CN101024197A - High-molecular fabric load palladium catalyst and preparing method - Google Patents
High-molecular fabric load palladium catalyst and preparing method Download PDFInfo
- Publication number
- CN101024197A CN101024197A CN 200710037421 CN200710037421A CN101024197A CN 101024197 A CN101024197 A CN 101024197A CN 200710037421 CN200710037421 CN 200710037421 CN 200710037421 A CN200710037421 A CN 200710037421A CN 101024197 A CN101024197 A CN 101024197A
- Authority
- CN
- China
- Prior art keywords
- palladium
- fabric
- catalyst
- reaction
- molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a macromolecule tissue load Pd catalyst of using the above preparation method. The catalyst used the general goods acrylics tissue as framing, through lewis acid catalysis graft, with Pd formed macromolecule tissue load Pd catalyst; or used the general goods acrylics tissue as framing, through multi-ethene polyamine low linking, hydrolyze formed carboxylic acid salt in the base solution, ion exchange with Pd salt to form macromolecule tissue load Pd catalyst. Macromolecule tissue load Pd catalyst of the invention no need reducer active Pd before the catalysis Heck reaction, in the Heck reaction used the cheap price, environmental protection ethanol and water mixture, no need inert gases protection, no need add any phase-transfer catalyst, have high catalyst activity. It achieved the 'green environmental protection' catalyst procession.
Description
Technical field
The present invention relates to a kind of load type palladium catalyst and preparation method thereof, particularly a kind of high-molecular fabric load palladium catalyst and preparation method thereof.
Background technology
The Heck reaction of palladium catalysis is the effective ways that form the C-C key.Homogeneous palladium catalysts can be under temperate condition, high efficiency and this type of reaction of highly selective catalysis, but homogeneous catalyst in actual applications, usually run into problems such as being difficult to separation, recovery and cycling and reutilization difficulty, and when meeting water and air, easily decompose, thereby be restricted in actual applications.
In order to solve the problem that homogeneous catalyst exists in actual applications, obtaining very much progress aspect the research and development of heterogeneous catalysis both at home and abroad in recent years.The used kind of carrier of loaded catalyst is a lot, and aluminium oxide (Kr ǒ ckl, S.S. are arranged; Kleist, W.; K ǒ kler, K.Tetrahedron, 2005,61,9855-9859), silica (Karimi, B.; Enders, D.Org.Lett.2006,8 (6), 1237-1240) and inorganic material such as activated carbon, but these carrier loaded catalyst lose when reclaiming easily.The catalyst that with the organic polymer is carrier has the comprehensive advantage of homogeneous phase and heterogeneous catalysis, be easier to the final recovery (Liu Pu of palladium than inorganic carrier, Wang Lan, Li Limin, Wang Xiangning, organic chemistry, 2004,24 (1), 59-62), therefore, to do the research and development of catalyst of carrier very fast for organic polymer.The kind of organic polymer is also quite a lot of, and synthetic high polymer is arranged, as polyethylene glycol (Hagio, H.; Sugiura, M.; Kobayashi, S.Org.Lett.2006,8 (3), 375-378), polystyrene (Byun, J.W.; Lee, Y.S.Tetrahedron Lett.2004,45,1837-1840; Molnar, A.; Galvacs, G.; Papp, A.Tetrahedron Lett.2005,46,7725-7728), polyvinyl chloride (Zhang Lei, Cui Yuanchen, chemical journal, 2005,63 (10), 924-928), natural polymer is also arranged, as shitosan (Liu Pu, Wang Lan, Li Limin, Wang Xiangning, organic chemistry, 2004,24 (1), 59-62), sesbania gum (Cui Yuanchen, Zhang Lei, macromolecule journal, 2005,30,423) and starch etc., people such as Kantam has reported that cellulose makes carrier synthetic palladium catalyst (Reddy, K.R. recently; Kumar, N.S.; Reddy, P.S.; Sreedhar, B.; Kantam, M.L.J.Mol.Catal.A:Chem.2006,252,12-16).
The synthesis step that these catalyst have is many, cost is higher, and what have contains phosphino-(Phan, N.T.S.; Shys, M.V.D.; Jones, C.W.Adv.Synth.Catal.2006,348,609; Hii, K.K.; Guino, M.Tetrahedron Lett.2005,46,7363-7366; Dahan, A.; Portnoy, M.Org.Lett.2003,5 (8), 1197-1200), and phosphorus is environmentally harmful, when the synthetic high polymer carrier, should avoid using phosphorus-containing compound as far as possible.
Remarkable progress (Altava, B. have been obtained aspect the phosphine macromolecule load catalyst not containing both at home and abroad in recent years; Burguets, M.I.; Luis, S.V.Tetrahedron Lett.2006,47,2311-2314; Yang Yuanfa, Ceng Chaoxia, Luo Mengfei etc., chemical journal, 2005,63 (16), 1469-1473; Sch ǒ nfelder, D.; Nuyken, D.; Weberskirch, R.J.Organomet.Chem.2005,690,4648-4655), but use textile material to make the report that rarely has of carrier.People such as Colacot have reported application (Colacot, the T.J. of fibre grafting phosphino-loaded palladium catalyst in the Suzuki reaction; Gore, E.S.; Kuber, A.Organometallics 2002,21 (16), and 3301-3304), its commercial prod has been obtained quite successful (as FiberCat 1001).Notification number CN1401667A has reported and has contained heterocyclic polymer carried metal palladium complex and the application in the Heck reaction thereof that this catalyst catalytic performance is good.
Summary of the invention
One of purpose of the present invention is to provide a kind of high-molecular fabric load palladium catalyst.
Two of purpose of the present invention is to provide this Preparation of catalysts method.
Because polyacrylonitrile weaving cloth (PAN) has cheap, specific area is bigger, advantages such as swellability is good, therefore the inventive method is a main material with the general goods fabric, utilize the functional group on the fabric, earlier it is carried out graft modification, and then the carried metal palladium, thereby high-molecular fabric load palladium catalyst obtained.
According to above-mentioned mechanism, the present invention adopts following technical scheme:
A kind of high-molecular fabric load palladium catalyst is characterized in that this catalyst is a skeleton with polyacrylonitrile weaving cloth, Jie Zhi oxazoline, and form high-molecular fabric load palladium catalyst with the palladium ion coordination; The percent grafting of Qi Zhong oxazoline is 10%～50%, with the coordination ratio of palladium ion be 2: 1～1: 2.
The percent grafting of Shang Shu De oxazoline is 25%～40%.
A kind of method for preparing above-mentioned high-molecular fabric load palladium catalyst is characterized in that the concrete steps of this method are as follows:
A. synthetic vectors: polyacrylonitrile weaving cloth is immersed in the mixed solution of the monoethanolamine that contains lewis acid catalyst and chlorobenzene, and soak time is 10～60 minutes; The mass ratio of described monoethanolamine and chlorobenzene is 1: 10～100, and described lewis acid catalyst is 2～5% with respect to the mole of itrile group in the polyacrylonitrile weaving cloth, and the mol ratio of itrile group and monoethanolamine is 2～0.5: 1 in the polyacrylonitrile weaving cloth; Under 100～150 ℃ of temperature, carried out graft reaction 1.0～3.0 hours then, rocked once in per 30 minutes; Take out weaving cloth and drain chlorobenzene, it is most neutral to be washed to PH, embathes with ethanol again, and vacuum drying obtains fabric carrier;
B. carried metal palladium: step a gained fabric carrier is soaked in the alcoholic solution of saturated palladium salt N
2Protection room temperature lucifuge was down reacted 24～48 hours, and reaction finishes, and the fabric carrier that will contain palladium leaches, and embathes to solution colourless with solvent alcohol; Vacuum drying obtains high-molecular fabric load palladium catalyst; Described solvent alcohol is absolute methanol or absolute ethyl alcohol.
Above-mentioned Lewis acid catalyst is ZnCl
2Or Zn (OAc)
2Described palladium salt is palladium, palladium bichloride, palladium bichloride sodium or palladium bichloride potassium.
The above-mentioned monoethanolamine and the mass ratio of chlorobenzene are 1: 20～30; The temperature of graft reaction is 110 ℃ during the synthetic textiles carrier.
The reaction mechanism of said method is:
In above-mentioned course of reaction, the factor that generates high-molecular fabric load palladium catalyst has following several:
1. the percent grafting of fabric carrier should be with 10-50% for well, and be best with 25-40%, when percent grafting 10% when following, because of coordination site is few, poor to the load capacity of palladium; And when percent grafting greater than 50% the time, the variable cirrhosis of textile material is crisp, mechanical performance is damaged, though the load capacity of palladium is strengthened, because of its catalytic performance and reusability reduce.
2. the temperature of graft reaction when reaction temperature is lower than 100 ℃, reacts and carry out very slowly, and when reaction temperature was higher than 150 ℃, it is too fast that reaction is carried out, and the extent of reaction is inhomogeneous.So ， oxazoline graft reaction temperature is 100-150 ℃, is the best with 110 ℃.
3. better to the swellability of fabric because of chlorobenzene, so can chlorobenzene be the solvent of graft reaction.When monoethanolamine concentration was too low, reaction was carried out very slow, thereby the mass ratio of chlorobenzene and monoethanolamine is 10: 1-100: 1, and with 20: 1-30: 1 is good.The mol ratio of nitrile group content and monoethanolamine is with 2 in the fabric: 1-0.5: 1 is good.
4. the complexation reaction of fabric carrier and palladium salt is at room temperature carried out.Water can produce bigger adverse effect to reaction, makes the hydrolysis and running off before complexation reaction takes place of palladium salt, in generally general solvent, the dissolubility of palladium salt is all not so good, and the solvability in alcohol still can, thereby can adopt absolute methanol or absolute ethyl alcohol to make solvent, and absolute methanol the best.Complexation reaction also must lucifuge be carried out.When reaction temperature is high (as refluxing in absolute methanol), palladium forms the seal complex rapidly and stops internal layer functional group participation coordination on the fabric carrier surface, and palladium only stockpiles on the surface like this, and its stability reduces, and runs off easily when reusing and wash.And slow down in room temperature reaction speed, the not only coordinating group on surface participation palladium coordination in the fabric carrier, the coordinating group of internal layer has also participated in complexation reaction after swelling, so palladium is combined on the fabric more securely, helps it and recycle.The dentate of fabric carrier and the coordination ratio of palladium should be 2: 1-1: 2 is good.
A kind of high-molecular fabric load palladium catalyst is characterized in that this catalyst is a skeleton with polyacrylonitrile weaving cloth, and is crosslinked with polyamine, and forms high-molecular fabric load palladium catalyst with the palladium ion coordination; Wherein the crosslinking rate of polyamine is 0.1%～6%, with the coordination ratio of palladium ion be 2: 1～1: 2.
A kind of method for preparing above-mentioned high-molecular fabric load palladium catalyst is characterized in that the concrete steps of this method are as follows:
A. synthetic vectors: the polyacrylonitrile cloth of weaving is immersed in the ethylene glycol solution of crosslinking agent polyamine 10～60 minutes, and ethylene glycol and crosslinking agent mass ratio are 20: 1～60: 1, and the mol ratio of itrile group and monoethanolamine is 1～0.5: 1 in the polyacrylonitrile weaving cloth; Under 100～150 ℃ of temperature, carried out cross-linking reaction 1.0～3.0 hours then, rocked once in per 30 minutes; Reaction leaches fabric after finishing, and it is most neutral to be washed to PH, embathes with ethanol again, and vacuum drying gets crosslinked fabric; Again will this crosslinked fabric join in 4% the NaOH or potassium hydroxide solution, reaction 1～3 hour is hydrolyzed under 80 ℃; Reaction is filtered crosslinked fabric after finishing, and it is most neutral to be washed to PH, embathes with ethanol again, and vacuum drying gets fabric carrier;
B. carried metal palladium: step a gained fabric carrier is soaked in the aqueous solution of palladium salt, and wherein the mol ratio of fabric carrier and palladium salt is: 3: 1～1: 1; N
2Protection room temperature lucifuge was down reacted 24～48 hours, and reaction finishes, and the fabric carrier that will contain palladium leaches, and water embathes to solution colourless; Vacuum drying obtains high-molecular fabric load palladium catalyst.
Above-mentioned polyamine crosslinking agent diethylenetriamine, triethylene tetramine or ethylenediamine; Described palladium salt is palladium, palladium bichloride, palladium bichloride sodium or palladium bichloride potassium.
Above-mentioned ethylene glycol and crosslinking agent mass ratio are 30: 1～40: 1; The temperature of cross-linking reaction is 110 ℃ during synthetic vectors.
The reaction mechanism of said method is:
In this course of reaction, crosslinked purpose is in order to form network structure in fabric, to guarantee the stability of fabric in the hydrolysis of back and practical application from now on, choose crosslinking rate between 0.1-6%, be under the prerequisite that guarantees weave machine intensity, keep more itrile groups and participate in next step hydrolysis.Fabric hydrolysis in 4% aqueous slkali, percent hydrolysis are less than 10%, and the itrile group hydrolysis very little, and is few with the palladium coordination site; Percent hydrolysis is greater than 70%, and water absorption of fabrics is strong, is dispersed in the aqueous solution, and the fabric loss is big.So percent hydrolysis is best at 10%-70% with 30%-60%.Hydrolysis of the present invention generates carboxyl so that obtain to be similar to the catalytic activity point of simple little molecule palladium.
The complexation reaction of fabric carrier and palladium is to carry out under the normal temperature in the aqueous solution of palladium bichloride sodium.If make solvent with ethanol or methyl alcohol, the fabric swellability is poor, and palladium only carries out ion-exchange on the surface, and the load capacity of palladium seldom, and is also unstable.The swellability of fabric after the hydrolysis in water is better, and for this reason, we select water as solvent for use.Fabric complete swelling in water is opened, and the palladium ion exchange is more complete, and the palladium load capacity is bigger, and more stable.Palladium bichloride sodium or palladium bichloride sylvite are better than palladium bichloride at water stability, and the present invention adopts the palladium bichloride sodium salt to provide Metal Palladium to carry out ion-exchange reactions.The coordination ratio of dentate and palladium should be 2: 1-1: 2 is good.
Compared with prior art; the advantage of the inventive method is: high-molecular fabric load palladium catalyst of the present invention does not need to activate palladium with reducing agent before catalysis Heck reaction; when reacting, uses catalysis Heck the mixed solvent of second alcohol and water inexpensive, environmental protection; do not need inert gas shielding in the catalytic process; need not add any phase transfer catalyst, have very high catalytic activity.Really realized the catalytic process of " environmental protection ".
Description of drawings
Fig. 1 is the preceding SEM figure of the high-molecular fabric load palladium of Jie Zhi oxazoline.
Fig. 2 is the SEM figure behind the high-molecular fabric load palladium of Jie Zhi oxazoline.
Fig. 3 is the preceding SEM figure of the high-molecular fabric load palladium of crosslinked polyamine
Fig. 4 is the SEM figure behind the high-molecular fabric load palladium of crosslinked polyamine.
The specific embodiment
When not being particularly limited among the embodiment, the ratio of reactive material is that the percent hydrolysis of percent grafting, crosslinking rate and the itrile group of mass ratio ， oxazoline calculates by the heavy method of difference, and palladium content is respectively by heavy method of difference and aas determination.The evaluation of the oxazoline ring U.S. Buddhist nun high-tensile strength AVATAR370 of company type infrared spectrometer.SEM photo JSM-6700F sem observation, shooting.Elementary analysis is measured with Vario EL III.The polyacrylonitrile fabric is that PAN fiber (3.33dtex, 65mm, Shanghai Kingsoft Co.) forms single face polyacrylonitrile knitted fabric, 280-310g/m through weaving
2
One, the preparation of the high-molecular fabric load palladium catalyst of Jie Zhi oxazoline
1. synthetic vectors: take by weighing the monoethanolamine of 1mmol, add chlorobenzene solvent, add the anhydrous ZnCl of lewis acid catalyst then with respect to itrile group 2-5% mole in table 1 ratio
2Or Zn (OAc)
2Stirring makes the lewis acid catalyst dissolving, stops to stir.The fabric that takes by weighing nitrile group-containing 1mmol adds reaction system and soaked 30 minutes, is warming up to 110 ℃ of reactions then, rocks once in per 30 minutes, be incubated after 1-3 hour, take out fabric and drain chlorobenzene, be washed to neutrality, ethanol embathes, vacuum drying, and the percent grafting of Ji Suan oxazoline is with oxazoline content.
Table 1: the grafting result of embodiment 1-5 oxazoline
| Sequence number | Carrier | Chlorobenzene/monoethanolamine | Reaction time/h | Percent grafting/% | Oxazoline content/mmolg -1 |
| 1 2 3 4 5 | I II III IV V | 58∶1 45∶1 28∶1 28∶1 28∶1 | 2 2 1.5 3 5 | 9.8 14.0 23.7 43.3 49.4 | 2.03 2.81 4.35 6.87 7.51 |
2. carried metal palladium: embodiment 6-8, the reaction result of different solvents Zhong oxazoline grafting fabric and palladium coordination sees Table 2,
A certain amount of fabric carrier is soaked in the excessive saturated palladium salting liquid N
2Protection is room temperature lucifuge reaction certain hour down, and reaction finishes, will contain the palladium fabric to leach, when embathing, product constant weight colourless to solution with solvent till.Weigh after the vacuum drying, survey palladium content, obtain the high-molecular fabric load palladium catalyst of Jie Zhi oxazoline.
Table 2: embodiment 6-8 fabric carrier and palladium coordination result
| Sequence number | Carrier | Catalyst | Palladium salt | Solvent | Reaction time/h | Palladium content/mmolg -1 |
| 6 7 8 | I I IV | A B C | PdCl 2 Na 2PdCl 4 Pd(OAc) 2 | Absolute ethyl alcohol absolute ethyl alcohol absolute methanol | 72 72 24 | 0.46 0.38 1.06 |
The high-molecular fabric load palladium catalyst of method for preparing characterizes raw material PAN, fabric carrier and high-molecular fabric load palladium catalyst with the U.S. AVATAR370 of Buddhist nun's high-tensile strength company type infrared spectrometer.2242cm in the INFRARED ABSORPTION of fabric carrier
-1The itrile group absorption peak strength at place obviously weakens than raw material PAN; 1654cm in the fabric carrier
-1C=N stretching vibration absworption peak, 1255cm have appearred in the place
-1C-O-C asymmetric stretching vibration absworption peak, 1172cm have appearred in the place
-1, 1060cm
-1C-O-C symmetrical stretching vibration absworption peak, 954cm have appearred in the place
-1, 923cm
-1C-O-C flexural vibrations absworption peak, the generation of these Biao Ming oxazoline rings have appearred in the place.1654cm in the fabric carrier
-1, 1255cm
-1, 1172cm
-1, 1060cm
-1The absworption peak at place has become 1625cm respectively in high-molecular fabric load palladium catalyst
-1, 1232cm
-1, 1164cm
-1, 1043cm
-1, N and O and palladium have carried out complexation reaction on the Biao Ming oxazoline ring, make the absworption peak position that displacement take place.As can see from Figure 1, there are many concavo-convex grooves at fabric Jie Zhi oxazoline place.Behind the fabric load palladium, it is mild relatively that the surface becomes, and load has the granule of palladium component to be dispersed in fabric face, referring to Fig. 2.
The reaction equation that oxazoline forms is as follows:
The computational methods of the content of oxazoline: calculate the content of the grafting De of institute oxazoline according to the weight difference of textile material before and after the graft reaction, it is as follows to calculate general formula:
X: oxazoline content (mmol/g), W: reaction back fabric carrier quality (mg), W
o: fabric carrier PAN quality (mg) before the reaction, 17:NH
3Molal weight.
The oxazoline percent grafting is calculated as follows:
I%: oxazoline percent grafting, W: reaction back fabric carrier quality (mg), W
o: fabric carrier PAN quality (mg) before the reaction.
Two, the preparation of the high-molecular fabric load palladium catalyst of crosslinked polyamine
1. synthetic vectors: the fabric 0.64g of nitrile group-containing joined in the 20ml ethylene glycol solution that contains the 6mmol diethylenetriamine soaked 30 minutes, be warmed up to 110 ℃ then, rocked once insulation 2h in per 30 minutes.Reaction leaches fabric after finishing, and is washed to neutrality, and ethanol embathes, and after the vacuum drying, calculates crosslinking rate, gets crosslinked fabric 0.6535g, and crosslinking rate is 2%.The crosslinked fabric 0.6535g of gained joined in 4% the sodium hydroxide solution 80 ℃ of reactions 2 hours down.After reaction finished, filter fiber was washed to neutrality.Ethanol embathes.After the vacuum drying, calculate percent hydrolysis, get carrier VI 1.0301g, percent hydrolysis 57.6%, carboxyl-content 9.37mmol/g.
The carried metal palladium: embodiment 11-13, the reaction of carrier VI and palladium coordination in the different solvents, referring to table 3, step is as follows:
A certain amount of carrier VI is soaked in the excessive palladium salting liquid N
2Protection is room temperature lucifuge reaction certain hour down, and reaction finishes, filtering catalyst, when embathing, product constant weight colourless to solution with solvent till.Weigh after the vacuum drying, survey palladium content, obtain the high-molecular fabric load palladium catalyst of crosslinked diethylenetriamine.
Table 3: embodiment 11-13 hydrolysis fabric and palladium coordination result
| Sequence number | Catalyst | Palladium salt | Solvent | Reaction time/h | Palladium content/mmolg -1 |
| 11 12 13 | D E F | PdCl 2Pd(OAc) 2Na 2PdCl 4 | Absolute ethyl alcohol absolute methanol water | 48 72 24 | 0.13 0.25 0.95 |
The high-molecular fabric load palladium catalyst of method for preparing characterizes crosslinked fabric, hydrolysis fabric carrier and high-molecular fabric load palladium catalyst with the U.S. AVATAR370 of Buddhist nun's high-tensile strength company type infrared spectrometer.2243cm in the crosslinked fabric carrier
-1It is very little that itrile group absorption peak strength and the PAN raw material at place compared variation, illustrates that crosslinking degree is very little, and obviously weaken in the hydrolysis fabric carrier, illustrates that hydrolysis has taken place the itrile group major part.1646cm in the crosslinked fabric carrier
-1C=N stretching vibration absworption peak has appearred in the place, the crosslinked imidazoline that generated of fabric is described, and there is the flexural vibrations absworption peak of N-H at 1608 places.1668cm in the hydrolysis fabric carrier
-1The C=O stretching vibration absworption peak of acid amides has appearred in the place, and 1560cm
-1And 1402cm
-1The C-O stretching vibration absworption peak of carboxylate has appearred in the place.1731cm in high-molecular fabric load palladium catalyst
-1The C=O stretching vibration absworption peak of carboxylic acid has appearred in the place, has illustrated that the part carboxylate is hydrolyzed into carboxylic acid.And 1558cm
-1And 1396cm
-1The place absorbs and hydrolysis fabric 1560cm
-1And 1402cm
-1The place absorbs displacement has taken place, and shows that coordination has taken place for carboxyl and palladium.As can see from Figure 3, fabric hydrolysis rear surface is uneven, and the palladium particulate that accumulation is arranged after the supported palladium is on the surface, referring to Fig. 4.
The computational methods of crosslinking rate Tong oxazoline percent grafting.
The percent hydrolysis of itrile group
M%: itrile group percent hydrolysis, W: reaction back fabric carrier quality (mg), W
o: the quality (mg) of carrying out the fabric of crosslinked mistake before the reaction.
The content of carboxyl
Y: carboxyl-content (mmol/g), W: reaction back fabric carrier quality (mg), W
o: carry out the quality (mg) of the fabric of crosslinked mistake before the reaction, Ma: the molal weight of carboxylate, Mn: the molal weight of itrile group.
Three, catalysis Heck reaction
Select best two kinds of high-molecular fabric load palladium catalyst C and F to carry out following catalytic reaction.
Embodiment 14-29, catalysis Heck reaction in the different solvents, referring to table 4 and table 5, step was as follows: with iodobenzene (1mmol), ethyl acrylate, triethylamine and palladium-containing catalyst 1: 1.5: 2.5 in molar ratio: 1% joins in the solvent of 5ml, the back flow reaction certain hour, the some plate detects, after reaction finishes, cross silica gel plate and isolate product, calculated yield after the vacuum drying.The products therefrom warp
1H-NMR turns out to be transconfiguration.
Table 4: embodiment 14-21 catalyst C catalysis Heck reaction result
| Sequence number | Solvent | Time/h | Conversion ratio a/% |
| 14 | Oxolane | 65 | 99 |
| 15 | Acetonitrile | 16 | 100 |
| 16 | Toluene | 4 | 85 |
| 17 | 1, the 4-dioxane | 4 | 95 |
| 18 | Ethanol | 16 | 95 |
| 19 | Ethanol/water=5/1 | 4 | 98 |
| 20 | Water | 7 | 100 b |
| 21 | N, dinethylformamide c | 4 | 100 |
A: be the conversion ratio of iodobenzene
B: cinnamic acid/ethyl cinnamate=21.4/78.6
C:80 ℃ of reaction
Table 5: embodiment 22-29 catalyst F catalysis Heck reaction result
| Sequence number | Solvent | Time | Conversion ratio a/% |
| 22 | Oxolane | 48 | ＜5 |
| 23 | Acetonitrile | 67 | 95 |
| 24 | Toluene | 48 | 85 |
| 25 | 1, the 4-dioxane | 97 | 55 |
| 26 | Ethanol | 29 | 97 |
| 27 | Ethanol/water=5/1 | 24 | 97 |
| 28 | Water | 22 | 100 b |
| 29 | N, dinethylformamide c | 4 | 100 |
A: be the conversion ratio of iodobenzene
B: cinnamic acid/ethyl cinnamate=32.8/67.2
C:80 ℃ of reaction
Embodiment 30-32, catalyst circulation catalysis Heck reaction, referring to table 6, step is as follows:
With iodobenzene (1mmol), ethyl acrylate, triethylamine and palladium-containing catalyst 1: 1.5: 2.5 in molar ratio: 1% joined in the solvent of 5ml, the back flow reaction certain hour, the point plate is followed the tracks of, after reaction finishes, the decant product, small amount of ethanol washing catalyst three times is again with a small amount of washed with dichloromethane three times, after the drying, the reinforced again catalytic reaction next time of carrying out.
Table 6: embodiment 30-32 circulation catalysis Heck reaction result
| Sequence number | Catalyst | Solvent | Iodobenzene conversion ratio/% | |||
| 1 | 2 | 3 | 4 | |||
| 30 a 31 a 32 b | C C F | 1,4-dioxane ethanol/water=5/1 ethanol/water=5/1 | 95 98 97 | 96 98 95 | 95 97 95 | 92 95 90 |
A: react 4 hours b: reacted 24 hours
Claims (9)
1. a high-molecular fabric load palladium catalyst is characterized in that this catalyst is a skeleton with polyacrylonitrile weaving cloth, connects an oxazoline, and forms high-molecular fabric load palladium catalyst with the palladium ion coordination; The percent grafting of Qi Zhong oxazoline is 10%～50%, with the coordination ratio of palladium ion be 2: 1～1: 2.
2. high-molecular fabric load palladium catalyst according to claim 1 is characterized in that the percent grafting of Suo Shu De oxazoline is 25%～40%.
3. method for preparing high-molecular fabric load palladium catalyst according to claim 1 is characterized in that the concrete steps of this method are as follows:
A. synthetic vectors: polyacrylonitrile weaving cloth is immersed in the mixed solution of the monoethanolamine that contains lewis acid catalyst and chlorobenzene, and soak time is 10-60 minute; The mass ratio of described monoethanolamine and chlorobenzene is 1: 10～100, and described lewis acid catalyst is 2～5% with respect to the mole of itrile group in the polyacrylonitrile weaving cloth, and the mol ratio of itrile group and monoethanolamine is 2～0.5: 1 in the polyacrylonitrile weaving cloth; Under 100～150 ℃ of temperature, carried out graft reaction 1～3 hour then, rocked once in per 30 minutes; Take out weaving cloth and drain chlorobenzene, it is most neutral to be washed to PH, embathes with ethanol again, and vacuum drying obtains fabric carrier;
B. carried metal palladium: step a gained fabric carrier is soaked in the alcoholic solution of saturated palladium salt N
2Protection is room temperature lucifuge reaction 2-48 down, and reaction finishes, and the fabric carrier that will contain palladium leaches, and embathes to solution colourless with solvent alcohol; Vacuum drying obtains high-molecular fabric load palladium catalyst; Described solvent alcohol is absolute methanol or absolute ethyl alcohol.
4. the preparation method of high-molecular fabric load palladium catalyst according to claim 3 is characterized in that described Lewis acid catalyst is ZnCl
2Or Zn (OAc)
2Described palladium salt is palladium, palladium bichloride, palladium bichloride sodium or palladium bichloride potassium.
5. the preparation method of high-molecular fabric load palladium catalyst according to claim 3, the mass ratio that it is characterized in that described monoethanolamine and chlorobenzene is 1: 20～30; The temperature of graft reaction is 110 ℃ during the synthetic textiles carrier.
6. a high-molecular fabric load palladium catalyst is characterized in that this catalyst is a skeleton with polyacrylonitrile weaving cloth, and is crosslinked with polyamine, and forms high-molecular fabric load palladium catalyst with the palladium ion coordination; Wherein the crosslinking rate of polyamine is 0.1%～6%, with the coordination ratio of palladium ion be 2: 1～1: 2.
7. method for preparing high-molecular fabric load palladium catalyst according to claim 6 is characterized in that the concrete steps of this method are as follows:
A. synthetic vectors: the polyacrylonitrile cloth of weaving is immersed in the ethylene glycol solution of crosslinking agent polyamine 1-3 hour, and ethylene glycol and crosslinking agent mass ratio are 20: 1～60: 1, and the mol ratio of itrile group and monoethanolamine is 1～0.5: 1 in the polyacrylonitrile weaving cloth; Under 100～150 ℃ of temperature, carried out cross-linking reaction 1～3 hour then, rocked once in per 30 minutes; Reaction leaches fabric after finishing, and it is most neutral to be washed to PH, embathes with ethanol again, and vacuum drying gets crosslinked fabric; Again will this crosslinked fabric join in 4% the NaOH or potassium hydroxide solution, reaction 1-3 hour is hydrolyzed under 80 ℃; Reaction is filtered crosslinked fabric after finishing, and it is most neutral to be washed to PH, embathes with ethanol again, and vacuum drying gets fabric carrier;
B. carried metal palladium: step a gained fabric carrier is soaked in the aqueous solution of palladium salt, and wherein the mol ratio of fabric carrier and palladium salt is: 3: 1-1: 1; N
2Protection is room temperature lucifuge reaction 2-24 down, and reaction finishes, and the fabric carrier that will contain palladium leaches, and water embathes to solution colourless; Vacuum drying obtains high-molecular fabric load palladium catalyst.
8. the preparation method of high-molecular fabric load palladium catalyst according to claim 7 is characterized in that described polyamine crosslinking agent diethylenetriamine, triethylene tetramine or ethylenediamine; Described palladium salt is palladium, palladium bichloride, palladium bichloride sodium or palladium bichloride potassium.
9. the preparation method of high-molecular fabric load palladium catalyst according to claim 7 is characterized in that described ethylene glycol and crosslinking agent mass ratio are 30: 1～40: 1; The temperature of cross-linking reaction is 110 ℃ during synthetic vectors.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710037421 CN101024197A (en) | 2007-02-09 | 2007-02-09 | High-molecular fabric load palladium catalyst and preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710037421 CN101024197A (en) | 2007-02-09 | 2007-02-09 | High-molecular fabric load palladium catalyst and preparing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101024197A true CN101024197A (en) | 2007-08-29 |
Family
ID=38743020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710037421 Pending CN101024197A (en) | 2007-02-09 | 2007-02-09 | High-molecular fabric load palladium catalyst and preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101024197A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105921173A (en) * | 2016-04-21 | 2016-09-07 | 河南大学 | Nano-silver composite textile catalyst and application thereof |
| CN107321388A (en) * | 2017-06-29 | 2017-11-07 | 天津工业大学 | A kind of manufacture method of fibrous heterogeneous Fenton catalyst |
| CN110656391A (en) * | 2019-09-25 | 2020-01-07 | 翁菀蕾 | Composite conductive fabric and manufacturing method thereof |
| CN113828305A (en) * | 2021-10-11 | 2021-12-24 | 盱眙凹土能源环保材料研发中心 | Preparation method of Pd/attapulgite catalyst for cross-coupling reaction |
-
2007
- 2007-02-09 CN CN 200710037421 patent/CN101024197A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105921173A (en) * | 2016-04-21 | 2016-09-07 | 河南大学 | Nano-silver composite textile catalyst and application thereof |
| CN107321388A (en) * | 2017-06-29 | 2017-11-07 | 天津工业大学 | A kind of manufacture method of fibrous heterogeneous Fenton catalyst |
| CN110656391A (en) * | 2019-09-25 | 2020-01-07 | 翁菀蕾 | Composite conductive fabric and manufacturing method thereof |
| CN113828305A (en) * | 2021-10-11 | 2021-12-24 | 盱眙凹土能源环保材料研发中心 | Preparation method of Pd/attapulgite catalyst for cross-coupling reaction |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101024197A (en) | High-molecular fabric load palladium catalyst and preparing method | |
| CN100431704C (en) | Method for preparing chitose magnetic microsphere metal palladium complex catalyst | |
| CN109894153A (en) | A kind of catalyst preparation and application of N-heterocyclic carbine covalent organic frame material supported palladium | |
| CN104607248A (en) | Pyrene-4,5,9,10-quadri-imine-(arylamine) palladium chloride and application thereof in Heck reaction | |
| CN102921466A (en) | Heterogeneous Au/Ze-MOF catalyst and preparation method and application thereof | |
| He et al. | Insight into the reversible behavior of Lewis–Brønsted basic poly (ionic liquid) s in one-pot two-step chemical fixation of CO 2 to linear carbonates | |
| CN103788034A (en) | Preparation method for 5-hydroxymethylfurfural | |
| CN103254408A (en) | Self-immobilized porous organic polymer material, preparation method and application thereof | |
| CN106905526A (en) | Rigid backbone porous polymer with gas absorption performance and its preparation method and application | |
| Zhang et al. | Metal-salen-bridged ionic networks as efficient bifunctional solid catalysts for chemical fixation of CO2 into cyclic carbonates | |
| CN109897190A (en) | A kind of covalent organic frame material and its synthetic method of N-heterocyclic carbine functionalization | |
| CN107739444B (en) | Based on amino functionalization of YbIIIMetal organic framework material with hexanuclear molecular structural unit and preparation method and application thereof | |
| CN112221540A (en) | Pd2+Loaded metal organic framework composite catalyst, preparation method and application | |
| CN107987015A (en) | A kind of asymmetric double pyridine radicals olefin(e) compounds and its preparation method and application | |
| CN114733566A (en) | Chiral super-strong carbonic acid catalyst based on BINOL skeleton and preparation method and application thereof | |
| CN113198538A (en) | Preparation method of superstrong fiber-loaded Schiff base palladium catalyst | |
| Mikhailov et al. | Chiral acyclic diaminocarbene complexes of palladium (II) immobilized on a polymeric support as promising catalysts of the Suzuki reaction | |
| CN114805120A (en) | Synthesis process of m-cyanomethyl benzoate | |
| CN107519937A (en) | A kind of short immobilized azepine Cabbeen Ag composition catalysts of fibre and preparation method thereof | |
| CN102320916A (en) | Method for preparing diiodomethane by solid-supported phase transfer catalyst | |
| CN114570353A (en) | Non-noble metal composite catalyst and preparation method and application thereof | |
| CN111841587A (en) | Solid base catalyst and preparation method thereof | |
| CN101121147A (en) | Novel catalyzing technology for preparing dimethyl carbonate and its catalyst and preparation | |
| CN116174038B (en) | Polyaza ligand palladium functionalized fiber and preparation method and application thereof | |
| CN112279821B (en) | Synthesis method of 4, 4-difluoro-3-oxo-2-piperidine-1-yl methylene ethyl butyrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |