CN103406150B - Polymer-supported metal palladium complex catalyst and preparation method and application thereof - Google Patents
Polymer-supported metal palladium complex catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a polymer-supported metal palladium complex catalyst and a preparation method and an application thereof. The complex catalyst is formed in the way of loading palladium onto a polyacrylic acid supported 5-acrylamide radical-1,10 phenanthroline compound, wherein the loading capacity is calculated according to weight ratio, that is, the ratio of the palladium to the polyacrylic acid supported 5-acrylamido -1,10 phenanthroline compound is 5:100. The preparation method comprises the steps of nitration reaction of phenanthroline, amination reaction, acylation reaction, high-molecular polymerization reaction and high-molecular supported metal palladium complex catalyst preparation. When the complex catalyst provided by the invention is applied to the chlorinated aromatics hydrogenation dechlorination reaction, the reaction can be performed at the normal temperature and under 0.1 Mpa hydrogen atmosphere condition, the reaction conditions are mild, the final products are easy to separate and purify, and the conversion rate can be up to 90 percent.
Description
Technical field
The present invention relates to a kind of macromolecule loading metal palladium complex catalyst and preparation method thereof with its chlorinated aromatic hydrocarbons hydrogenation-dechlorination reaction in application.
Background technology
In the past few years, along with developing rapidly of organic chemical industry, the chlorinated organics being widely used in the field such as agricultural, industry discharges in a large number, the series of environmental problems caused thus causes the concern of people just day by day, because most of chlorinated organics has good chemical stability and heat endurance, not easily be decomposed or biodegradation, therefore these materials constantly accumulate at occurring in nature, the destructive power of environment is also highlighted day by day, as the destruction of the earth atmosphere ozone layer that fluorochlorohydrocarbon causes, the water quality that Polychlorinated biphenyls causes, the severe contamination etc. of soil property.
Hydrogenation catalyst dehalogenation be halides be decomposed reduction an important method, tradition use chlorinated aromatic hydrocarbons hydrogenation-dechlorination catalysts for precious metals pd catalyst cupport is at charcoal
[1], aluminium oxide
[2], titanium oxide
[3]on carrier, between metal Pd and carrier except chemical bonding, it is more physisorption, catalyst is solid-state existence, can not be soluble in the aqueous phase equal solvent, and the reaction of quite a few chlorinated aromatic hydrocarbons hydrogenation-dechlorination occurs in liquid phase reactor, thus have impact on the raising of catalytic reaction conversion ratio.And according to the literature
[4], when using traditional chlorinated aromatic hydrocarbons hydrogenation-dechlorination catalysts to carry out the reaction of chlorinated aromatic hydrocarbons hydrogenation-dechlorination, pressure is 4MPa, and reaction temperature is 150 DEG C, and reaction conversion ratio is only 74.8%.
bibliography
[1]?Chu,wenyi?Wang,man?Li,xinmin?Hou,yanjun?Sun,zhizhong.Pd/C-catalyzed?highly?efficient?and?green?suzuki?cross-coupling?reaction.?Chin?J?Org?Chem.?2012,?32,?1666-1672
Santiago?Gómez?Quero?Fernando?Cárdenas?Lizana?Mark?A?Keane.Solvent?effects?in?the?hydrodechlorination?of?2,4-dichlorophenol?over?Pd/Al
2O
3.?AIChe?J.?2010,?56,756-767
[3] opening hole distal apertures great waves, once to help rich Tan Zhen bright. and alkaline assistant modified support is to Pd/Al
2o
3-TiO
2the impact of catalyst. petroleum refining and Journal of Chemical Industry and Engineering. 2011,07,38-42
[4]?Shu,Jianzhi,?Zhang,Dongbao,?Lu,Mohong,?Li,Mingshi,?Shan,Yuhua,?Zhu,jianjun.Hydrogenation?of?Carbon?Tetrachloride?over?Ag-Pd/C?Catalysts?in?Liquid?Phase.Chin?Uni?J?Chem?Engi.2010,5,24-25。
Summary of the invention
When an object of the present invention carries out the reaction of chlorinated aromatic hydrocarbons hydrogenation-dechlorination to solve above-mentioned traditional chlorinated aromatic hydrocarbons hydrogenation-dechlorination catalysts, the reaction condition that palpus high temperature, high pressure etc. are harsh, and the technical problems such as low conversion rate, and a kind of macromolecule loading metal palladium complex catalyst is provided.When this macromolecule loading metal palladium complex catalyst is used for the reaction of chlorinated aromatic hydrocarbons hydrogenation-dechlorination, can carry out under normal temperature, low pressure (0.1Mpa hydrogen) reaction condition, and reaction condition is gentle, end product is easy to separation and purification, and conversion ratio can reach 90%.
Two of object of the present invention is to provide the preparation method of above-mentioned a kind of macromolecule loading metal palladium complex catalyst.
Three of object of the present invention is to provide a kind of macromolecule loading metal palladium complex catalyst of above-mentioned gained to be applied to the method for chlorinated aromatic hydrocarbons hydrogenation-dechlorination reaction.
Technical scheme of the present invention
A kind of macromolecule loading metal palladium complex catalyst, i.e. polyacrylic acid load 5-acrylamido-1, the 10 Phen compound of supported palladium, its load capacity is by weight calculating, i.e. palladium: polyacrylic acid load 5-acrylamido-1,10 Phen compound is 5:100.
The preparation method of above-mentioned a kind of macromolecule loading metal palladium complex catalyst, specifically comprises the steps:
(1), the nitration reaction of Phen, namely at 135 DEG C, obtain 5-nitro-1,10 Phen through nitration reaction in Phen and the concentrated sulfuric acid and red fuming nitric acid (RFNA)
Phen is joined in the concentrated sulfuric acid, then oil bath is heated to Phen and dissolves completely, continuation heating is back to reacting liquid temperature and reaches 100 DEG C, controlling drop rate in half an hour is after 2ml/min slowly adds red fuming nitric acid (RFNA), controlling heating rate is that temperature is slowly risen to 135 DEG C by 5 DEG C/min, control speed of agitator is 1000r/min, after carrying out nitration reaction 12h under reflux state, extremely neutral by 10mol/L NaOH adjust ph after being down to room temperature, controlling vavuum pump vacuum is carry out filtration under diminished pressure under 0.08MPa condition and wash precipitation with water, until filtrate is water white transparency, control temperature is 40 DEG C of vacuum drying sediments, obtain faint yellow 5-nitro-1, 10 Phen solids,
The amount of Phen, the concentrated sulfuric acid and red fuming nitric acid (RFNA) that above-mentioned nitration reaction is used, by Phen: the concentrated sulfuric acid: red fuming nitric acid (RFNA) is 1g:20ml:20ml;
(2), aminating reaction, namely there is aminating reaction and obtain 5-amido-1,10 Phen in 5-nitro-1,10 Phen under the effect of palladium carbon in 0.1MPa nitrogen atmosphere, anhydrous ethanol solvent
By step (1) gained 5-nitro-1,10 Phens are dissolved among absolute ethyl alcohol, then Pd/C is added, under 0.1MPa nitrogen atmosphere, normal temperature controls speed of agitator is after 1000r/min carries out aminating reaction 12h, filter, the filter cake control temperature of gained is 65 DEG C and carries out rotary evaporation drying, obtains 5-amido-1,10 Phen;
The amount of 5-nitro-1,10 Phen, absolute ethyl alcohol and Pd/C that above-mentioned aminating reaction is used, by 5-nitro-1,10 Phen: absolute ethyl alcohol: Pd/C is 1.10g:200ml:0.055g;
(3), acylation reaction, namely there is acylation reaction and generate 5-acrylamido-1,10 Phen in 5-amido-1,10 Phen and acryloyl chloride in ice-water bath, triethylamine organic base condition, dichloromethane solvent
By step (2) gained 5-amido-1,10 Phens join in carrene and form suspension, then under condition of ice bath, control drop rate is that 1g/min slowly adds acryloyl chloride, Keep agitation, and to control drop rate after being warming up to room temperature be that 2g/min slowly adds triethylamine, carries out acylation reaction 4h under reflux state, after having reacted by reactant liquor control temperature be 65 DEG C and rotate evaporate to dryness, obtain adorned Phen monomer, i.e. 5-acrylamido-1,10 Phen;
5-amido-1,10 Phen that above-mentioned acylation reaction is used: carrene: acryloyl chloride: triethylamine is 1:40ml:1.38g:3.06g;
(4), macromolecular polymerization reaction
With the 5-acrylamido-1 of step (3) gained, 10 Phens are monomer, take acrylic acid as polymerization single polymerization monomer, n-hexane is solvent, azodiisobutyronitrile is initator, n-dodecyl mercaptan is molecular weight regulator, first lauryl mercaptan is joined in n-hexane, obtain the hexane solution containing n-dodecyl mercaptan, by 5-acrylamido-1, 10 Phens and azodiisobutyronitrile are dissolved in acrylic acid, controlling drop rate by constant pressure funnel, to be that 1ml/min is slowly added drop-wise to above-mentioned containing in the hexane solution of n-dodecyl mercaptan, control temperature is carry out macromolecular polymerization reaction 4h under the reflux state of 65 DEG C, after having reacted by reactant liquor control temperature be 65 DEG C and rotate evaporate to dryness, obtain polyacrylic acid load 5-acrylamido-1, 10 Phen compounds,
The 5-acrylamido-1 that above-mentioned macromolecular polymerization reaction is used, the amount of 10 Phens, azodiisobutyronitrile, acrylic acid and n-dodecyl mercaptan, calculate in mass ratio, i.e. 5-acrylamido-1,10 Phen: 0.5g azodiisobutyronitrile: acrylic acid: n-dodecyl mercaptan is 1:2.5:24:1.87;
The amount of above-mentioned n-hexane used, calculates, i.e. n-dodecyl mercaptan in mass ratio: n-hexane is 1:30;
(5), the preparation of macromolecule loading metal palladium complex catalyst
By the polyacrylic acid load 5-acrylamido-1 of step (4) gained, 10 Phen compounds are dissolved in ethanol, obtain the polyacrylic acid load 5-acrylamido-1 that concentration is preferably 40g/L, the ethanolic solution of 10 Phen compounds, then controlled drop rate be 1ml/min be added drop-wise to concentration be preferably 5.2g/L containing palladium bichloride acetonitrile solution in, control temperature is 40 DEG C, rotating speed is carry out polymerisation 1h under 1000r/min, the reactant liquor control temperature that polymerisation terminates rear gained is 65 DEG C of rotation evaporates to dryness, namely secure satisfactory grades sub-carried metal palladium complex catalyst,
The amount of above-mentioned polyacrylic acid load adorned 5-acrylamido-1,10 Phen compound used and palladium bichloride calculates in mass ratio, i.e. polyacrylic acid load adorned 5-acrylamido-1,10 Phen compound: palladium bichloride is 1:0.05.
The macromolecule loading metal palladium complex catalyst of above-mentioned gained is used for the reaction of chlorinated aromatic hydrocarbons hydrogenation-dechlorination.
The structural formula of described chlorinated aromatic hydrocarbons is as follows:
When the substituent R on chlorinated aromatic hydrocarbons is respectively H, CH
3, OCH
3, F
3during C or Cl, chlorinated aromatic hydrocarbons be respectively chlorobenzene, parachlorotoluene, to chloroanisole, to 4-Chlorobenzotrifluoride or paracide;
When the structural formula of described chlorinated aromatic hydrocarbons is as follows:
When the substituent R on chlorinated aromatic hydrocarbons ' be respectively CH
3, OCH
3, F
3during C or Cl, chlorinated aromatic hydrocarbons is respectively ortho-chlorotolu'ene, o-chloro-anisole, o-trifluoromethyl chlorobenzene or o-dichlorohenzene.
The macromolecule loading metal palladium complex catalyst of above-mentioned gained is used for the reaction of chlorinated aromatic hydrocarbons hydrogenation-dechlorination, and it carries out the method for hydrogenation-dechlorination reaction in the reaction of chlorinated aromatic hydrocarbons hydrogenation-dechlorination, and concrete steps are as follows:
By the macromolecule loading metal palladium complex catalyst of above-mentioned gained and chlorinated aromatic hydrocarbons in molar ratio, i.e. macromolecule loading metal palladium complex catalyst: chlorinated aromatic hydrocarbons is the ratio of 1:20, first macromolecule loading metal palladium complex catalyst is dissolved in absolute ethyl alcohol, then triethylamine and sodium borohydride is added, water and chlorinated aromatic hydrocarbons is added after stirring 1h, carry out hydrogenation-dechlorination reaction 12h in 0.1MPa hydrogen atmosphere after, namely complete the reaction of chlorinated aromatic hydrocarbons hydrogenation-dechlorination;
Above-mentioned chlorinated aromatic hydrocarbons hydrogenation-dechlorination reacts the amount of chlorinated aromatic hydrocarbons, triethylamine and sodium borohydride used, calculates in mass ratio, i.e. chlorinated aromatic hydrocarbons: triethylamine: sodium borohydride is 1:11.25:0.5.
Beneficial effect of the present invention
A kind of macromolecule loading metal palladium complex catalyst of the present invention, because Metal Palladium is directly carried on macromolecule by chemical bonding, more stable than the catalyst of the load P d of physical absorption gained, and due to the effect of carboxyl functional group on macromolecular chain, the macromolecule loading metal palladium complex catalyst of gained can be made to be soluble in the aqueous phase better, in the common solvent such as ethanol, therefore when it reacts for chlorinated aromatic hydrocarbons hydrogenation-dechlorination, can under the reaction condition of gentleness, realize safety, efficient chlorinated aromatic hydrocarbons hydrogenation-dechlorination reaction, namely when macromolecule loading metal palladium complex catalyst of the present invention is used for the reaction of chlorinated aromatic hydrocarbons hydrogenation-dechlorination, can at normal temperature, carry out under low pressure and 0.1Mpa hydrogen atmosphere condition, and reaction condition is gentle, end product is easy to separation and purification, reaction conversion ratio can up to 90%.
Accompanying drawing explanation
The schematic diagram of the nitration reaction process of the Phen in the preparation of Fig. 1 a, macromolecule loading metal palladium complex catalyst;
The schematic diagram of the aminating reaction process of the Phen in the preparation of Fig. 1 b, macromolecule loading metal palladium complex catalyst;
The schematic diagram of the acylation reaction process of the Phen in the preparation of Fig. 1 c, macromolecule loading metal palladium complex catalyst;
The hydrogen nuclear magnetic spectrogram of 5-nitro-1,10 Phen of step (1) gained of Fig. 2, embodiment 1;
5-amido-1, the 10 Phen hydrogen nuclear magnetic spectrogram of step (2) gained of Fig. 3, embodiment 1;
The infrared spectrum of 5-acrylamido-1,10 Phen of step (3) gained of Fig. 4, embodiment 1;
The infrared spectrum of polyacrylic acid load 5-acrylamido-1, the 10 Phen compound of polyacrylic acid used and the middle gained of step (4) in the step (4) of Fig. 5, embodiment 1;
TEM figure after the macromolecule loading metal palladium complex catalyst of step (5) gained of Fig. 6, embodiment 1 is reduced.
Detailed description of the invention
Also by reference to the accompanying drawings the present invention is set forth further below by specific embodiment, but do not limit the present invention.
The initial concentration of the concentration/chlorinated aromatic hydrocarbons at the end of the conversion ratio=1-chlorinated aromatic hydrocarbons reaction of hydrogenation-dechlorination reaction.
Palladium bichloride used in various embodiments of the present invention, ethanol, carrene, n-hexane are AR level, provide by Chemical Reagent Co., Ltd., Sinopharm Group;
Triethylamine used, sodium borohydride, acrylic acid, azodiisobutyronitrile, n-dodecyl mercaptan, Phen, the concentrated sulfuric acid, red fuming nitric acid (RFNA), acryloyl chloride are RG level, provide by Chemical Reagent Co., Ltd., Sinopharm Group.
embodiment 1
A kind of macromolecule loading metal palladium complex catalyst, i.e. polyacrylic acid load 5-acrylamido-1, the 10 Phen compound of supported palladium, its load capacity is by weight calculating, i.e. palladium: polyacrylic acid load 5-acrylamido-1,10 Phen compound is 5:100.
The preparation method of above-mentioned a kind of macromolecule loading metal palladium complex catalyst, specifically comprises the steps:
(1), the nitration reaction of Phen, the schematic diagram of its course of reaction as shown in Figure 1a, namely obtains 5-nitro-1,10 Phen through nitration reaction in Phen and the concentrated sulfuric acid and red fuming nitric acid (RFNA) at 135 DEG C
1g Phen is joined in the 20ml concentrated sulfuric acid, then oil bath is heated to Phen and dissolves completely, continuation heating is back to reacting liquid temperature and reaches 100 DEG C, controlling drop rate in half an hour is after 2ml/min slowly adds 20ml red fuming nitric acid (RFNA), controlling heating rate is that temperature is slowly risen to 135 DEG C by 5 DEG C/min, control speed of agitator is 1000r/min, after carrying out nitration reaction 12h under reflux state, be that the NaOH adjust ph of 10mol/L is to neutral by concentration after being down to room temperature, can see and have tan precipitate to produce, filtration under diminished pressure under control vavuum pump vacuum 0.08MPa condition also washes precipitation with water, until filtrate is water white transparency, control temperature is for DEG C carrying out vacuum drying sediment 2h, obtain faint yellow solid 5-nitro-1, 10 Phen 1.10g, productive rate 90.0%,
The hydrogen nuclear magnetic spectrogram of Bruker 500MHZ Advance type NMR to the yellow solid of above-mentioned gained of Bruker company is adopted to measure, its hydrogen nuclear magnetic spectrogram as shown in Figure 2, can calculate from Fig. 2, the number of hydrogen is 7, meet nitration product 5-nitro-1, the sum of the hydrogen of 10 Phens, and the chemical shift of each hydrogen atom all with 5-nitro-1, on the standard diagram of 10 Phens, the position of hydrogen atom conforms to, the yellow solid indicating above-mentioned gained is thus 5-nitro-1,10 Phen;
(2), aminating reaction, as shown in Figure 1 b, namely there is aminating reaction and obtain 5-amido-1,10 Phen in 5-nitro-1,10 Phen to the schematic diagram of its course of reaction under the effect of palladium carbon in 0.1MPa hydrogen atmosphere, anhydrous ethanol solvent
By step (1) gained 1.1g5-nitro-1,10 Phens are dissolved among 200ml absolute ethyl alcohol, then 0.055gPd/C is added, under 0.1MPa nitrogen atmosphere, stirring at normal temperature 12h, filter, gained filter cake control temperature is 65 DEG C and carries out rotation evaporate to dryness, obtains 1.0g solid 5-amido-1,10 Phen;
The solid of Bruker 500MHZ Advance type NMR to above-mentioned gained of Bruker company is adopted to measure its nuclear magnetic spectrum, its nuclear magnetic spectrum as shown in Figure 3, the number that can be calculated hydrogen by Fig. 3 is 9, meet aminate 5-amido-1, the sum of the hydrogen of 10 Phens, and the chemical shift of each hydrogen atom all conforms to the position of hydrogen atom on the standard diagram of 5-amido-1,10 Phen, the solid indicating above-mentioned gained is thus 5-amido-1,10 Phen;
(3), acylation reaction; the schematic diagram of its course of reaction as illustrated in figure 1 c; namely there is acylation reaction generation 5-acrylamido-1,10 Phen in 5-amido-1,10 Phen and acryloyl chloride in ice-water bath, triethylamine organic base condition, dichloromethane solvent
By 0.5g step (2) gained solid 5-amido-1,10 Phens join in 20ml carrene and form suspension, then under condition of ice bath, control drop rate is that 1g/min slowly adds 0.69g acryloyl chloride, Keep agitation, question response controls drop rate after rising to room temperature be that 2g/min slowly adds 1.53g triethylamine, acylation reaction 4h is carried out under reflux state, after having reacted by reactant liquor control temperature be 65 DEG C and rotate evaporate to dryness, obtain adorned Phen monomer, i.e. 5-acrylamido-1,10 Phen;
Adopt the infrared spectrum of Nicolet 380 type Fourier transformation infrared spectrometer to the adorned o-phenanthrolin monomer of above-mentioned gained of Thermo Nicolet company to measure, its infrared spectrum as shown in Figure 4, as can be seen from Figure 4,3500cm
-1the broad peak at place is the stretching vibration peak of N-H, 1667cm
-1for the stretching vibration peak of C=O in acid amides, 1617cm
-1for the vibration peak of C=C, show that the adorned o-phenanthrolin monomer generated is 5-acrylamido-1,10 Phen thus;
(4), polymerisation
By the 5-acrylamido-1 of 0.2g step (3) gained, 10 Phens and 0.5g azodiisobutyronitrile initator are dissolved in 4.8g acrylic acid, controlling drop rate by constant pressure funnel is in the 10.25g n-hexane that is slowly added drop-wise to containing 0.375g chain-transferring agent n-dodecyl mercaptan of 1ml/min, control temperature be 65 DEG C be heated to reflux state under carry out macromolecular polymerization reaction 4h, after polymerisation terminates by reactant liquor control temperature be 65 DEG C and rotate evaporate to dryness, obtain polyacrylic acid load 5-acrylamido-1,10 Phen compound;
Adopt the Nicolet 380 type Fourier transformation infrared spectrometer of Thermo Nicolet company, to the polyacrylic acid load 5-acrylamido-1 of polyacrylic acid (hereinafter referred to as PAA) with above-mentioned gained, the infrared spectrum of 10 Phen compounds measures, the infrared spectrum of gained as shown in Figure 5, as can see from Figure 5, polyacrylic acid load 5-acrylamido-1, the 10 Phen compound of above-mentioned gained is at 1667 cm
-1there is absworption peak in place, can be attributed to the stretching vibration peak of acid amides C=O, 3500cm
-1the broad peak at place is attributed to the stretching vibration peak of N-H, illustrates in polyacrylic acid load 5-acrylamido-1, the 10 Phen compound of above-mentioned gained containing 5-acrylamido-1,10 Phen;
Further, known from the infrared spectrum contrast of the PAA Fig. 5 and polyacrylic acid load 5-acrylamido-1,10 Phen compound, the two figure spectral shape is similar, and obvious displacement does not occur in peak position, at 1617cm
-1place does not all occur the vibration peak of C=C showing thus: 1, polyacrylic acid load 5-acrylamido-1, the 10 Phen compound of above-mentioned gained and PAA similar, all double bonds rupture, have formed polyacrylic acid macromolecule; 2, the double bond in 5-acrylamido-1,10 Phen also ruptures, and 5-acrylamido-1,10 Phen and polyacrylic acid create chemical bonding effect;
Above 2 fully indicate above-mentioned polymerisation and have defined polyacrylic acid load 5-acrylamido-1,10 Phen compound;
(5), the preparation of palladium-containing catalyst
By the polyacrylic acid load 5-acrylamido-1 of 1g step (4) gained, 10 Phen compounds are dissolved in 25ml ethanolic solution, control again drop rate be 1ml/min be slowly added drop-wise to 25ml containing 0.13g palladium bichloride acetonitrile solution in, control temperature is 40 DEG C, rotating speed is carry out polymerisation 1h under 1000r/min, it is 65 DEG C of rotation evaporates to dryness that polymerisation terminates rear control temperature, obtain the polyacrylic acid load 5-acrylamido-1 of supported palladium, 10 Phen compounds, are macromolecule loading metal palladium complex catalyst.
Get the macromolecule loading metal palladium complex catalyst of above-mentioned gained and polyacrylic acid supported palladium and 5-acrylamido-1,10 Phen compound 0.05g, with the sodium borohydride of 0.018g in 10ml absolute ethyl alcohol in the hydrogen atmosphere of 0.1MPa after reduction reaction 1h, the reactant liquor of gained is rotated at 65 DEG C evaporate to dryness can obtain reducing after palladium be the catalyst of 0 valency.By the JEOL JEM-3000F type transmission electron microscope of JEOL company, under the condition of accelerating potential 80Kv, the macromolecule appendix metal palladium complex catalyst be reduced is scanned, the scintigram of gained as shown in Figure 6, in Fig. 6, light color is macromolecule, black particle is the Metal Palladium particle after being reduced, and as can be seen from Figure 6, Metal Palladium particle presents dispersity, do not reunite, show that Metal Palladium is carried on macromolecule well.
application Example 1
The macromolecule loading metal palladium complex catalyst of embodiment 1 gained is used for chlorinated aromatic hydrocarbons and the reaction of chlorobenzene hydrogenation-dechlorination
The macromolecule loading metal palladium complex catalyst 0.3554g taking embodiment 1 gained is dissolved in 30ml absolute ethyl alcohol, then 4.5g triethylamine and 0.2g sodium borohydride is added, 20ml water and 0.4g chlorobenzene is added after stirring 1h, react 12h in 0.1Mpa hydrogen atmosphere after, get 0.3ml reactant liquor, with carrene, chlorobenzene wherein and product benzene are extracted, analyze the conversion ratio of chlorobenzene hydrogenation-dechlorination reaction and selective with gas-chromatography work station.Analysis result is in table 1:
The amount of above-mentioned macromolecule loading metal palladium complex catalyst used and chlorinated aromatic hydrocarbons in molar ratio, i.e. macromolecule loading metal palladium complex catalyst: chlorinated aromatic hydrocarbons is 1:20;
Above-mentioned chlorinated aromatic hydrocarbons hydrogenation-dechlorination reacts the amount of chlorinated aromatic hydrocarbons, triethylamine and sodium borohydride used, calculates in mass ratio, i.e. chlorinated aromatic hydrocarbons: triethylamine: sodium borohydride is 1:11.25:0.5.
application Example 2
The macromolecule loading metal palladium complex catalyst of embodiment 1 gained is used for chlorinated aromatic hydrocarbons and the reaction of parachlorotoluene hydrogenation-dechlorination
The macromolecule loading metal palladium complex catalyst 0.316g taking embodiment 1 gained is dissolved in 30ml absolute ethyl alcohol, then 4.5g triethylamine and 0.2g sodium borohydride is added, 20ml water and 0.4g parachlorotoluene is added after stirring 1h, react 12h in 0.1Mpa hydrogen atmosphere after, get 0.3ml reactant liquor, with carrene, parachlorotoluene wherein and product toluene are extracted, analyze the conversion ratio of parachlorotoluene hydrogenation-dechlorination reaction and selective with gas-chromatography work station.Analysis result is in table 1:
The amount of above-mentioned macromolecule loading metal palladium complex catalyst used and chlorinated aromatic hydrocarbons in molar ratio, i.e. macromolecule loading metal palladium complex catalyst: chlorinated aromatic hydrocarbons is 1:20;
Above-mentioned chlorinated aromatic hydrocarbons hydrogenation-dechlorination reacts the amount of chlorinated aromatic hydrocarbons, triethylamine and sodium borohydride used, calculates in mass ratio, i.e. chlorinated aromatic hydrocarbons: triethylamine: sodium borohydride is 1:11.25:0.5.
application Example 3
The macromolecule loading metal palladium complex catalyst of embodiment 1 gained is used for chlorinated aromatic hydrocarbons and namely reacts chloroanisole hydrogenation-dechlorination
The macromolecule loading metal palladium complex catalyst 0.281g taking embodiment 1 gained is dissolved in 30ml absolute ethyl alcohol, then 4.5g triethylamine and 0.2g sodium borohydride is added, stir and to add 20ml water and 0.4g after 1h to chloroanisole, react 12h in 0.1Mpa hydrogen atmosphere after, get 0.3ml reactant liquor, with carrene by extracting chloroanisole and product methyl phenyl ethers anisole wherein, analyze the conversion ratio of chloroanisole hydrogenation-dechlorination reaction and selective with gas-chromatography work station.Analysis result is in table 1:
The amount of above-mentioned macromolecule loading metal palladium complex catalyst used and chlorinated aromatic hydrocarbons in molar ratio, i.e. macromolecule loading metal palladium complex catalyst: chlorinated aromatic hydrocarbons is 1:20;
Above-mentioned chlorinated aromatic hydrocarbons hydrogenation-dechlorination reacts the amount of chlorinated aromatic hydrocarbons, triethylamine and sodium borohydride used, calculates in mass ratio, i.e. chlorinated aromatic hydrocarbons: triethylamine: sodium borohydride is 1:11.25:0.5.
application Example 4
The macromolecule loading metal palladium complex catalyst of embodiment 1 gained is used for chlorinated aromatic hydrocarbons and namely reacts 4-Chlorobenzotrifluoride hydrogenation-dechlorination
The macromolecule loading metal palladium complex catalyst 0.222g taking embodiment 1 gained is dissolved in 30ml absolute ethyl alcohol, then 4.5g triethylamine and 0.2g sodium borohydride is added, stir and to add 20ml water and 0.4g after 1h to 4-Chlorobenzotrifluoride, react 12h in 0.1Mpa nitrogen atmosphere after, get 0.3ml reactant liquor, with carrene by extracting 4-Chlorobenzotrifluoride and product benzenyl fluoride wherein, analyze the conversion ratio of 4-Chlorobenzotrifluoride hydrogenation-dechlorination reaction and selective with gas-chromatography work station.Analysis result is in table 1:
The amount of above-mentioned macromolecule loading metal palladium complex catalyst used and chlorinated aromatic hydrocarbons in molar ratio, i.e. macromolecule loading metal palladium complex catalyst: chlorinated aromatic hydrocarbons is 1:20;
Above-mentioned chlorinated aromatic hydrocarbons hydrogenation-dechlorination reacts the amount of chlorinated aromatic hydrocarbons, triethylamine and sodium borohydride used, calculates in mass ratio, i.e. chlorinated aromatic hydrocarbons: triethylamine: sodium borohydride is 1:11.25:0.5.
application Example 5
The macromolecule loading metal palladium complex catalyst of embodiment 1 gained is used for chlorinated aromatic hydrocarbons and the reaction of paracide hydrogenation-dechlorination
The macromolecule loading metal palladium complex catalyst 0.272g taking embodiment 1 gained is dissolved in 30ml absolute ethyl alcohol, then 4.5g triethylamine and 0.2g sodium borohydride is added, 20ml water and 0.4g paracide is added after stirring 1h, react 12h in 0.1Mpa hydrogen atmosphere after, get 0.3ml reactant liquor, with carrene, paracide wherein and product benzene are extracted, analyze the conversion ratio of paracide hydrogenation-dechlorination reaction and selective with gas-chromatography work station.Analysis result is in table 1:
The amount of above-mentioned macromolecule loading metal palladium complex catalyst used and chlorinated aromatic hydrocarbons in molar ratio, i.e. macromolecule loading metal palladium complex catalyst: chlorinated aromatic hydrocarbons is 1:20;
Above-mentioned chlorinated aromatic hydrocarbons hydrogenation-dechlorination reacts the amount of chlorinated aromatic hydrocarbons, triethylamine and sodium borohydride used, calculates in mass ratio, i.e. chlorinated aromatic hydrocarbons: triethylamine: sodium borohydride is 1:11.25:0.5.
application Example 6
The macromolecule loading metal palladium complex catalyst of embodiment 1 gained is used for chlorinated aromatic hydrocarbons and the reaction of ortho-chlorotolu'ene hydrogenation-dechlorination
The macromolecule loading metal palladium complex catalyst 0.316g taking embodiment 1 gained is dissolved in 30ml absolute ethyl alcohol, then 4.5g triethylamine and 0.2g sodium borohydride is added, 20ml water and 0.4g ortho-chlorotolu'ene is added after stirring 1h, react 12h in 0.1Mpa hydrogen atmosphere after, get 0.3ml reactant liquor, with carrene, ortho-chlorotolu'ene wherein and product toluene are extracted, analyze the conversion ratio of ortho-chlorotolu'ene hydrogenation-dechlorination reaction and selective with gas-chromatography work station.Analysis result is in table 1:
The amount of above-mentioned macromolecule loading metal palladium complex catalyst used and chlorinated aromatic hydrocarbons in molar ratio, i.e. macromolecule loading metal palladium complex catalyst: chlorinated aromatic hydrocarbons is 1:20;
Above-mentioned chlorinated aromatic hydrocarbons hydrogenation-dechlorination reacts the amount of chlorinated aromatic hydrocarbons, triethylamine and sodium borohydride used, calculates in mass ratio, i.e. chlorinated aromatic hydrocarbons: triethylamine: sodium borohydride is 1:11.25:0.5.
application Example 7
The macromolecule loading metal palladium complex catalyst of embodiment 1 gained is used for chlorinated aromatic hydrocarbons and the reaction of o-chloro-anisole hydrogenation-dechlorination
The macromolecule loading metal palladium complex catalyst 0.281g taking embodiment 1 gained is dissolved in 30ml absolute ethyl alcohol, then 4.5g triethylamine and 0.2g sodium borohydride is added, 20ml water and 0.4g o-chloro-anisole is added after stirring 1h, react 12h in 0.1Mpa hydrogen atmosphere after, get 0.3ml reactant liquor, with carrene, o-chloro-anisole wherein and product methyl phenyl ethers anisole are extracted, analyze the conversion ratio of o-chloro-anisole hydrogenation-dechlorination reaction and selective with gas-chromatography work station.Analysis result is in table 1:
The amount of above-mentioned macromolecule loading metal palladium complex catalyst used and chlorinated aromatic hydrocarbons in molar ratio, i.e. macromolecule loading metal palladium complex catalyst: chlorinated aromatic hydrocarbons is 1:20;
Above-mentioned chlorinated aromatic hydrocarbons hydrogenation-dechlorination reacts the amount of chlorinated aromatic hydrocarbons, triethylamine and sodium borohydride used, calculates in mass ratio, i.e. chlorinated aromatic hydrocarbons: triethylamine: sodium borohydride is 1:11.25:0.5.
application Example 8
The macromolecule loading metal palladium complex catalyst of embodiment 1 gained is used for chlorinated aromatic hydrocarbons and the reaction of o-trifluoromethyl chlorobenzene hydrogenation-dechlorination
The macromolecule loading metal palladium complex catalyst 0.222g taking embodiment 1 gained is dissolved in 30ml absolute ethyl alcohol, then 4.5g triethylamine and 0.2g sodium borohydride is added, 20ml water and 0.4g o-trifluoromethyl chlorobenzene is added after stirring 1h, react 12h in 0.1Mpa hydrogen atmosphere after, get 0.3ml reactant liquor, with carrene, o-trifluoromethyl chlorobenzene wherein and product benzenyl fluoride are extracted, analyze the conversion ratio of o-trifluoromethyl chlorobenzene hydrogenation-dechlorination reaction and selective with gas-chromatography work station.Analysis result is in table 1:
The amount of above-mentioned macromolecule loading metal palladium complex catalyst used and chlorinated aromatic hydrocarbons in molar ratio, i.e. macromolecule loading metal palladium complex catalyst: chlorinated aromatic hydrocarbons is 1:20;
Above-mentioned chlorinated aromatic hydrocarbons hydrogenation-dechlorination reacts the amount of chlorinated aromatic hydrocarbons, triethylamine and sodium borohydride used, calculates in mass ratio, i.e. chlorinated aromatic hydrocarbons: triethylamine: sodium borohydride is 1:11.25:0.5.
application Example 9
The macromolecule loading metal palladium complex catalyst of embodiment 1 gained is used for chlorinated aromatic hydrocarbons and the reaction of o-dichlorohenzene hydrogenation-dechlorination, step is as follows:
The macromolecule loading metal palladium complex catalyst 0.272g taking embodiment 1 gained is dissolved in 30ml absolute ethyl alcohol, then 4.5g triethylamine and 0.2g sodium borohydride is added, 20ml water and 0.4g o-dichlorohenzene is added after stirring 1h, react 12h in 0.1Mpa hydrogen atmosphere after, get 0.3ml reactant liquor, with carrene, o-dichlorohenzene wherein and product benzene are extracted, analyze the conversion ratio of o-dichlorohenzene hydrogenation-dechlorination reaction and selective with gas-chromatography work station.Analysis result is in table 1:
The amount of above-mentioned macromolecule loading metal palladium complex catalyst used and chlorinated aromatic hydrocarbons in molar ratio, i.e. macromolecule loading metal palladium complex catalyst: chlorinated aromatic hydrocarbons is 1:20;
Above-mentioned chlorinated aromatic hydrocarbons hydrogenation-dechlorination reacts the amount of chlorinated aromatic hydrocarbons, triethylamine and sodium borohydride used, calculates in mass ratio, i.e. chlorinated aromatic hydrocarbons: triethylamine: sodium borohydride is 1:11.25:0.5.
Table 1, different chlorinated aromatic hydrocarbons carry out the reacted conversion ratio of hydrogenation-dechlorination and selective
| ? | Chlorinated aromatic hydrocarbons | Target product | Conversion ratio % | Selective % |
| 1 | Chlorobenzene | Benzene | 90.3 | 100 |
| 2 | Parachlorotoluene | Toluene | 95.1 | 100 |
| 3 | To chloroanisole | Methyl phenyl ethers anisole | 92.3 | 100 |
| 4 | To 4-Chlorobenzotrifluoride | Benzenyl fluoride | 96.6 | 100 |
| 5 | Paracide | Benzene | 93.8 | 100 |
| 6 | Ortho-chlorotolu'ene | Toluene | 90.2 | 100 |
| 7 | O-chloro-anisole | Methyl phenyl ethers anisole | 90.4 | 100 |
| 8 | O-trifluoromethyl chlorobenzene | Benzenyl fluoride | 92.1 | 100 |
| 9 | O-dichlorohenzene | Benzene | 90.6 | 100 |
Data as can be seen from table 1, in chlorinated aromatic hydrocarbons structure, no matter substituent position is in contraposition or at ortho position, at normal temperature, 0.1MPa hydrogen atmosphere, adopt macromolecule loading metal palladium complex catalyst of the present invention, the conversion ratio of the hydrogenation-dechlorination of chlorinated aromatic hydrocarbons reaction is all close to even more than 90%.And because only have the existence of target product in all employing chromatography results, so the selective of all target products is 100%.
In sum, a kind of macromolecule loading metal palladium complex catalyst of the present invention is used for the reaction of chlorinated aromatic hydrocarbons hydrogenation-dechlorination, carries out under normal temperature, low pressure and 0.1MPa hydrogen atmosphere, and reaction condition is gentle, product is easy to separation and purification, and reaction conversion ratio can up to 90%.
Above embodiment is just described in further detail technical scheme of the present invention; can not be interpreted as the restriction to technical solution of the present invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (6)
1. one kind is carried on the metal palladium complex catalyst on macromolecule, it is characterized in that the described metal palladium complex catalyst be carried on macromolecule is that palladium loads to polyacrylic acid load 5-acrylamido-1, gained on 10 Phen compounds, its load capacity is by weight calculating, i.e. palladium: polyacrylic acid load 5-acrylamido-1,10 Phen compound is 5:100;
Described polyacrylic acid load 5-acrylamido-1,10 Phen compound, is prepared by a method comprising the following steps:
(1), the nitration reaction of Phen
Namely at 135 DEG C, 5-nitro-1,10 Phen is obtained through nitration reaction in Phen and the concentrated sulfuric acid and red fuming nitric acid (RFNA);
The amount of Phen, the concentrated sulfuric acid and red fuming nitric acid (RFNA) that above-mentioned nitration reaction is used, by Phen: the concentrated sulfuric acid: red fuming nitric acid (RFNA) is 1g:20ml:20ml;
(2), aminating reaction
Under the effect of palladium carbon, in 0.1MPa nitrogen atmosphere, anhydrous ethanol solvent, be there is aminating reaction in step (1) gained 5-nitro-1,10 Phen and obtain 5-amido-1,10 Phen;
The amount of 5-nitro-1,10 Phen, absolute ethyl alcohol and Pd/C that above-mentioned aminating reaction is used, by 5-nitro-1,10 Phen: absolute ethyl alcohol: Pd/C is 1.10g:200ml:0.055g;
(3), acylation reaction
Step (2) gained 5-amido-1,10 Phen and acryloyl chloride be there is in ice-water bath, triethylamine organic base condition, dichloromethane solvent acylation reaction and generate 5-acrylamido-1,10 Phen;
5-amido-1,10 Phen that above-mentioned acylation reaction is used: carrene: acryloyl chloride: triethylamine is 1g:40ml:1.38g:3.06g;
(4), macromolecular polymerization reaction
With 5-acrylamido-1,10 Phen of step (3) gained for monomer, take acrylic acid as polymerization single polymerization monomer, n-hexane is solvent, and azodiisobutyronitrile is initator, and n-dodecyl mercaptan is that molecular weight regulator carries out macromolecular polymerization reaction;
The 5-acrylamido-1 that above-mentioned macromolecular polymerization reaction is used, the amount of 10 Phens, azodiisobutyronitrile, acrylic acid, n-dodecyl mercaptan, calculate in mass ratio, i.e. 5-acrylamido-1,10 Phen: azodiisobutyronitrile: acrylic acid: n-dodecyl mercaptan is 1:2.5:24:1.87;
The amount of above-mentioned n-hexane used, calculates, i.e. n-dodecyl mercaptan in mass ratio: n-hexane is 1:30;
The described metal palladium complex catalyst be carried on macromolecule is that palladium loads to polyacrylic acid load 5-acrylamido-1, gained on 10 Phen compounds, by polyacrylic acid load 5-acrylamido-1, 10 Phen compounds are dissolved in ethanol, the polyacrylic acid load 5-acrylamido-1 obtained, it is in the acetonitrile solution that it is slowly added drop-wise to containing palladium bichloride of 1ml/min that the ethanolic solution of 10 Phen compounds controls drop rate, control temperature is 40 DEG C, rotating speed is carry out polymerisation 1h under 1000r/min, the reactant liquor that polymerisation terminates rear gained is 65 DEG C in control temperature and rotates evaporates to dryness, the metal palladium complex catalyst on macromolecule must be carried on,
The amount of above-mentioned polyacrylic acid load adorned 5-acrylamido-1,10 Phen compound used and palladium bichloride calculates in mass ratio, i.e. polyacrylic acid load adorned 5-acrylamido-1,10 Phen compound: palladium bichloride is 1:0.05.
2. the preparation method of a kind of metal palladium complex catalyst be carried on macromolecule as claimed in claim 1, is characterized in that specifically comprising the steps:
(1), the nitration reaction of Phen
Phen is joined in the concentrated sulfuric acid, then oil bath is heated to Phen and dissolves completely, continuation heating is back to reacting liquid temperature and reaches 100 DEG C, controlling drop rate in half an hour is after 2ml/min slowly adds red fuming nitric acid (RFNA), controlling heating rate is that temperature is slowly risen to 135 DEG C by 5 DEG C/min, control speed of agitator is 1000r/min, after carrying out nitration reaction 12h under reflux state, extremely neutral by 10mol/L NaOH adjust ph after being down to room temperature, controlling vacuum is carry out filtration under diminished pressure under 0.08MPa condition and wash precipitation with water, until filtrate is water white transparency, control temperature is 40 DEG C of vacuum drying sediments, obtain 5-nitro-1, 10 Phens,
The amount of Phen, the concentrated sulfuric acid and red fuming nitric acid (RFNA) that above-mentioned nitration reaction is used, by Phen: the concentrated sulfuric acid: red fuming nitric acid (RFNA) is 1g:20ml:20ml;
(2), aminating reaction
Step (1) gained 5-nitro-1,10 Phen is dissolved among absolute ethyl alcohol, then adds Pd/C, after under 0.1MPa nitrogen atmosphere, stirring at normal temperature carries out aminating reaction 12h, filter, the filter cake control temperature of gained is 65 DEG C and carries out rotary evaporation drying, obtain 5-amido-1,10 Phen;
The amount of 5-nitro-1,10 Phen, absolute ethyl alcohol and Pd/C that above-mentioned aminating reaction is used, by 5-nitro-1,10 Phen: absolute ethyl alcohol: Pd/C is 1.10g:200ml:0.055g;
(3), acylation reaction
By step (2) gained 5-amido-1,10 Phens join in carrene and form suspension, then under condition of ice bath, control drop rate is that 1g/min slowly adds acryloyl chloride, Keep agitation, and to control drop rate after being warming up to room temperature be that 2g/min slowly adds triethylamine, carries out acylation reaction 4h under reflux state, after having reacted by reactant liquor control temperature be 65 DEG C and rotate evaporate to dryness, obtain adorned Phen monomer, i.e. 5-acrylamido-1,10 Phen;
5-amido-1,10 Phen that above-mentioned acylation reaction is used: carrene: acryloyl chloride: triethylamine is 1g:40ml:1.38g:3.06g;
(4), macromolecular polymerization reaction
With 5-acrylamido-1,10 Phen of step (3) gained for monomer, take acrylic acid as polymerization single polymerization monomer, n-hexane is solvent, and azodiisobutyronitrile is initator, and n-dodecyl mercaptan is molecular weight regulator;
First lauryl mercaptan is joined in n-hexane, obtain the hexane solution containing n-dodecyl mercaptan, then by 5-acrylamido-1, 10 Phens and azodiisobutyronitrile are dissolved in acrylic acid, controlling drop rate by constant pressure funnel, to be that 1ml/min is slowly added drop-wise to above-mentioned containing in the hexane solution of n-dodecyl mercaptan, control temperature is carry out macromolecular polymerization reaction 4h under the reflux state of 65 DEG C, after having reacted by reactant liquor control temperature be 65 DEG C and rotate evaporate to dryness, obtain polyacrylic acid load 5-acrylamido-1, 10 Phen compounds,
The 5-acrylamido-1 that above-mentioned macromolecular polymerization reaction is used, 10 Phens, azodiisobutyronitrile, acrylic acid and n-dodecyl mercaptan amount, calculate in mass ratio, i.e. 5-acrylamido-1,10 Phen: azodiisobutyronitrile: acrylic acid: n-dodecyl mercaptan is 1:2.5:24:1.87;
The described hexane solution containing n-dodecyl mercaptan, calculates, i.e. n-dodecyl mercaptan: n-hexane is 1:30 in mass ratio;
(5), the preparation of macromolecule loading metal palladium complex catalyst
By the polyacrylic acid load 5-acrylamido-1 of step (4) gained, 10 Phen compounds are dissolved in ethanol, the polyacrylic acid load 5-acrylamido-1 obtained, it is in the acetonitrile solution that it is slowly added drop-wise to containing palladium bichloride of 1ml/min that the ethanolic solution of 10 Phen compounds controls drop rate, control temperature is 40 DEG C, rotating speed is carry out polymerisation 1h under 1000r/min, the reactant liquor that polymerisation terminates rear gained is 65 DEG C of rotation evaporates to dryness in control temperature, and namely secure satisfactory grades sub-carried metal palladium complex catalyst;
The amount of above-mentioned polyacrylic acid load adorned 5-acrylamido-1,10 Phen compound used and palladium bichloride calculates in mass ratio, i.e. polyacrylic acid load adorned 5-acrylamido-1,10 Phen compound: palladium bichloride is 1:0.05.
3. the preparation method of a kind of metal palladium complex catalyst be carried on macromolecule as claimed in claim 2, it is characterized in that, polyacrylic acid load 5-acrylamido-1 described in step (5), the concentration of the ethanolic solution of 10 Phen compounds is 40g/L, and the concentration of the acetonitrile solution containing palladium bichloride is 5.2g/L.
4. a kind of application of metal palladium complex catalyst in the reaction of chlorinated aromatic hydrocarbons hydrogenation-dechlorination be carried on macromolecule as claimed in claim 1.
5. a kind of metal palladium complex catalyst be carried on macromolecule carries out the method for hydrogenation-dechlorination in the reaction of chlorinated aromatic hydrocarbons hydrogenation-dechlorination as claimed in claim 4, it is characterized in that step is as follows:
By macromolecule loading metal palladium complex catalyst and chlorinated aromatic hydrocarbons in molar ratio, i.e. macromolecule loading metal palladium complex catalyst: chlorinated aromatic hydrocarbons is the ratio of 1:20, first macromolecule loading metal palladium complex catalyst is dissolved in ethanolic solution, then triethylamine and sodium borohydride is added, water and chlorinated aromatic hydrocarbons is added after stirring 1h, carry out hydrogenation-dechlorination reaction 12h in 0.1MPa nitrogen atmosphere after, namely complete the reaction of chlorinated aromatic hydrocarbons hydrogenation-dechlorination;
The triethylamine added and the amount of sodium borohydride, calculate by its mass ratio relative to chlorinated aromatic hydrocarbons, i.e. chlorinated aromatic hydrocarbons: triethylamine: sodium borohydride is 1:11.25:0.5.
6. be a kind ofly as claimed in claim 5 carried on the method that metal palladium complex catalyst on macromolecule carries out hydrogenation-dechlorination in the reaction of chlorinated aromatic hydrocarbons hydrogenation-dechlorination, it is characterized in that described chlorinated aromatic hydrocarbons be chlorobenzene, parachlorotoluene, to chloroanisole, to 4-Chlorobenzotrifluoride, paracide, ortho-chlorotolu'ene, o-chloro-anisole, o-trifluoromethyl chlorobenzene or o-dichlorohenzene.
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