CN102060990B - Magnetic supported catalyst and application thereof in preparing polyphenyleneoxide in aqueous medium - Google Patents

Magnetic supported catalyst and application thereof in preparing polyphenyleneoxide in aqueous medium Download PDF

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CN102060990B
CN102060990B CN2010105617090A CN201010561709A CN102060990B CN 102060990 B CN102060990 B CN 102060990B CN 2010105617090 A CN2010105617090 A CN 2010105617090A CN 201010561709 A CN201010561709 A CN 201010561709A CN 102060990 B CN102060990 B CN 102060990B
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polyvinyl imidazol
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CN102060990A (en
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张文丽
王奂
申屠宝卿
翁志学
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Zhejiang University ZJU
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Abstract

The invention discloses a magnetic supported catalyst, which is a complex of a nano magnetic particle surface grafted polyvinyl imidazol ligand and metal ions. A molar ratio of imidazol groups to the metal ions in the complex is (0.5-300):1; and the polyvinyl imidazol ligand is homopolymer of N-polyvinyl imidazol monomers or copolymer of N-polyvinyl imidazol monomers and one or more types of water-soluble monomers. The catalyst has high catalytic efficiency, and can be separated from a reaction medium by applying a magnetic field, so that the catalyst is recycled, and solves the problem that the conventional catalyst has low catalytic efficiency of preparing polyphenyleneoxide (PPO) in a reaction medium, particularly in an aqueous medium, and is difficult to recycle. The invention also discloses a preparation method and application of the magnetic supported catalyst. The preparation method is easy to operate and control, and is suitable for industrial production.

Description

A kind of magnetic loading type catalyzer and the application that in water medium, prepares ppe thereof
Technical field
The present invention relates to the polymer-metal complex catalyst field, be specifically related to a kind of magnetic loading type Catalysts and its preparation method, and magnetic loading type catalyzer prepares the application of ppe in water medium.
Background technology
The catalyst recovery recycle utilization can reduce production cost of products significantly, thereby obtains research extensively and profoundly.Usually the method that adopts is that homogeneous catalyst is loaded on (normally micron order carrier) on the inert support, forms heterogeneous catalyst, and reaction finishes the back through simple filtration or centrifugation method Separation and Recovery catalyzer, further recycle.Yet, to compare with homogeneous catalyst, the catalytic activity of the heterogeneous catalyst of gained and selectivity all have decline by a relatively large margin after the load.The size of carrier is reduced to the nano level scope can makes loaded catalyst keep the catalytic activity and the selectivity of homogeneous catalyst basically, reason is that the nano-carrier yardstick is little, and specific surface area is big, fully contacts with reaction substrate easily.But manometer load-type catalyst can not separate from reaction system through methods such as simple filtration; Therefore the recycle and reuse of catalyzer remains a technical barrier (Aiguo Hu; Gordon T.Yee, and Wenbin Lin, Magnetically Recoverable Chiral Catalysts Immobilized on Magnetite Nanoparticles for Asymmetric Hydrogenation of Aromatic Ketones; J.Am.Chem.Soc.; 2005,127 (36), 12486-12487).
Superparamagnetic material self does not have magnetic, but in the presence of external magnetic field, can be magnetized.This characteristic makes superparamagnetic material be widely used in biomedicine fields such as protein purification, targeted drug conveying.Select for use the nanoscale, superparamagnetic material to be expected to high catalytic activity and the selectivity that solves a catalyst recovery round-robin difficult problem and keep the load rear catalyst as the carrier of homogeneous catalyst.U.S. Pat 2008021179-A1, US20070277649-A1, Japanese Patent JP 2008221076, Chinese patent CN 101181687A and Chinese patent CN 1583270A etc. adopt the carrier of magnetic particle as catalyzer, and reaction finishes the back and reclaims catalyzer through externally-applied magnetic field.Jin-Kyu Lee etc. adopt the carrier of magnetic nano-particle as ruthenium catalyst, the load rear catalyst are applied to the hydroformylation reaction of alkene, through the foreign field Separation and Recovery; After the recycle 6 times, catalyzer still can keep high catalytic activity and selectivity (Tae-Jong Yoon, Woo Lee; Yoon-Seuk Oh and Jin-Kyu Lee; Magnetic nanoparticles as a catalyst vehicle for simple and easy recycling, New J.Chem., 2003; 27,227-229).
Gather 2,6-dialkyl group phenylate is called for short ppe (PPO), because of its excellent physical strength, thermotolerance, electrical insulating property, dimensional stability etc., has purposes widely in fields such as electric, automotive industry, machinofacture.U.S. Pat 3,306,874, US3,306,875, US 3,257,357, US 3,257,358 grades announced the method that the phenol compound oxidative coupling polymerization is produced ppe in the organic solvent.This method is the good solvent that phenol compound is dissolved in ppe, adds metals ion-amine complex compound catalyst, under the atmosphere of oxygen-containing gas, carries out the oxypolymerization of phenol compound.After the finishing polymerization, add the poor solvent of ppe, the ppe deposition is separated out, filtering separation obtains ppe.The shortcoming of this method is to use a large amount of organic solvents, and serious environment pollution does not meet the requirement of Green Chemistry, and needs solvent recuperation and high temperature devolatilization device, has increased production cost.
Patent WO2006030670-A1, US2008071059-A1, JP4022925-B2, JP2006535779-X etc. have announced the method for preparing PPO in the water medium.This method is in full water medium, to adopt basic cpd to make phenol compound slough proton; Generate water miscible benzene oxygen anion; Add metals ion-amine complex compound catalyst and tensio-active agent, under the atmosphere of oxygenant oxygen-containing gas, carry out the oxypolymerization of phenol compound.After the finishing polymerization, adopt the metal-salt breakdown of emulsion, filtering separation obtains ppe.This method has overcome the shortcoming of PPO traditional preparation process method, with full water medium replace organic solvent, meets the requirement of Green Chemistry, but catalytic efficiency (still remains to be improved.
Specific functions such as in recent years, polymer-metal complex is owing to have a highly selective, high catalytic activity and receiving much concern.Metallic ion-polyvinyl imidazol complex is a kind of in numerous polymer-metal complexs because the polyvinyl imidazol molecular chain contains numerous imidazole group, can with Cu 2+, Zn 2+, Cd 2+, Ag +, Hg 2+Form stable complex compound Deng metals ion, be widely used in the fields such as recovery of industrial sewage processing and heavy metal.Like document " using poly N-vinyl imidazoles hydrogel to remove the mercury (II) in the acidic aqueous solution " (Removal of Hg (II) from Acid Aqueous Solutions by Poly (N-Vinylimidazole) Hydrogel, M.J.MOLINA, M.R.GO MEZ-ANTO N; B.L.RIVAS; H.A.MATURANA, I.F.PIE ' ROLA, Journal of Applied Polymer Science; Vol.79,1467-1475 (2001)) disclose in a kind of N-vinyl imidazole polymkeric substance can and Hg 2+Complexing is used for removing the Hg of the aqueous solution 2+The application that discloses the preparation method of metallic ion-polyvinyl imidazol complex catalyst in the one Chinese patent application 200910097970.7 and in water medium, prepared ppe; Find that its catalytic efficiency (is better than metals ion-low molecular weight ligands complex compound; Though this catalyzer has higher catalytic efficiency, still there is the problem that catalyzer can not recycling.
The recovery and reuse of catalyzer can significantly reduce production costs, and economize on resources, and have very high practical value.At present; The recycling use of synthetic ppe catalyst system therefor remains a technical barrier in the water medium; Reason is that the reaction of synthetic ppe in the water medium is an inhomogeneous reaction; Monomer generates water-soluble benzene oxygen anion under the effect of alkali, along with the carrying out of oxidative coupling polymerization reaction, form low-molecular-weight oligomer.After the polymerization degree was greater than 6, low-molecular-weight oligomer was water insoluble and deposition is separated out, through the stable polymer particle that forms of tensio-active agent; Make the oxidative coupling polymerization reaction continue to carry out, reaction is used the metal-salt breakdown of emulsion after finishing; Ppe is separated out, and filtration can obtain the ppe product.Yet the metal-salt that catalyzer, emulsifying agent and breakdown of emulsion are used all is present in the filtrating, and the filtrating of containing catalyzer can't recycle; And if adopt traditional method, with catalyst cupport (polymkeric substance or silica gel) on inert support, then the catalyzer after the load can't separate with the ppe product.Therefore, the recovery and reuse problem of the catalyzer of preparation PPO is still the unresolved technical problem that gets in the water medium.
Summary of the invention
The invention provides the magnetic loading type catalyzer that a kind of catalytic efficiency (is high, be easy to reclaim.
The present invention also provides a kind of magnetic loading type Preparation of catalysts method, and this method is simple to operate, be easy to control, is suitable for suitability for industrialized production.
The present invention also provides a kind of magnetic loading type catalyzer in water medium, to prepare the application method of PPO, and the catalyzer in this method can be for recycling and reuse.
A kind of magnetic loading type catalyzer is the polyvinyl imidazol class part of magnetic nanoparticle surface grafting and the title complex of metals ion;
The mol ratio of imidazole group and metals ion is 0.5～300: 1 in the described title complex; The mol ratio of preferred imidazole group and metals ion is 2～30: 1, and in this scope, speed of reaction is faster; By-products content still less, the ppe yield is higher and molecular weight is higher.
Described magnetic nanoparticle is the nano ferriferrous oxide particle;
Described metals ion is cupric ion or mn ion;
Described polyvinyl imidazol class part is the multipolymer of the monomeric homopolymer of N-vinyl imidazole class or N-vinyl imidazole class monomer and other one or more water-soluble monomers;
Wherein, described N-vinyl imidazole class monomer is the compound shown in formula (I) structural formula:
Figure BDA0000034527720000031
Formula (I);
In the formula (I), R 1Be hydrogen, C 1～C 4Alkyl or phenyl, R 2Be hydrogen, C 1～C 4Alkyl or phenyl, R 3Be hydrogen, C 1～C 4Alkyl or phenyl, R 1, R 2And R 3Identical or different;
Described water-soluble monomer can be N-vinyl amide monomer, acrylamide monomers, (methyl) acrylic acid hydroxy alkyl ester class monomer, unsaturated carboxylic acid or anhydrides monomer.
Wherein, the N-vinyl amide monomer comprises N-vinyl pyrrolidone, N-caprolactam, N-vinyl acetamide or N-methyl-N-vinyl acetamide etc.
Acrylamide monomers comprises acrylic amide, USAF RH-1, N, N '-DMAA or N-methylol methacrylamide etc.
(methyl) acrylic acid hydroxy alkyl ester class monomer comprises (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate or the many glycol esters of (methyl) vinylformic acid etc.
Unsaturated carboxylic acid and anhydrides monomer comprise vinylformic acid, methylacrylic acid, methylene-succinic acid, toxilic acid, fumaric acid, maleic anhydride, fumaric acid anhydride etc.
The preferred N-vinyl amide monomer of described water-soluble monomer, preferred especially N-vinyl pyrrolidone.
The weight percentage of described water-soluble monomer in polyvinyl imidazol class part is 0～99%, is preferably 10%～50%.
The monomeric quality percentage composition of N-vinyl imidazole class is preferably 1%～100% in the described polyvinyl imidazol class part, further is preferably 50%～90%.
The weight-average molecular weight of described polyvinyl imidazol class part is preferably 10 3～10 7, further be preferably 10 3～10 5Molecular weight is less than 10 3The time, grafted chain length is short, and it is not obvious to concentrate effect, and catalytic efficiency (is low; Molecular weight is greater than 10 7The time, tangle each other between the grafted chain, be unfavorable for that catalyzer fully contacts with reaction substrate.
Described cupric ion is from water-soluble cupric salt, cuprous salt or its mixture; Can select at least a in cuprous chloride, cuprous bromide, cuprous sulfate, cuprous nitrate, cupric chloride, cupric bromide, copper sulfate, the cupric nitrate for use, preferred cuprous chloride, cuprous bromide, cupric chloride or cupric bromide.
Described mn ion is from water-soluble manganese salt, can select at least a in Manganous chloride tetrahydrate, Manganese dibromide, manganese iodide, manganous carbonate, manganese acetate, manganous nitrate, manganous sulfate, the manganous phosphate etc. for use.
Described magnetic loading type Preparation of catalysts method may further comprise the steps:
(1) in the presence of silane coupling agent, synthesizes the polyvinyl imidazol class part that an end has silane coupling agent through the method for radical initiation N-vinyl imidazole class monomer homopolymerization or N-vinyl imidazole class monomer and other one or more water-soluble monomer copolymerization;
Wherein silane coupling agent and the monomeric mol ratio of N-vinyl imidazole class be preferably 1: 10～100;
(2) the polyvinyl imidazol class part that an end that makes in magnetic nanoparticle and the step (1) is had a silane coupling agent carries out linked reaction through silane coupling agent; Polyvinyl imidazol class part is grafted to the magnetic nanoparticle surface, obtains the polyvinyl imidazol class part of magnetic nanoparticle surface grafting;
Wherein the end mass ratio that has polyvinyl imidazol class part and a magnetic nanoparticle of silane coupling agent be preferably 1: 1～100;
(3) with the aqueous solution of the aqueous solution with the metals ion of the polyvinyl imidazol class part of the magnetic nanoparticle surface grafting that makes in the step (2) (can through stir or ultrasonication mix); Make imidazole group and metals ion generation coordination reaction, make magnetic loading type catalyzer.Because metals ion and polyvinyl imidazol class part are easy to react, so coordination reaction can be carried out under normal temperature, normal pressure, the reaction times is also very short, and general reaction system mixes the just basic end of afterreaction.
In the step (1), the method detailed process of homopolymerization of radical trigger monomer or copolymerization is: decomposition of initiator is a radical, and this radical is captured the sulfydryl hydrogen in the silane coupling agent, generates the sulfydryl radical, further trigger monomer homopolymerization of sulfydryl radical or copolymerization; Perhaps decomposition of initiator is a radical; This radical trigger monomer polymerization generates monomer or free polymer readical; Monomer or free polymer readical are captured the sulfydryl hydrogen in the silane coupling agent, generate the sulfydryl radical, further trigger monomer homopolymerization of sulfydryl radical or copolymerization.Initiator also possibly directly cause partial monosomy homopolymerization or copolymerization; Generate homopolymer or multipolymer that a part does not contain silane coupling agent; This part homopolymer or multipolymer that does not contain silane coupling agent can't be grafted to the magnetic nanoparticle surface, but can't influence effect of the present invention.Wherein, Used initiator can be the water-soluble and oil-soluble superoxide of routine, in the azo cpd one or more, for example alkali-metal persulphate, ammonium persulphate, BPO, ditertiary butyl peroxide, tertbutyl peroxide, Diisopropyl azodicarboxylate etc.; Also can be the redox initiator system, like tertbutyl peroxide-sodium disulfide redox initiator system or tertbutyl peroxide-sodium hydroxymethanesulfinate redox initiator system etc.The consumption of initiator generally is 0.05%～5% (mass percent) of polymerization single polymerization monomer consumption.Homopolymerization of described radical trigger monomer or copolyreaction time were generally 12～72 hours.
Described silane coupling agent comprises one or more in 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercapto propyl group methyl dimethoxysilane, 3-mercapto propyl group methyldiethoxysilane, 4-mercapto butyl trimethoxy silane, the 4-mercapto butyl triethoxyl silane etc.
The present invention is employed in preparation magnetic loading type catalyzer in the water solution system, is because the magnetic loading type catalyzer that in water solution system, prepares can directly use, and need not special processing.
Described magnetic loading type catalyzer can be used for preparing ppe in the water medium, and can be used for catalysis is raw material prepares ppe in water medium oxidative polymerization with phenol monomer, basic cpd, tensio-active agent and oxygenant.
Described magnetic loading type catalyzer finishes back externally-applied magnetic field capable of using at oxidative polymerization and recycles.
Concrete utilize magnetic loading type catalyzer in water medium, prepare the ppe method to be: the employing basic cpd makes the phenol monomer slough proton in water medium; Generate water-soluble benzene oxygen anion; Add magnetic loading type catalyzer and tensio-active agent, in the presence of oxygenant, carry out the monomeric oxypolymerization of phenol, after polyreaction finishes; Utilize externally-applied magnetic field that magnetic loading type catalyzer is separated with reaction product; Magnetic loading type catalyzer after the recovery is dried through washing, and capable of circulation being used for reacts next time; Reaction product adopts the metal-salt breakdown of emulsion, and filtering separation obtains ppe.
The mol ratio of each raw material consists of in the described oxidative polymerization:
Phenol monomer 1;
Metals ion 0.0001～1 in the magnetic loading type catalyzer;
Tensio-active agent 0.001～1;
Basic cpd 0.1～100;
Oxygenant is an amount of.
Described phenol monomer is the compound shown in formula (II) structural formula:
Figure BDA0000034527720000061
Formula (II)
In the formula (II), R 4Be C 1～C 4Alkyl or phenyl, R 5Be C 1～C 4Alkyl or phenyl, R 6Be hydrogen or halogen; R 4And R 5Identical or different.
Described phenol monomer can select 2 for use; 6-xylenol, 2; 6-diethyl phenol, 2; 6-DI-tert-butylphenol compounds, 2-methyl-6-ethylphenol, 2,6-dipropyl phenol, 2-methyl-6-propylphenol, 2-ethyl-6-propylphenol, 2,6-phenylbenzene phenol, 2-methyl-6-phenylphenol, 2-ethyl-6-phenylphenol, 2-propyl group-6-phenylphenol, 2; 6-dimethyl--4-bromophenol, 2; 6-diethylammonium-4-bromophenol, 2-methyl-6-ethyl-4-bromophenol, 2,6-dipropyl-4-bromophenol, 2-methyl-6-propyl group-4-bromophenol, 2-ethyl-6-propyl group-4-bromophenol, 2,6-phenylbenzene-4-bromophenol, 2-methyl-6-phenyl-4-bromophenol, 2-ethyl-6-phenyl-4-bromophenol, 2-propyl group-6-phenyl-4-bromophenol, 2; 6-dimethyl--4-chlorophenol, 2; 6-diethylammonium-4-chlorophenol, 2-methyl-6-ethyl-4-chlorophenol, 2,6-dipropyl-4-chlorophenol, 2-methyl-6-propyl group-4-chlorophenol, 2-ethyl-6-propyl group-4-chlorophenol, 2, one or more in 6-phenylbenzene-4-chlorophenol, 2-methyl-6-phenyl-4-chlorophenol, 2-ethyl-6-phenyl-4-chlorophenol, the 2-propyl group-6-phenyl-4-chlorophenol etc.; Preferred employing 2, the 6-xylenol.
The monomeric mol ratio of described basic cpd and phenol is 0.1～100: 1, is preferably 1～50: 1.When basic cpd and the monomeric mol ratio of phenol greater than 100 the time, magnetic loading type catalyzer is under the highly basic condition, inactivation easily is unfavorable for the carrying out of oxidative polymerization; When mol ratio less than 0.1 the time, the phenol monomer is difficult to slough proton, generates water-soluble benzene oxygen anion, and oxidizing potential is high, is unfavorable for the carrying out of oxidative polymerization.
Described basic cpd can adopt one or more in Pottasium Hydroxide, sodium hydroxide, Lithium Hydroxide MonoHydrate, sodium methylate, yellow soda ash, salt of wormwood, saleratus, the sodium hydrogencarbonate etc.
Metals ion and the monomeric mol ratio of phenol are 0.0001～1 in the described magnetic loading type catalyzer, are preferably 0.001～0.1; Metals ion and the monomeric mol ratio of phenol are less than 0.0001 in the magnetic loading type catalyzer, and the ppe productive rate reduces, and molecular weight of product reduces, and by product increases; Mol ratio is greater than 1, and the catalyzer add-on is big, and catalytic efficiency (reduces, and the metals ion residual quantity is big, influences the thermostability of ppe.
Described tensio-active agent is one or more in AS, the nonionogenic tenside.Wherein, described aniorfic surfactant can be selected one or more in carboxylate surface active agent, alkyl sulfate surfactant, alkyl sulfonate surfactants, the alkyl benzene sulfonate surfactant for use.
The general formula of described carboxylate surface active agent is RCOOM, and wherein R is alkyl (preferred C 12-C 18Alkyl), M is a metals ion, for example the dodecyl carboxylic acid sodium.
The general formula of described alkyl sulfate surfactant is ROSO 3M, wherein R is alkyl (preferred C 8-C 18Alkyl), M is a metals ion, for example sodium lauryl sulphate, Sodium palmityl sulfate, sodium stearyl sulfate etc.
The general formula of described AS is R-SO 3M, R is alkyl (preferred C in the formula 12-C 16Alkyl), M is a metals ion, sodium sulfosuccinate for example, sodium cetanesulfonate etc.
The general formula of described sulfonated alkylbenzene is R-C 6H 4-SO 3M, R is alkyl (preferred C in the formula 12-C 16Alkyl), M is a metals ion, X 2073 for example, hexadecyl Supragil GN etc.
Described non-ionics can be selected one or more in AEO, polyoxyethylene alkylphenol ether, the polyvalent alcohol alkyl esters tensio-active agent for use, for example dodecyl glyceryl ester etc.
The monomeric mol ratio of described tensio-active agent and phenol is 0.001～1; Mol ratio is less than 0.001, and the ppe molecular weight reduces, and physicals descends; Mol ratio is greater than 1, and the tensio-active agent residual quantity is big, influences the ppe performance.
Described oxygenant can be selected oxygen-containing gas for use; Like oxygen, air or oxygen and rare gas element with various ratios (oxygen proportion can not be 0) blended gas; What play oxygenizement in the mixed gas is oxygen, thus the present invention when mentioning the oxygenant consumption all with oxymeter.
When every moles of phenol class monomer and oxygen reaction, can know that according to reaction formula the oxygen of participating in reaction in theory is 0.5 mole, but oxygen does not measure in the actually operating, generally all can add excess of oxygen, therefore the upper limit of not strict restriction oxygenant consumption.
The temperature of described oxidative polymerization is preferably 1～80 ℃, further is preferably 40～60 ℃, and the time of oxidative polymerization is preferably 2～30 hours.Mainly be that speed of reaction is slow when being lower than 1 ℃ owing to temperature of reaction; When temperature of reaction was higher than 80 ℃, by product increased, and the ppe productive rate reduces.
Compared with prior art, the present invention has following advantage:
Catalyzer of the present invention has combined the characteristics of magnetic nanoparticle and metallic ion-polyvinyl imidazol class ligand complex; Magnetic nanoparticle is little as the carrier yardstick of catalyzer, has very big specific surface area, and catalyzer is fully contacted with reaction substrate; Have higher catalytic efficiency, help the useful load and the catalysis of catalyzer, magnetic nanoparticle is the magnetic core of catalyzer simultaneously; Can reclaim catalyzer through externally-applied magnetic field, therefore, catalyzer of the present invention not only catalytic efficiency (is high; And can from reaction medium, separate through externally-applied magnetic field, reclaim, thereby realize recycling of catalyzer; Solved present catalyzer in reaction medium especially in the water medium catalytic efficiency (of preparation PPO lower, and catalyzer is difficult to the problem of recycle and reuse.
Preparing method of the present invention is simple to operate, be easy to control, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is for the polyvinyl imidazol part that has silane coupling agent of preparation among the embodiment 1 1H-NMR figure.
Embodiment
Embodiment 1 magnetic loading type polyvinyl imidazol class part-metal ion match Preparation of catalysts
(1) preparation of nano ferriferrous oxide
The aqueous sodium hydroxide solution 250mL of preparation 0.5mol/L adds in the there-necked flask.Under nitrogen protection, be warmed up to 80 ℃.Preparation FeCl 36H 2O concentration is 1mol/L, FeCl 24H 2O concentration is that 0.5mol/L, HCl concentration are the aqueous solution 25mL of 0.4mol/L, under 1200 rev/mins of mechanical stirring, it is dropped in the above-mentioned aqueous sodium hydroxide solution.Reacted 30 minutes.After reaction finishes, clean respectively 5 times, utilize the vacuum-drying 24 hours under room temperature of the separating obtained solid of externally-applied magnetic field, prepare the nano ferriferrous oxide of black with zero(ppm) water and ethanol.
(2) one ends have polyvinyl imidazol class part synthetic of silane coupling agent
N-vinyl imidazole 2.72mL (30mmol), the 3-mercaptopropyl trimethoxysilane 0.3mL (1.5mmol) of underpressure distillation are dissolved in the distilled methyl alcohol of 30mL; Add N-vinyl imidazole monomer mass mark and be 2% Diisopropyl azodicarboxylate as initiator, N 2Atmosphere, stirring reaction is 48 hours under 65 ℃ of reflux temperatures.Reaction finishes back underpressure distillation concentration response product, and-20 ℃ add anhydrous diethyl ether, stir; Obtain white depositions, filter, anhydrous diethyl ether washing 3 times; Vacuum-drying 48 hours makes the polyvinyl imidazol part that an end has silane coupling agent, and the nuclear magnetic spectrogram of this part is as shown in Figure 1.The weight-average molecular weight that gained one end has the polyvinyl imidazol part of silane coupling agent is 3.4 * 10 3
The feed ratio that changes N-vinyl imidazole and 3-mercaptopropyl trimethoxysilane can make the polyvinyl imidazol class part of the band silane coupling agent of different molecular weight.
(3) nano ferriferrous oxide and an end have the reaction of the polyvinyl imidazol part of silane coupling agent
Under the mechanical stirring, the polyvinyl imidazol part (1.7g) that an end is had a silane coupling agent and nano ferriferrous oxide (1.9g) 110 ℃ of back flow reaction 48 hours in the mixing solutions of 100mL toluene and methanol=80: 20 (volume ratio).After reaction finished, product was with methanol wash 3 times, and deionized water wash 3 times utilizes externally-applied magnetic field to separate, and separating obtained solid makes the polyvinyl imidazol class part of magnetic nanoparticle surface grafting through vacuum-drying 48 hours.
(4) the polyvinyl imidazol class part and the metallic ion coordination of magnetic nanoparticle surface grafting
With CuCl 22H 2O (0.0086g; 0.05mmol) and the polyvinyl imidazol class part (0.1724g of magnetic nanoparticle surface grafting; Wherein imidazole group content is 0.2mmol) be dissolved in respectively in the water of 5mL; Mix and ultrasonic 30 minutes, make cupric ion and imidazole group coordination, obtain magnetic loading type polyvinyl imidazol class part-metal ion match catalyzer.
Embodiment 2～4
Except the mixture that adopts N-vinyl imidazole monomer and water-soluble comonomer replaces the N-vinyl imidazole among the embodiment 1; All the other operations all are same as embodiment 1; Prepare the polyvinyl imidazol class part that an end has silane coupling agent; Concrete parameter is seen table 1, finally obtains magnetic loading type polyvinyl imidazol class part-metal ion match catalyzer.
Table 1
Figure BDA0000034527720000101
Embodiment 5～6
Except the ingredient proportion that changes N-vinyl imidazole and 3-mercaptopropyl trimethoxysilane; All the other operations all are same as embodiment 1; Prepare the polyvinyl imidazol class part that an end has silane coupling agent; Concrete parameter is seen table 2, finally obtains magnetic loading type polyvinyl imidazol class part-metal ion match catalyzer.
Table 2
The embodiment sequence number N-vinyl imidazole/3-mercaptopropyl trimethoxysilane The part weight-average molecular weight
5 5.44mL(60mmol)/0.3mL(1.5mmol) 6.7×10 3
6 10.88mL(120mmol)/0.3mL(1.5mmol) 1.2×10 4
Embodiment 7～8
Except adopting Potassium Persulphate or tertbutyl peroxide/sodium disulfide initiator system to replace the Diisopropyl azodicarboxylate among the embodiment 1; All the other operations all are same as embodiment 1; Prepare the polyvinyl imidazol class part that an end has silane coupling agent; Concrete parameter is seen table 3, finally obtains magnetic loading type polyvinyl imidazol class part-metal ion match catalyzer.
Table 3
The embodiment sequence number Initiator The part weight-average molecular weight
7 Potassium Persulphate 7.3×10 3
8 Tertbutyl peroxide/sodium disulfide 7.9×10 3
Embodiment 9～10
Except the time that changes polyreaction; All the other operations all are same as embodiment 1; Prepare the polyvinyl imidazol class part that an end has silane coupling agent, concrete parameter is seen table 4, finally obtains magnetic loading type polyvinyl imidazol class part-metal ion match catalyzer.
Table 4
The embodiment sequence number Reaction times The part weight-average molecular weight
9 12h 3.8×10 3
10 72h 4.6×10 3
Embodiment 11～12
Except the mass ratio that changes polyvinyl imidazol class part and nano ferriferrous oxide, all the other operations all are same as embodiment 1, and concrete parameter is seen table 5, finally obtains magnetic loading type polyvinyl imidazol class part-metal ion match catalyzer.
Table 5
The embodiment sequence number The mass ratio of polyvinyl imidazol class part and nano ferriferrous oxide
11 1/20
12 1/50
Embodiment 13～15
Except adopting among the embodiment 2～4 the polyvinyl imidazol class part of preparation respectively, and change outside the metal compound species, all the other operations all are same as embodiment 1, finally prepare magnetic loading type polyvinyl imidazol class part-metal ion match catalyzer, see table 6.
Table 6
The embodiment sequence number Metallic compound and consumption thereof Part (containing the 0.2mmol imidazole group)
13 0.05mmol manganese acetate N-vinyl imidazole/N-vinylpyrrolidone copolymer
14 0.05mmol Manganous chloride tetrahydrate N-vinyl imidazole/PEMULEN TR2
15 0.05mmol manganous nitrate N-vinyl imidazole/Rocryl 400 multipolymer
Embodiment 16～18
Except changing the mol ratio of imidazole group in metals ion and the polyvinyl imidazol class part; And change metal compound beyond the region of objective existence; All the other operations all are same as embodiment 1, finally prepare magnetic loading type polyvinyl imidazol class part-metal ion complex catalyzer, see table 7.
Table 7
The embodiment sequence number Metallic compound and consumption thereof Imidazole group content in the part
16 0.5mmol cupric chloride lmmol
17 0.05mmol cupric nitrate 0.4mmol
18 0.005mmol copper sulfate 0.15mmol
Prepare ppe in embodiment 19 water mediums
In the reaction kettle that is connected with TM, stirring rake, prolong and gas inlet and outlet; Add 0.2083g sodium hydroxide (being 5mmol), 0.6162g 2; 6-xylenol (DMP; 5mmol), 1.6941g sodium lauryl sulphate (being 5mmol) and 90mL zero(ppm) water, after stirring reaction kettle is warmed up to 50 ℃.Magnetic loading type polyvinyl imidazol-metal ion match catalyzer (the institute's metal ion and 2 in loading type polyvinyl imidazol-metal ion match catalyzer that in reaction kettle, adds embodiment 1 preparation; The monomeric mol ratio of 6-xylenol is 1/100) aqueous solution; Aerating oxygen; Under the stirring velocity of 600 commentaries on classics/min, reacted 24 hours.
Polyreaction is utilized externally-applied magnetic field Separation and Recovery catalyzer after finishing, cleans 5 times with zero(ppm) water, and vacuum baking at room temperature 24 hours, catalyst recovery yield is 90.2%.Reaction product after the catalyst recovery is regulated pH to neutral with hydrochloric acid soln, adds sodium-chlor and saltouts, and leaves standstill, filter, and washing, drying obtains polymerisate.The gained polymerisate is removed by product 3 with the acetonitrile extracting, 3 ', 5,5 '-tetramethyl--4,4 '-diphenoquinone (DPQ) obtains the 0.5626g white powder, i.e. PPO, yield is 91.3%, the PPO viscosity-average molecular weight is 4.1 * 10 4
Embodiment 20
Method according to embodiment 19 prepares PPO in water medium, difference is to replace original catalyzer with the catalyzer that embodiment 19 reclaims.Catalyst recovery yield is 91.8%.Make the 0.5546g polymerisate, yield is 90.0%, and the PPO viscosity-average molecular weight is 3.8 * 10 4
Embodiment 21
Method according to embodiment 19 prepares PPO in water medium, difference is to replace original catalyzer with the catalyzer that embodiment 20 reclaims.Catalyst recovery yield is 90.6%.Obtain 0.5478gPPO, yield is 88.9%, and viscosity-average molecular weight is 3.2 * 10 4
Embodiment 22～23
Method according to embodiment 19 prepares PPO in water medium, difference is to adopt respectively the aqueous solution of the catalyzer of embodiment 11～12 preparations, and polymerization result is seen table 8.
Table 8
Figure BDA0000034527720000131
Embodiment 24～26
Method according to embodiment 19 prepares PPO in water medium, difference is to adopt respectively the aqueous solution of the catalyzer of embodiment 13～15 preparations, and polymerization result is seen table 9.
Table 9
Figure BDA0000034527720000132
Embodiment 27～29
Method according to embodiment 19 prepares PPO in water medium, difference is to adopt respectively the aqueous solution of the catalyzer of embodiment 16～18 preparations, and polymerization result is seen table 10.
Table 10
Figure BDA0000034527720000133
Embodiment 30
Method according to embodiment 19 prepares ppe in water medium, different is adopts 2.8000g Pottasium Hydroxide (50mmol) to replace sodium hydroxide, obtains the 0.4024g white powder, i.e. PPO, and the PPO yield is 65.3%, the PPO viscosity-average molecular weight is 2.2 * 10 4
Embodiment 31
Method according to embodiment 19 prepares ppe in water medium, different is to adopt 2,6-5 tert.-butyl phenol (1.0300g; 5mmol) replace 2, the 6-xylenol obtains the 0.9280g white powder; Be PPO, the PPO yield is 90.1%, and the PPO viscosity-average molecular weight is 4.2 * 10 4
Embodiment 32
Method according to embodiment 19 prepares ppe in water medium; Different is to adopt 0.7020g sodium cetanesulfonate (2mmol) to replace sodium lauryl sulphate, obtains the 0.5466g white powder, i.e. PPO; The PPO yield is 88.7%, and the PPO viscosity-average molecular weight is 2.6 * 10 4
Embodiment 33
Method according to embodiment 19 prepares ppe in water medium, different is adopts air to replace oxygen, obtains the 0.5533g white powder, i.e. PPO, and the PPO yield is 89.8%, the PPO viscosity-average molecular weight is 3.5 * 10 4
Embodiment 34
Method according to embodiment 19 prepares ppe in water medium, different is that temperature of reaction is 60 ℃, and the reaction times is 2 hours, obtains the 0.5170g white powder, i.e. PPO, and the PPO yield is 83.9%, the PPO viscosity-average molecular weight is 2.0 * 10 4
Embodiment 35
Method according to embodiment 19 prepares ppe in water medium, different is that temperature of reaction is 40 ℃, and the reaction times is 30 hours, obtains the 0.5712g white powder, i.e. PPO, and the PPO yield is 92.7%, the PPO viscosity-average molecular weight is 4.6 * 10 4

Claims (6)

1. a magnetic loading type catalyzer is that raw material prepares the application in the oxidative polymerization of ppe with phenol monomer, basic cpd, tensio-active agent and oxygenant in water medium in catalysis; It is characterized in that the polyvinyl imidazol class part that described magnetic loading type catalyzer is the magnetic nanoparticle surface grafting and the title complex of metals ion;
The mol ratio of imidazole group and metals ion is 0.5 ~ 300: 1 in the described title complex;
Described magnetic nanoparticle is the nano ferriferrous oxide particle;
Described metals ion is cupric ion or mn ion;
Described polyvinyl imidazol class part is the multipolymer of the monomeric homopolymer of N-vinyl imidazole class or N-vinyl imidazole class monomer and other one or more water-soluble monomers;
Wherein, described N-vinyl imidazole class monomer is the compound shown in the formula I structural formula:
Figure FDA00001689196000011
In the formula I, R 1Be hydrogen, C 1~ C 4Alkyl or phenyl, R 2Be hydrogen, C 1~ C 4Alkyl or phenyl, R 3Be hydrogen, C 1~ C 4Alkyl or phenyl, R 1, R 2And R 3Identical or different;
Described water-soluble monomer is N-vinylamide monomers, acrylamide monomer, (methyl) acrylic acid hydroxy alkyl ester monomer, unsaturated carboxylic acid or anhydride monomers;
The weight-average molecular weight of described polyvinyl imidazol class part is 10 3~ 10 7
2. application as claimed in claim 1 is characterized in that, at least a from cuprous chloride, cuprous bromide, cuprous sulfate, cuprous nitrate, cupric chloride, cupric bromide, copper sulfate, the cupric nitrate of described cupric ion;
Perhaps, at least a from Manganous chloride tetrahydrate, Manganese dibromide, manganese iodide, manganous carbonate, manganese acetate, manganous nitrate, manganous sulfate, the manganous phosphate of described mn ion.
3. application as claimed in claim 1 is characterized in that, described magnetic loading type catalyzer utilizes externally-applied magnetic field to recycle after oxidative polymerization finishes.
4. application as claimed in claim 1 is characterized in that, the mol ratio of each raw material consists of in the described oxidative polymerization:
Figure FDA00001689196000021
5. application as claimed in claim 1 is characterized in that, described phenol monomer is the compound shown in the formula II structural formula:
Figure FDA00001689196000022
In the formula II, R 4Be C 1～C 4Alkyl or phenyl, R 5Be C 1～C 4Alkyl or phenyl, R 6Be hydrogen or halogen; R 4And R 5Identical or different.
6. application as claimed in claim 1 is characterized in that, the temperature of described oxidative polymerization is 1～80 ℃, and the time of oxidative polymerization is 2～30 hours.
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