CN100441610C - Polymer xifualkali phthalocyanin bimetal compound, its preparation method and application - Google Patents
Polymer xifualkali phthalocyanin bimetal compound, its preparation method and application Download PDFInfo
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- CN100441610C CN100441610C CNB2006101049190A CN200610104919A CN100441610C CN 100441610 C CN100441610 C CN 100441610C CN B2006101049190 A CNB2006101049190 A CN B2006101049190A CN 200610104919 A CN200610104919 A CN 200610104919A CN 100441610 C CN100441610 C CN 100441610C
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- phthalocyanin
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Abstract
This invention discloses a giant molecule Schiff's base-phthalocyanine thermometal coordination compound and its preparation. The preparation of this giant molecule Schiff's base-phthalocyanine thermometal coordination compound is made by interface fasculation of orth-benzene di-imido mini-(4,4'-di-hydroxy group )salicylaldehyde Schiff's base transition metal coordination compound and phthalocyanine sulfochlorides transition metal coordination compound. This giant molecule Schiff's base-phthalocyanine thermometal coordination compound contains double active center, possessing very strong Catalytic Properties.it can be used to catalyze molecule oxidizing reaction, especially to produce catalyst of allotri-propylbenzene hydrogen dioxide.
Description
Technical field
The invention belongs to technical field of macromolecules, relate to a kind of polymer catalyst, relate in particular to a kind of polymer catalyst---polymer xifualkali phthalocyanin bimetal compound that utilizes Schiff base metal complexes and metal phthalocyanine complex preparation.
Background technology
Because porphyrin has particular structure and performance, has a wide range of applications in fields such as chemistry, biological chemistry, medical science, Materials science.Studies show that metal porphyrin complex catalytic activation, especially micromolecular compound and polymer porphyrin metal complex to molecular oxygen under mild conditions is subjected to paying close attention to widely in bionic catalysis oxidation field.But people have also found many preparations and have used many unfavorable factors of porphyrin that wherein synthetic yield is low, the performance that costs an arm and a leg is particularly outstanding in the process of experiment.In the porphyrin-like metallic compound, the most outstanding representative is exactly Salen type schiff bases and metal phthalocyanine complex.Because Salen schiff bases and metal phthalocyanine (Metallophthalocyanine with the big member ring systems of 18-πDian Zi fragrance, being abbreviated as MPc) structure and porphyrin be all quite similar, be easy to synthesize, but also be easy to form title complex with most of metal ion, therefore Salen type schiff bases and metal phthalocyanine metal complexes more and more cause people's attention, especially aspect simulation protoheme reversible adsorption molecular oxygen and analog cytochrome P-450 catalyzed oxidation, make it to become the catalyzer that a class has development and application prospect very much.
Characteristics such as phthalocyanine-like compound is inexpensive owing to having, low toxicity, Heat stability is good, and spectral response range is wide, it is one of important function material, be applied in all many-sides, as: the eelctro-catalyst of redox reaction in the sensitizing agent in the photodynamic therapy, the desulfurization catalyst in the refining of petroleum, the fuel cell, and as materials such as fluorescent probe, electroluminescent and information storage.The phthalocyanine polymerization is one of important channel of improving its performance, polymerized phthalocyanine can be divided into following a few class according to phthalocyanine mode of connection in the polymerized phthalocyanine or one-tenth key type:
(1) the netted polymerized phthalocyanine that constitutes by part: this class polymerization phthalocyanine structure height unanimity, typical preparation method has: A) eight substituted benzene nitrile direct polymerization obtain the inflexible polymerized phthalocyanine, and this type of network polymer can be used for removing metal ion in the water (as Na
+, K
+, Rb
+, Cs
+, Ag
+Deng).B) 1,2,4,5-four benzonitriles or pyromellitic dianhydride directly generate the phthalocyanine network polymer, and this polymkeric substance has electron conductivity.C) by small molecules metal phthalocyanine and the polycondensation of active small molecular compound and get.
(2) polymerized phthalocyanine of coplane accumulation: such polymerized phthalocyanine is to conspire to create by the coordinate metal ion, and this kind accumulation mode has electroconductibility and photoconductivity.
(3) link polymerized phthalocyanine on the polymeric chain by covalent linkage, can be divided into backbone chain type and side chain type.
(4) by the polymerized phthalocyanine on the polymeric chain to body formation coordinate bond or electrostatic interaction formation.
The characteristics of above-mentioned a few class polymerization phthalein mountain valley with clumps of trees and bamboos are to have monometallic title complex active centre, have certain catalysed oxidn, but its catalytic performance a little less than.
Summary of the invention
The purpose of this invention is to provide a kind of polymer catalyst with catalytic molecular oxygen oxidative function---polymer xifualkali phthalocyanin bimetal compound that utilizes small molecules Salen Schiff base metal complexes and metal phthalocyanine complex preparation.
Another object of the present invention provides the preparation method of this polymer xifualkali phthalocyanin bimetal compound.
A further object of the invention, i.e. the application of polymer xifualkali phthalocyanin bimetal compound in catalytic molecular oxygen oxidizing reaction, especially its application in the reaction of catalytic molecular oxygen oxidation isopropyl benzene.
(1) polymer xifualkali phthalocyanin bimetal compound
The structure of polymer xifualkali phthalocyanin bimetal compound of the present invention is shown below:
M in the formula
1, M
2Be transition metal (being mainly copper, cobalt, nickel, manganese etc.) that m, n are 〉=3 integer; M
1, M
2Can be identical transition metal, also can be different transition metals.
From top structural formula as can be seen, two catalytic active centers are arranged in the polymer xifualkali phthalocyanin bimetal compound of the present invention, have very strong catalytic performance.
In order to prove the structure of polymer xifualkali phthalocyanin bimetal compound, with polymer schiff bases cobalt-CuPc bimetal complexes (PSalphCo-PcCu) is example, adopt characterization techniques such as infrared spectra, ultimate analysis, heat analysis that the structure of polymer schiff bases cobalt-CuPc bimetal complexes is characterized, the result shows and has obtained the polymer schiff bases cobalt-CuPc bimetal complexes consistent with said structure.Concrete data are summarized as follows:
(1) infrared spectrum characterization
CuPc metal complexes (CuPc), four SULPHURYL CHLORIDE substituted phthalocyanine copper metal complexes (CuPcSO have been measured
2Cl) and the infrared spectra of polymer schiff bases cobalt-CuPc bimetal complexes (PSalphCo-PcCu).In the infared spectrum of CuPc, at 1615-1089cm
-1Plane C-C or C-N stretching vibration absorption peak that the big ring of phthalocyanine occurred are at 1167-1005cm
-1The in-plane bending vibration absorption peak of C-H on the phenyl ring has appearred, 897-726cm
-1The out-of-plane deformation vibration absorption peak of C-H on the phenyl ring has appearred, 638-435cm
-1Be phenyl ring skeleton out-of-plane deformation vibration absorption peak.CuPcSO
2Cl is at 1377cm
-1And 1175cm
-1ν has appearred respectively in the place
As(S=O) and ν
s(S=O) charateristic avsorption band shows CuPcSO
2Cl is successfully synthesized.In the infared spectrum of PSalphCo-PcCu, ν
As(S=O) charateristic avsorption band moves to the lower wave number direction, is 1365cm
-1, ν
s(S=O) charateristic avsorption band moves to high wave number, is 1193cm
-1Show that polymkeric substance is successfully synthesized.
(2) ultraviolet-visible spectrum
Metal phthalocyanine compound all has absorption in ultraviolet region and visible region, and is stronger in the visible region absorption, is called the Q absorption band; And a little less than the ultraviolet region absorbs generally, be called the B band, and Salen type schiff bases absorption peak is very weak.CuPc can be partially soluble in tetrahydrofuran (THF), and its B band and Q band appear at 324nm and 656nm place respectively.Adopt the ultraviolet-visible diffuse reflection spectrum to measure the PSalphCo-PcCu solid sample, tested Salen type schiff bases cobalt complex Co (di-OHSalphen), CuPc and CuPcSO simultaneously
2The Cl solid sample.Because part and polymkeric substance thereof all contain aromatic structure, thus at ultraviolet region B band absorption is arranged all, and basicly stable at the 310nm place; But bigger, and certain rules is arranged in visible region Q band variation range.Can find that from figure the Q of CuPc takes present 560nm place out of, compare that the Q band moves to the ultraviolet region direction with this sample liquids ultraviolet-visible spectrum test result.Since the effect of chromophore, CuPcSO
2The Q absorption band of Cl and PSalphCo-PcCu is respectively to the visible region red shift.
(3) TG-DTA analyzes
Polymer schiff bases cobalt-CuPc bimetal complexes PSalphCo-PcCu does not decompose in 100 ℃ substantially, and also very slow 100-600 ℃ of scope interpolymer thermolysis speed, weightlessness is no more than 20%, surpasses 90% and Co (di-OHSalphen) is weightless.PSalphCo-PcCu compares stability significantly to be increased with small molecules Salen schiff bases part and metal complexes thereof, compares heat decomposition temperature with CuPc and has reduced about about 200 ℃.
(4) metal content analysis of PSalphCo-PcCu
The metal content analysis result of PSalphCo-PcCu shows Co: Cu/2.2: structural unit Co (Salphen) in 1 (atomic ratio), this and polymer xifualkali phthalocyanin bimetal compound PSalphCo-PcCu: CuPc/2: 1 is approaching.
In addition, the surperficial image that adopted scanning electron microscope observation, micromolecular Co (di-Salphen) and CuPc thereof are typical needle-like crystals, polymer PSalphCo-PcCu then presents the planar sheet structure.Therefore can inference, the high molecular polymer of Co (di-Salphen) and CuPc carries out polycondensation with the planar direction, is a regular flush type macromole polymer.
(2) preparation of polymer xifualkali phthalocyanin bimetal compound
A certain amount of adjacent benzene diimine is contracted (4,4 '-dihydroxyl) salicylic aldehyde schiff bases transition metal complex fully is dissolved in the basic solution, the phase-transfer catalyst that adds described raw material title complex quality 1～10%, the dichloroethane solution that adds the transition metal phthalocyanine SULPHURYL CHLORIDE that is dissolved with 1～2 times of raw material title complex quality again, under agitation react 1～5h, suction filtration, use the NaOH aqueous solution, ethanol and water washing then respectively, vacuum-drying obtains black sheet polymer---polymer xifualkali phthalocyanin bimetal compound
Described adjacent benzene diimine contracts, and transition metal is respectively copper, cobalt, nickel, manganese etc. in (4,4 '-dihydroxyl) salicylic aldehyde schiff bases transition metal complex.Described basic solution is the NaOH aqueous solution, and its percentage concentration is 1～5%.
Described phase-transfer catalyst is a cetyl trimethylammonium bromide.
Described transition metal phthalocyanine SULPHURYL CHLORIDE is copper phthalocyanine SULPHURYL CHLORIDE, cobalt phthalocyanine SULPHURYL CHLORIDE, nickel phthalocyanine SULPHURYL CHLORIDE, manganese phthalocyanine SULPHURYL CHLORIDE etc.
(3) the catalytic molecular oxygen oxidation susceptibility of polymer xifualkali phthalocyanin bimetal compound
From the structure of polymer xifualkali phthalocyanin bimetal compound as can be seen, contain double activity center in the polymer xifualkali phthalocyanin bimetal compound, make this condensation complex have very strong catalytic oxidation performance, can be applicable to catalytic molecular oxygen oxidizing reaction.Be example with PSalphCo-PcCu below, the catalytic molecular oxygen oxidation susceptibility of polymer xifualkali phthalocyanin bimetal compound be described:
With the isopropyl benzene is substrate, with polymer schiff bases cobalt-CuPc bimetal complexes (PSalphCo-PcCu) is catalyzer, with oxygen is that oxygenant carries out the catalyzed oxidation isopropyl benzene: in the time of 100 ℃, reacted 8 hours, cumene oxidation product mainly is 2-phenyl-2-propyl alcohol (PP) and isopropyl benzene hydroperoxide (CHP).Reaction equation is as follows:
Polymer schiff bases cobalt-CuPc bimetal complexes has very strong catalytic activity, and substrate conversion efficiency reaches 76%, and the selectivity of isopropyl benzene hydroperoxide (CHP) has reached 89%.Under promotor participates in isopropyl benzene is had very high transformation efficiency and selectivity, the selectivity of oxidation products isopropyl benzene hydroperoxide (CHP) has reached 95%, and overall selectivity reaches 99%, so this catalyzer can be used as the special-purpose catalyst of producing CHP.
Embodiment
Embodiment 1, a certain amount of adjacent benzene diimine is contracted (4,4 '-dihydroxyl) salicylic aldehyde schiff bases cobalt complex Co (di-OHSalphen) is dissolved in 3.1% the NaOH aqueous solution solution, the cetyl trimethylammonium bromide that adds raw material title complex quality 10%, the dichloroethane solution that under vigorous stirring, adds the copper phthalocyanine SULPHURYL CHLORIDE that is dissolved with 1～2 times of raw material title complex quality, after continuing stirring reaction 2h, suction filtration, use 2% the NaOH aqueous solution respectively, the second alcohol and water respectively washs 3 times, vacuum-drying, obtaining the black sheet polymer---polymer schiff bases cobalt-CuPc bimetal complexes, productive rate are 60%.
Embodiment 2, a certain amount of adjacent benzene diimine is contracted (4,4 '-dihydroxyl) salicylic aldehyde schiff bases cobalt complex Co (di-OHSalphen) is dissolved in 3.1% the NaOH aqueous solution, the cetyl trimethylammonium bromide that adds raw material title complex quality 8%, after under vigorous stirring, adding the dichloroethane solution continuation stirring reaction 2h of the nickel phthalocyanine SULPHURYL CHLORIDE that is dissolved with 1 times of raw material title complex quality, suction filtration, use 2% the NaOH aqueous solution respectively, the second alcohol and water respectively washs 3 times, vacuum-drying, obtaining sheet polymer---polymer schiff bases cobalt-phthalocyanine nickel bimetal title complex, productive rate is 60%.
Embodiment 3, a certain amount of adjacent benzene diimine is contracted (4,4 '-dihydroxyl) salicylic aldehyde schiff bases cobalt complex Co (di-OHSalphen) is dissolved in 3.1% the NaOH aqueous solution, the cetyl trimethylammonium bromide that adds described raw material title complex quality 1～10%, the dichloroethane solution that under vigorous stirring, adds the manganese phthalocyanine SULPHURYL CHLORIDE that is dissolved with 1～2 times of raw material title complex quality, after continuing stirring reaction 2h, suction filtration, use 2% the NaOH aqueous solution respectively, the second alcohol and water respectively washs 3 times, vacuum-drying, obtain polymer schiff bases cobalt-manganese phthalocyanine bimetal complexes, productive rate is 61%.
Embodiment 4, a certain amount of adjacent benzene diimine is contracted (4,4 '-dihydroxyl) salicylic aldehyde schiff bases copper complex Cu (di-OHSalphen) is dissolved in 3.1% the NaOH aqueous solution, the cetyl trimethylammonium bromide that adds raw material title complex quality 1～10%, the dichloroethane solution that under vigorous stirring, adds the copper phthalocyanine SULPHURYL CHLORIDE that is dissolved with 2 times of raw material title complex quality, after continuing stirring reaction 2h, suction filtration, use 2% the NaOH aqueous solution respectively, the second alcohol and water respectively washs 3 times, vacuum-drying, obtaining sheet polymer---polymer schiff bases copper-CuPc bimetal complexes, productive rate are 58%.
Embodiment 5, a certain amount of adjacent benzene diimine is contracted (4,4 '-dihydroxyl) salicylic aldehyde schiff bases copper complex Cu (di-OHSalphen) is dissolved in 3.1% the NaOH aqueous solution, the cetyl trimethylammonium bromide that adds described raw material title complex quality 5%, the dichloroethane solution that under vigorous stirring, adds the nickel phthalocyanine SULPHURYL CHLORIDE that is dissolved with 2 times of raw material title complex quality, after continuing stirring reaction 2h, suction filtration, use 2% the NaOH aqueous solution respectively, the second alcohol and water respectively washs 3 times, vacuum-drying obtains sheet polymer---polymer schiff bases copper-phthalocyanine nickel bimetal title complex.
Embodiment 6, a certain amount of adjacent benzene diimine is contracted (4,4 '-dihydroxyl) salicylic aldehyde schiff bases copper complex Cu (di-OHSalphen) is dissolved in 1% the NaOH aqueous solution, the cetyl trimethylammonium bromide that adds described raw material title complex quality 5%, the dichloroethane solution that under vigorous stirring, adds the manganese phthalocyanine SULPHURYL CHLORIDE that is dissolved with 2 times of raw material title complex quality, after continuing stirring reaction 2h, suction filtration, respectively wash 3 times with 3% the NaOH aqueous solution, second alcohol and water respectively, vacuum-drying obtains polymer schiff bases copper-manganese phthalocyanine bimetal complexes.
Embodiment 7, a certain amount of adjacent benzene diimine is contracted (4,4 '-dihydroxyl) salicylic aldehyde schiff bases nickel complex Ni (di-OHSalphen) is dissolved in 1% the NaOH aqueous solution, the cetyl trimethylammonium bromide that adds described raw material title complex quality 5%, the dichloroethane solution that under vigorous stirring, adds the cobalt phthalocyanine SULPHURYL CHLORIDE that is dissolved with 1.5 times of raw material title complex quality, after continuing stirring reaction 2h, suction filtration, respectively wash 3 times with 2% the NaOH aqueous solution, second alcohol and water respectively, vacuum-drying obtains polymer schiff bases nickel-phthalocyanine cobalt dual-metal title complex.
Embodiment 8, a certain amount of adjacent benzene diimine is contracted (4,4 '-dihydroxyl) salicylic aldehyde schiff bases nickel complex Ni (di-OHSalphen) is dissolved in 1% the NaOH aqueous solution, the cetyl trimethylammonium bromide that adds described raw material title complex quality 5%, the dichloroethane solution that under vigorous stirring, adds the copper phthalocyanine SULPHURYL CHLORIDE that is dissolved with 1.5 times of raw material title complex quality, after continuing stirring reaction 2h, suction filtration, respectively wash 3 times with 1% the NaOH aqueous solution, second alcohol and water respectively, vacuum-drying obtains polymer schiff bases nickel-CuPc bimetal complexes.
Embodiment 9, a certain amount of adjacent benzene diimine is contracted (4,4 '-dihydroxyl) salicylic aldehyde schiff bases nickel complex Ni (di-OHSalphen) is dissolved in 3.1% the NaOH aqueous solution, the cetyl trimethylammonium bromide that adds described raw material title complex quality 3%, the dichloroethane solution that under vigorous stirring, adds the manganese phthalocyanine SULPHURYL CHLORIDE that is dissolved with 1 times of raw material title complex quality, after continuing stirring reaction 2h, suction filtration, respectively wash 3 times with 3% the NaOH aqueous solution, second alcohol and water respectively, vacuum-drying obtains polymer schiff bases nickel-manganese phthalocyanine bimetal complexes.
Embodiment 10, a certain amount of adjacent benzene diimine is contracted (4,4 '-dihydroxyl) salicylic aldehyde schiff bases manganese complex Mn (di-OHSalphen) is dissolved in 5% the NaOH aqueous solution, the cetyl trimethylammonium bromide that adds described raw material title complex quality 3%, the dichloroethane solution that under vigorous stirring, adds the cobalt phthalocyanine SULPHURYL CHLORIDE that is dissolved with 1.5 times of raw material title complex quality, after continuing stirring reaction 2h, suction filtration, respectively wash 3 times with 4% the NaOH aqueous solution, second alcohol and water respectively, vacuum-drying obtains polymer schiff bases manganese-phthalocyanine cobalt dual-metal title complex.
Embodiment 11, a certain amount of adjacent benzene diimine is contracted (4,4 '-dihydroxyl) salicylic aldehyde schiff bases manganese complex Mn (di-OHSalphen) is dissolved in 5% the NaOH aqueous solution, the cetyl trimethylammonium bromide that adds described raw material title complex quality 1%, the dichloroethane solution that under vigorous stirring, adds the copper phthalocyanine SULPHURYL CHLORIDE that is dissolved with 1 times of raw material title complex quality, after continuing stirring reaction 2h, suction filtration, respectively wash 3 times with 5% the NaOH aqueous solution, second alcohol and water respectively, vacuum-drying obtains polymer schiff bases manganese-CuPc bimetal complexes.
Embodiment 12, the application of polymer schiff bases cobalt-CuPc bimetal complexes in producing isopropyl benzene hydroperoxide (CHP): with the isopropyl benzene is raw material, polymer schiff bases cobalt-CuPc bimetal complexes is a catalyzer, molecular oxygen is an oxygenant, in the time of 100 ℃, reacted 8 hours, oxidation products mainly is 2-phenyl-2-propyl alcohol (PP) and isopropyl benzene hydroperoxide (CHP).The isopropyl benzene transformation efficiency reaches 76%, and the selectivity of isopropyl benzene hydroperoxide (CHP) has reached 89%.Under promotor participates in isopropyl benzene is had very high transformation efficiency and selectivity, the selectivity of oxidation products isopropyl benzene hydroperoxide (CHP) has reached 95%, and overall selectivity reaches 99%, so this catalyzer can be used as the special-purpose catalyst of producing CHP.
Claims (9)
1, a kind of polymer xifualkali phthalocyanin bimetal compound, its structure is shown below:
M in the formula
1, M
2Be transition metal, m, n are 〉=3 integer.
2, polymer xifualkali phthalocyanin bimetal compound according to claim 1 is characterized in that: M
1, M
2For identical transition metal or be different transition metals.
3, polymer xifualkali phthalocyanin bimetal compound as claimed in claim 1 or 2, it is characterized in that: described transition metal is copper, cobalt, nickel or manganese.
4, the preparation method of polymer xifualkali phthalocyanin bimetal compound according to claim 1, be that a certain amount of adjacent benzene diimine is contracted (4,4 '-dihydroxyl) salicylic aldehyde schiff bases transition metal complex fully is dissolved in the basic solution, the cetyl trimethylammonium bromide that adds described raw material title complex quality 1～10%, the dichloroethane solution that adds the transition metal phthalocyanine SULPHURYL CHLORIDE that is dissolved with 1～2 times of raw material title complex quality again, under agitation react 1～5h, suction filtration, use the NaOH aqueous solution then respectively, ethanol and water washing, vacuum-drying obtains black sheet polymer---polymer xifualkali phthalocyanin bimetal compound.
5, as the preparation method of polymer xifualkali phthalocyanin bimetal compound as described in the claim 4, it is characterized in that: described adjacent benzene diimine contracts (4,4 '-dihydroxyl) salicylic aldehyde schiff bases transition metal complex is the contract metal complexes of (4,4 '-dihydroxyl) salicylic aldehyde schiff bases copper or cobalt or nickel or manganese of adjacent benzene diimine.
6, as the preparation method of polymer xifualkali phthalocyanin bimetal compound as described in the claim 4, it is characterized in that: basic solution is the NaOH aqueous solution, and its concentration is 1～5%.
7, as the preparation method of polymer xifualkali phthalocyanin bimetal compound as described in the claim 4, it is characterized in that: described transition metal phthalocyanine SULPHURYL CHLORIDE is copper phthalocyanine SULPHURYL CHLORIDE or cobalt phthalocyanine SULPHURYL CHLORIDE or nickel phthalocyanine SULPHURYL CHLORIDE or manganese phthalocyanine SULPHURYL CHLORIDE.
8, polymer xifualkali phthalocyanin bimetal compound is used as catalyzer according to claim 1.
9, polymer xifualkali phthalocyanin bimetal compound is used as the catalyzer of producing isopropyl benzene hydroperoxide according to claim 1.
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2006
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| JP2000297083A (en) * | 1999-04-15 | 2000-10-24 | Mitsubishi Chemicals Corp | Production of 2,5-dihydrofuran |
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