20mL ethanol mixed solvent swelling are spent the night, and add N according to n (Cl): n (tertiary amine)=1:3, N-dimethyl lauryl amine, and behind the back flow reaction 12h, suction filtration, extracting 12h is dried in washing.Vacuum drying is to constant weight under the room temperature.Little yellow chloromethylated polystyrene be can make and a year N, N-polyethylene glycol dimethyl dodecyl ammonium propped up.Above-mentioned resin is spent the night for the sweller swelling with the 50mL absolute ethyl alcohol, adding is according to the peroxide phosphotungstic acid of n (N): n (P): n (W)=1:1:4, after normal temperature reacts 12h down, suction filtration, washing, drying promptly gets the yellowish green chloromethylated polystyrene and props up a year N, N-polyethylene glycol dimethyl dodecyl ammonium phosphorus heteropoly tungstic acid.
Embodiment 5, and the chloromethylated polystyrene resin props up and carries N, the preparation of N-dimethyl 14 ammonium phosphorus heteropoly tungstic acids
Dry chlorine ball 4g is placed there-necked flask, and with 40mL 1,2-dichloroethanes and 30mL ethanol mixed solvent swelling are spent the night, and add N according to n (Cl): n (tertiary amine)=1:2, N-dimethyl tetradecy lamine, and behind the back flow reaction 12h, suction filtration, washing is dried.Extracting 12h.Vacuum drying is to constant weight.Little yellow chloromethylated polystyrene be can make and a year N, N-dimethyl myristyl ammonium propped up.The results of FT-IR is as follows: 2923cm
-1, 2852cm
-1, 3026cm
-1, 1374cm
-1, 1119cm
-1Chloromethylated polystyrene is propped up a year N, N-dimethyl myristyl ammonium adds the 50mL absolute ethyl alcohol and spends the night for the sweller swelling, adding is according to the peroxide phosphotungstic acid of n (N): n (P): n (W)=1:2:10, after reacting 12h under the room temperature, suction filtration, washing, drying, promptly get chloromethylated polystyrene and prop up a year N, N-dimethyl myristyl ammonium quaternary ammonium salt phosphor-tungstic heteropoly acid catalyst.Ir data is as follows: 2921cm
-1, 2854cm
-1, 3027cm
-1, 1376cm
-1, 1077cm
-1, 943cm
-1, 885cm
-1, 814cm
-1
Embodiment 6, and the chloromethylated polystyrene resin props up the preparation of carrying the many wolframic acids of triphenyl phosphorus
Dry chlorine ball 4g is placed there-necked flask, use 40mL1,2-dichloroethanes and 30mL ethanol mixed solvent swelling are spent the night, and add triphenyl phosphorus according to n (Cl): n (triphenyl phosphorus)=1:2, behind the back flow reaction 12h, and suction filtration, washing is dried.Extracting 12h, vacuum drying to constant weight can make chloromethylated polystyrene and prop up a year triphenyl quaternary alkylphosphonium salt.Above-mentioned chloromethylated polystyrene is propped up a year triphenyl quaternary alkylphosphonium salt adding 50mL absolute ethyl alcohol to spend the night for the sweller swelling, adding is according to the many wolframic acids of peroxide of n (P): n (W)=1:2, after normal temperature reacts 12h down, suction filtration, washing, drying promptly gets chloromethylated polystyrene and props up year many wolframic acids of triphenyl quaternary alkylphosphonium salt.
Embodiment 7, and the chloromethylated polystyrene resin props up and carries N, the preparation of N-dimethyl benzyl ammonium phosphorus heteropoly tungstic acid
Dry chlorine ball 4g is placed there-necked flask, with 20mL 1,2-dichloroethanes and 50mL ethanol mixed solvent swelling are spent the night, according to n (Cl): n (tertiary amine)=1:2.5 N, the N-dimethyl benzylamine, behind the back flow reaction 12h, suction filtration, washing, dry, extracting 12h, vacuum drying to constant weight promptly gets the chloromethylated polystyrene resin and props up a year N, N-dimethyl benzyl ammonium under the room temperature.The chloromethylated polystyrene resin is propped up a year N, and the N-dimethyl benzyl ammonium adds the 50mL absolute ethyl alcohol and spends the night for the sweller swelling, adds the peroxide phosphotungstic acid according to n (N): n (P): n (W)=1:3:12, behind 80 ℃ of reaction 6h, and suction filtration, 0.5% NaHCO is used in washing
3Handle, vacuum drying promptly gets light brown chloromethylated polystyrene resin and props up a year N, N-dimethyl benzyl ammonium phosphorus heteropoly tungstic acid.
Embodiment 8, and Corvic props up and carries N, the preparation of N-dimethyl benzyl ammonium phosphorus heteropoly tungstic acid
Dry Corvic 4g is placed there-necked flask, with 40mL 1,2-dichloroethanes and 40mL ethanol mixed solvent swelling are spent the night, and add N, N-dimethyl benzylamine according to n (Cl): n (tertiary amine)=1:1.5, behind the back flow reaction 12h, suction filtration, washing is dried, extracting 12h, vacuum drying is to constant weight under the room temperature.Polyvinyl chloride be can make and a year N, N-dimethyl benzyl ammonium chloride propped up.Above resin is added the 50mL absolute ethyl alcohol spend the night, add according to n (N): n (H for the sweller swelling
3PW
12O
40)=1:1 adds phosphorus heteropoly tungstic acid H
3PW
12O
40The aqueous solution, behind 60 ℃ of reaction 8h, suction filtration, washing, drying is used 5% NH
4HCO
3The aqueous solution is handled, and promptly gets polyvinyl chloride and props up a year N, N-dimethyl benzyl ammonium phosphorus heteropoly tungstic acid.
Embodiment 9, and the Wang-resin props up and carries N, the preparation of N-dimethyl 22 ammonium phosphorus heteropoly tungstic acids
Wang resin 4g is spent the night with 20mL oxolane swelling, add thionyl chloride back flow reaction 6h, filter, oxolane washing, drying; Above resin is added 30mL 1, and 2-dichloroethanes and 50mL ethanol mixed solvent swelling are spent the night, and add N according to n (Cl): n (tertiary amine)=1:2, N-dimethyl two lauryl amines, and behind the back flow reaction 12h, suction filtration, extracting 12h is dried in washing.Vacuum drying to constant weight can make the Wang-resin and prop up a year N, N-dimethyl docosane ammonium chloride under the room temperature.Above resin is added the 50mL absolute ethyl alcohol spend the night, add according to n (N): n ((NH for the sweller swelling
4) P
2W
18O
62)=2:1 adds (NH
4)
6P
2W
18O
62The aqueous solution, behind the normal-temperature reaction 12h, suction filtration, washing, drying uses 10% chlorination cetyl quaternary ammonium salt to handle, and promptly get the Wang-resin and props up a year N, N-dimethyl docosyl ammonium phosphorus heteropoly tungstic acid catalyzer.
Embodiment 10, and benzylamine-resin props up and carries N, the preparation of N-dimethyl 12 ammonium arsenic vanadium heteropoly acids
Benzylamine resin 5g, 5mL formaldehyde and 10mL formic acid react 10h down at 100 ℃.Product water and methanol wash, dry behind the suction filtration.Above-mentioned resin is added in the reaction unit, add the 12mL chlorinated dodecane, this mixture under agitation reacts 42 ℃ of reaction 24h, benzinum and acetone washing, suction filtration, drying.Promptly get benzylamine and prop up a year N, N-dimethyl 12 ammonium resins.Above resin is added the 50mL absolute ethyl alcohol spend the night, add according to n (N): n (H for the sweller swelling
3AsV
12O
40)=1:1 adds H
3AsV
12O
40, behind 10 ℃ of reaction 14h, suction filtration, washing, drying promptly gets benzylamine and props up a year N, N-dimethyl dodecyl ammonium arsenic vanadium heteropoly acid.
Embodiment 11, and chlorodioxin silicon props up and carries N, the preparation of N-dimethyl stearyl ammonium phosphorus heteropoly tungstic acid
Take by weighing 5g silica gel, the dimethylbenzene that adds 40mL is made solvent, soaked overnight slowly adds the distilled water of 1.4ml with buret, at room temperature mixes 15min, again to 3-chloropropyl--the trimethoxy silane that wherein adds 7ml, at 80 ℃ of following back flow reaction 6h, filter extracting, drying under reduced pressure gets faint yellow chlorodioxin silicon.With chlorodioxin silicon with 1,2-dichloroethanes 50mL and ethanol 20mL swelling are spent the night, add N according to n (Cl): n (tertiary amine)=1:3 next day, Dymanthine, behind the back flow reaction 12h, suction filtration, the washing back is used absolute ethyl alcohol extracting 12h to get chlorodioxin silicon and is propped up a year N, N-dimethyl stearyl ammonium, ir data is as follows: 2927cm
-1, 2855cm
-1Chlorodioxin silicon is propped up a year N, N-dimethyl stearyl ammonium adds the 50mL absolute ethyl alcohol and spends the night for the sweller swelling, adding is according to the peroxide phosphotungstic acid of n (N): n (P): n (W)=1:3:12, behind the back flow reaction 12h, suction filtration, washing, drying, promptly get light brown chlorodioxin silicon and prop up a year N, N-dimethyl stearyl ammonium phosphorus heteropoly tungstic acid.Ir data is as follows: 2927cm
-1, 2855cm
-1, 979cm
-1(W=O), 894cm
-1(υ
As(W-O-W)).
Embodiment 12, and the chlorodioxin titanium props up and carries N, the preparation of N-dimethyl stearyl ammonium phosphorus heteropoly tungstic acid
Take by weighing 5g titanium dioxide, the toluene that adds 40mL is made solvent, soaked overnight slowly adds the distilled water of 1.4ml with buret, at room temperature mixes 15min, again to the 3-chloropropyl-triethoxysilane that wherein adds 7ml, at 80 ℃ of following back flow reaction 6h, filter extracting, drying under reduced pressure gets the chlorodioxin titanium.With the chlorodioxin titanium with 1, the mixed solvent of 2-dichloroethanes 50mL and ethanol 20mL spends the night for the sweller swelling, add N according to n (Cl): n (tertiary amine)=1:3 next day, and Dymanthine is behind the back flow reaction 12h, suction filtration, washing, extracting 12h makes the chlorodioxin titanium and props up a year N, N-dimethyl stearyl ammonium, ir data is as follows: 2921cm
-1, 2952cm
-1, 1466cm
-1The chlorodioxin titanium is propped up a year N, N-dimethyl stearyl ammonium, add the 50mL absolute ethyl alcohol and spend the night, add peroxide phosphotungstic acid, behind the back flow reaction 12h according to n (N): n (P): n (W)=1:3:12 for the sweller swelling, suction filtration, washing, vacuum drying promptly gets light brown chlorodioxin titanium and props up a year N, N-dimethyl stearyl ammonium phosphorus heteropoly tungstic acid, ir data is as follows: 2921cm
-1, 2952cm
-1, 1466cm
-1, 1077cm
-1, 977cm
-1, 820cm
-1
Embodiment 13, and the chlorodioxin titanium props up and carries N, the preparation of N-dimethyl cetyltrimethyl ammonium tungstates
Take by weighing the titanium dioxide that 5g has handled well, the toluene that adds 40mL is made solvent, soaked overnight, slowly add the distilled water of 1.4ml with buret, at room temperature mix 15min, again to the 3-r-chloropropyl trimethoxyl silane that wherein adds 7ml, at 80 ℃ of following back flow reaction 6h, filter extracting 12h, drying under reduced pressure 12h.Get the chlorodioxin titanium.With 1, the mixed solvent of 2-dichloroethanes 50mL and ethanol 20mL spends the night for the sweller swelling with the chlorodioxin titanium, and add N according to n (Cl): n (tertiary amine)=1:3 next day, N-dimethyl cetylamine, behind the back flow reaction 12h, suction filtration, absolute ethyl alcohol extracting 12h is used in the washing back.Make white chlorodioxin titanium and prop up a year N, N-dimethyl cetyltrimethyl ammonium, ir data is as follows: 2921cm
-1, 2952cm
-1, 1466cm
-1The chlorodioxin titanium is propped up a year N, N-dimethyl cetyltrimethyl ammonium, adding the 50mL absolute ethyl alcohol spends the night for the sweller swelling, adding is carried out ion-exchange reactions 12h according to the sodium tungstate of n (N): n (W)=1:2, suction filtration, washing, vacuum drying, promptly get the chlorodioxin titanium and prop up a year N, N-dimethyl cetyltrimethyl ammonium tungstates.
Three, catalyst is compound:
Embodiment 14, and the chloromethylated polystyrene resin props up and carries N, the preparation of N-dimethyl myristyl ammonium phosphorus heteropoly tungstic acid composite catalyst
The chloromethylated polystyrene resin of embodiment 5 is propped up a year N, N-dimethyl myristyl ammonium phosphorus heteropoly tungstic acid and sodium acid carbonate prop up a year N, N-dimethyl myristyl ammonium phosphorus heteropoly tungstic acid composite catalyst according to the compound chloromethylated polystyrene resin that promptly obtains of mass ratio 1:1.
Embodiment 15, and the chloromethylated polystyrene resin props up the preparation of carrying many wolframic acids of triphenyl phosphorus composite catalyst
The chloromethylated polystyrene resin of embodiment 6 propped up carry the many tungstic acid catalysts of triphenyl phosphorus and prop up year many wolframic acids of triphenyl phosphorus composite catalyst according to the compound chloromethylated polystyrene resin that promptly obtains of mass ratio 40:1 ratio with calcium sulfate and ammonium acetate.
Embodiment 16, and the Wang-resin props up and carries N, the preparation of N-dimethyl 22 ammonium phosphorus heteropoly tungstic acid composite catalysts
The Wang-resin of embodiment 9 is propped up a year N, and N-dimethyl 22 ammonium phosphorus heteropoly tungstic acids and sodium chloride prop up a year N, N-dimethyl 22 ammonium phosphorus heteropoly tungstic acid composite catalysts according to the compound Wang-resin that promptly obtains of mass ratio 100:1.
Four, the catalyst embodiment that is used to react:
Embodiment 17, and solventless method hydrogen peroxide oxidation cyclohexene prepares 7-oxa-bicyclo[4.1.0
Cyclohexene 40mL, 30% hydrogen peroxide 10mL, chloromethylated polystyrene prop up and carry N, N-dimethyl stearyl phosphorus heteropoly tungstic acid CaCl
2Composite catalyst (50:1) 2g, 55 ℃ of reaction 5h, filtering catalyst, organic facies is carried out gas chromatographic analysis, and water is measured hydrogen peroxide content, and the conversion ratio of hydrogen peroxide reaches 90.3%, the selectivity of 7-oxa-bicyclo[4.1.0 can reach 95.6%, and the yield of 7-oxa-bicyclo[4.1.0 can reach 86.3%.
The catalyst A component is filtered out, add 40mg CaCl
2, be reused for reaction, to reuse five times according to said procedure, the 7-oxa-bicyclo[4.1.0 yield is 85.4%.
Embodiment 18, and the hydrogen peroxide oxidation cyclohexene prepares adipic acid
6mL cyclohexene, 2g chloromethylated polystyrene are propped up a year N, and N-dimethyl stearyl ammonium joins in the 100mL there-necked flask, adds 30mL H
2O
2, stir, behind the heating reflux reaction 3h, in 1.5h, be warming up to 95 ℃, insulation reaction 6h.While hot catalyst is filtered out after reaction finishes, the filtrate crystallisation by cooling is weighed behind the filtration drying.The yield of adipic acid is 63%.
Reclaim catalyst through simple washing, be reused for reaction, do not add raw catelyst, the average yield 60% of five reaction repeated adipic acids.
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:
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.
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| CN103055940B (en) * | 2013-01-06 | 2014-12-10 | 郑州大学 | Composite catalyst with metal salt loaded on carrier, and preparation method thereof |
| CN103657696B (en) * | 2013-12-12 | 2015-12-02 | 中科院广州能源所盱眙凹土研发中心 | Preparation method of attapulgite-based solid acid catalyst for vegetable oil epoxidation |
| CN105085603B (en) * | 2015-08-26 | 2018-03-02 | 河北大学 | A kind of load type platinum complex oxidant that can be recycled and its preparation method and application |
| CN111097527A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Supported heteropolyacid catalyst, preparation method and application |
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