CN104190467B - A kind of preparation method of non-PNIPAm base temperature sensitive intelligence Raney nickel - Google Patents
A kind of preparation method of non-PNIPAm base temperature sensitive intelligence Raney nickel Download PDFInfo
- Publication number
- CN104190467B CN104190467B CN201410351103.2A CN201410351103A CN104190467B CN 104190467 B CN104190467 B CN 104190467B CN 201410351103 A CN201410351103 A CN 201410351103A CN 104190467 B CN104190467 B CN 104190467B
- Authority
- CN
- China
- Prior art keywords
- preparation
- catalyst
- pnipam
- temperature sensitive
- function monomer
- 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.)
- Active
Links
Landscapes
- Catalysts (AREA)
Abstract
The preparation method of a kind of non-PNIPAm base of the present invention temperature sensitive intelligence Raney nickel, belongs to high-molecular organic material technical field.Mimic biology body of the present invention heals function automatically, with self-healing polymer be carrier, nickel nano particle for active component, be directly realized can modulate, the preparation of temperature sensitive intelligence nickel-base catalyst.Preparation method of the present invention is simple, easy to operate, has certain universality, and equipment needed thereby is less demanding, it is easy to accomplish large-scale industrial production.
Description
Technical field
The invention belongs to high-molecular organic material technical field, be specifically related to a kind of non-poly-NThe preparation method of-N-isopropylacrylamide (PNIPAm) base temperature sensitive intelligence Raney nickel.
Background technology
For a long time, it is achieved the control of catalytic action process is always up, with regulating, the important scientific problems that industry is badly in need of solving.The realization developing into this target in synthesis chemistry and New Intelligent Material field creates condition.By the inspiration of drug controlled release technology, scientists finds, adopts poly-N-N-isopropylacrylamide (PNIPAm) is carrier, metal nanoparticle is active component, can develop the new ideas catalyst with temperature-responsive ability；When using polyacrylic acid, crown ether polymer, tritan. based polyalcohol etc. instead for metal nanoparticle carrier, the new catalyst with responding abilities such as pH, ion and light can be prepared.Compared with changing pH, ion etc., it is achieved the control of temperature is physically easier to perform, and equipment requirements is relatively low, therefore becomes most widely used modulation means.Owing to critical temperature condition is gentle, and response is rapidly, and PNIPAm is that current application is the most successful and temperature sensitive intelligent material the most widely.It is known that the construction features of the hydrophilic amide base-hydrophobicity isopropyl of PNIPAm makes it define the critical solution temperature (~ 32 of uniqueness in an aqueous mediumoC).When lower than critical temperature, in PNIPAm, amide groups has promoted its dissolving in water with the interaction of hydrogen bond of aqueous media, makes substrate obtain the passage towards active component, and catalytic action is " unpacked "；Otherwise, when higher than critical temperature, in polymer, the relative equilibrium of hydrophilic amide base-hydrophobicity isopropyl is broken, polymer becomes insoluble in, water from its internal discharge, causes " blocking " of substrate channels, so that catalytic action obtains " closedown " rapidly.In the way of this uniqueness, intelligent catalysis agent, by the temperature-sensitive phase transformation of PNIPAm under critical temperature condition, makes chemical reaction obtain transition immediately or " freezing ", skips or rest on default position, thus realizing the control to chemical action process and adjustment.
But, in actual applications, most polymer carrier is not as PNIPAm, it does not have temperature-sensitive transformation behavior and transformation temperature, it is impossible to meet can control, the requirement of scalable catalytic action, thus causing obvious obstacle to the application of intelligent catalysis agent.The report of the Chinese patent also temperature sensitive intelligent catalysis agent of PNIPAm nothing but.For overcoming this present situation, a few studies person has carried out exploratory work, have employed the polymer of several different shape and is used as the carrier of metal nanoparticle, as: hydrogel, egg yolk-core/shell nano particle, functionalization microsphere etc. (Angew.Chem.Int.Ed.,2012,51,9164-9168;NewJ.Chem.,2010,34,1355-1364;NanoLett., 2008,8,2643-2647), develop the function catalyst come in every shape.But, owing to these carrier polymers do not possess character and the ability of intelligent response, therefore the catalyst obtained cannot meet the requirement that can control, can modulate catalytic action, the intelligent catalysis agent of practicality cannot be produced, thus forcing people to develop the new method of more universality and higher intelligent catalysis material.
Summary of the invention
It is an object of the invention to be badly in need of the important scientific problems of solution for industry, the preparation method that a kind of non-PNIPAm base temperature sensitive intelligence Raney nickel is provided, the method adopts automatic healing polymerization thing to be carrier, authorize the catalyst temperature sensitive responding ability of intelligence, have raw material be easy to get, technique simple, and there is the features such as certain universality.
The preparation method of a kind of non-PNIPAm temperature sensitive intelligence Raney nickel, carries out: catalyst precursor one-step synthesis as steps described below: the required complementary interaction of healing is made up of vinyl imidazole and the acrylic acid (or the 2-acrylamide-2-methylpro panesulfonic acid and acrylamide by 1:1 mol ratio is constituted) of 1:1 mol ratio automatically.By initiator (azo-bis-isobutyl cyanide；0.30g), function monomer (1-vinyl imidazole and acrylic acid；Equal 5.5mmol), active constituent presoma (Nickelous nitrate hexahydrate；0.40g) with cross-linking agent (EGDMA；The function monomer amount of 6wt-%) it is dissolved in acetonitrile (10mL).After ultrasonic disperse and logical nitrogen deoxidation, seal test tube, be placed under room temperature and irradiate 24 hours in uviol lamp (365nm), aggregate into formation catalyst precursor.In presoma, nickel ion reduces (10 times of nickel ions) through excessive sodium borohydride, cleans through water and filters final vacuum after drying, obtains required catalyst.
Preparation method of the present invention is simple, easy to operate, and has certain universality, and equipment needed thereby is less demanding, it is easy to accomplish large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the processing technology routine of prepared catalyst in the embodiment of the present invention 1.
Fig. 2 is the FTIR spectrum of prepared catalyst in the embodiment of the present invention 1.
Fig. 3 is the TEM photo of prepared catalyst in the embodiment of the present invention 1.
Fig. 4 is the dynamic scattering DLS transformation curve of prepared catalyst in the embodiment of the present invention 1.
Fig. 5 is the modulation catalytic action of prepared catalyst temperature-responsive in the embodiment of the present invention 1.
Fig. 6 is the modulation catalytic action of prepared catalyst temperature-responsive in the embodiment of the present invention 2.
Fig. 7 is the modulation catalytic action of prepared catalyst temperature-responsive in the embodiment of the present invention 3.
Fig. 8 is the modulation catalytic action of prepared catalyst temperature-responsive in the embodiment of the present invention 4.
Detailed description of the invention
By embodiment, the present invention is for a more detailed description below.These embodiments are only the descriptions of best mode for carrying out the invention, rather than the limitative examples of the scope of the invention.
Embodiment 1:
The processing technology routine of catalyst preparing is shown in Fig. 1, and the required complementary interaction of healing is made up of vinyl imidazole and the acrylic acid of 1:1 mol ratio automatically.By initiator (azo-bis-isobutyl cyanide；0.30g), function monomer (1-vinyl imidazole and acrylic acid；Equal 5.5mmol), active constituent presoma (Nickelous nitrate hexahydrate；0.40g) with cross-linking agent (EGDMA；The function monomer amount of 6wt-%) it is dissolved in acetonitrile (10mL).After ultrasonic disperse and logical nitrogen deoxidation, seal test tube, be placed in uviol lamp (365nm) and irradiate 24 hours, aggregate into formation catalyst precursor.In presoma, nickel ion reduces (10 times of mol ratio nickel ions) through excessive sodium borohydride, cleans through water and filters final vacuum after drying, obtains required catalyst (i.e. " SP-Ni ").
For the purpose of contrast, the present embodiment is also prepared for NP-Ni and SP catalyst under similarity condition.Wherein, NP-Ni is that tradition supports Ni catalyst (i.e. non intelligent response Ni catalyst), and in its preparation process except not using comonomer acrylic acid, all the other and SP-Ni prepare identical.SP is SP-Ni carrier, and preparation process does not use outside Nickelous nitrate hexahydrate, and all the other and SP-Ni prepare identical.Fig. 2 to Fig. 4 gives the FTIR spectrum of these several catalyst, TEM photo, its composition and configuration has been characterized, it was shown that the SP-Ni catalyst of preparation is the form designed by the present invention, wherein containing the nickel nano particle of about 20nm size.
Automatic Healing i.e. poly-(1-vinyl imidazole)-poly-(acrylic acid) interacts and is measured by dynamic light scattering DLS, obtains the change of hydration radius by changing the temperature of catalyst system.Corresponding non-response catalyst is deducted by intelligent catalysis agent, it is thus achieved that contribution that poly-(1-vinyl imidazole)-poly-(acrylic acid) interacts (Angew.Chem.Int.Ed., 2006,45,813-816), its result is shown in Fig. 4.Automatic Healing induction NP-Ni phase in version is at 35-42oC, the NP-Ni catalyst of preparation demonstrates the ability of temperature-responsive.
Based on the mensuration (Fig. 4) to its transformation behavior, select respectively lower than transformation temperature and higher than transformation temperature (namely 30 and 50oC) it is measured.Catalytic performance test adopts following reduction system: with methylene blue for substrate (40 μ gmL-1;2mL), (60 μ gmL in sodium borohydride solution are joined-1;2mL).In triplicate, 2.5mg catalyst being added on above-mentioned system and is measured, its result is shown in Fig. 5.The SP-Ni catalyst relatively NP-Ni of activity under cryogenic of preparation is low by (30oC), activity relatively NP-Ni high (50 and under the high temperature conditionsoC).The SP-Ni catalyst of preparation demonstrates the automodulation catalytic action of temperature-responsive.
Embodiment 2:
Operate with embodiment 1, prepare required catalyst.Under catalysis test condition similarly to Example 1, substrate is changed methylene into green, it may be assumed that green for substrate (40 μ gmL with methylene-1;2mL), (60 μ gmL in sodium borohydride solution are joined-1;2mL).In triplicate, 2.5mg catalyst being added on above-mentioned system and is measured, its result is shown in Fig. 6.The SP-Ni catalyst of preparation presents the automodulation catalytic action of temperature-responsive equally.
Embodiment 3:
The preparation of catalyst in operating with embodiment 1, automatically the required complementary interaction that heals is changed the 2-acrylamide-2-methylpro panesulfonic acid by 1:1 mol ratio and acrylamide constitutes (equal 5.5mmol), other synthesis component and consumption are all constant, prepare SP-Ni and SP catalyst, the preparation of NP-Ni catalyst does not use 2-acrylamide-2-methylpro panesulfonic acid, and other is identical with SP-Ni.Under catalysis test condition similarly to Example 1, prepared catalyst being measured, its result is shown in Fig. 7.The SP-Ni catalyst of preparation also shows that the automodulation catalytic action of temperature-responsive.
Embodiment 4:
The preparation of catalyst in operating with embodiment 1, active component changes into platinum, and (presoma is six hydration chloroplatinic acids；0.30mmol), automatically the required complementary interaction that heals is changed the 1-vinyl imidazole by 1:1 mol ratio and 2-(trifluoromethyl) acrylic acid (equal 5.5mmol), other synthesis component and consumption are identical with embodiment 1 catalyst preparing, prepare SP-Pt and SP catalyst, the preparation of NP-Pt catalyst does not use 2-(trifluoromethyl) acrylic acid, and other is identical with SP-Pt.Under catalysis test condition similarly to Example 1, prepared catalyst is measured, changes substrate into uranin, it may be assumed that substrate luciferin is received (0.02 μm of olmL-1;2mL) join (0.01mmolmL in excess sodium borohydrate solution-1;2mL).In triplicate, 2.5mg catalyst being added on above-mentioned system and is measured, its result is shown in Fig. 8.The SP-Pt catalyst of preparation presents the automodulation catalytic action of temperature-responsive equally, it was shown that the preparation method of the present invention non-PNIPAm base temperature sensitive intelligence Raney nickel has certain suitability in other catalyst system and catalyzing.
Claims (1)
1. the preparation method of a non-PNIPAm temperature sensitive intelligence Raney nickel, it is characterised in that carry out as steps described below: initiator azodiisobutyronitrile, function monomer, active constituent presoma Nickelous nitrate hexahydrate and cross-linking agent EGDMA are dissolved in acetonitrile；After ultrasonic disperse and logical nitrogen deoxidation, seal test tube, be placed under room temperature in 365nm ultra violet lamp 24 hours, aggregate into formation catalyst precursor；In presoma, nickel ion reduces through excessive sodium borohydride, cleans through water and filters final vacuum after drying, obtains required catalyst；
Wherein said function monomer is mol ratio is the vinyl imidazole of 1:1 and the 2-acrylamide-2-methylpro panesulfonic acid of acrylic acid or mol ratio 1:1 and acrylamide；
Wherein said initiator azodiisobutyronitrile: function monomer: active constituent presoma Nickelous nitrate hexahydrate: acetonitrile is 0.30g:11mmol:0.40g:10mL；
It is 6% that wherein said cross-linking agent EGDMA accounts for the mass percent of function monomer amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410351103.2A CN104190467B (en) | 2014-07-23 | 2014-07-23 | A kind of preparation method of non-PNIPAm base temperature sensitive intelligence Raney nickel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410351103.2A CN104190467B (en) | 2014-07-23 | 2014-07-23 | A kind of preparation method of non-PNIPAm base temperature sensitive intelligence Raney nickel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104190467A CN104190467A (en) | 2014-12-10 |
| CN104190467B true CN104190467B (en) | 2016-07-06 |
Family
ID=52075916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410351103.2A Active CN104190467B (en) | 2014-07-23 | 2014-07-23 | A kind of preparation method of non-PNIPAm base temperature sensitive intelligence Raney nickel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104190467B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106311326B (en) * | 2016-07-25 | 2019-03-05 | 江苏大学 | A kind of preparation method of " selectivity/non-selective " adjustable Ni base catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747473A (en) * | 2008-12-12 | 2010-06-23 | 南开大学 | Surface-functionalized molecularly imprinted polymer microsphere and preparation method thereof |
| CN102977403A (en) * | 2012-12-24 | 2013-03-20 | 重庆大学 | Molecularly imprinted membrane based on porphyrin and acrylic monomers for organophosphorus pesticide and application thereof |
| CN103752237A (en) * | 2014-01-10 | 2014-04-30 | 陕西师范大学 | Preparation method of pH sensitive microgel loaded nanogold |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100915580B1 (en) * | 2007-10-02 | 2009-09-03 | 고려대학교 산학협력단 | Polymer catalysts comprising heteropoly acid having shape selectivity |
-
2014
- 2014-07-23 CN CN201410351103.2A patent/CN104190467B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747473A (en) * | 2008-12-12 | 2010-06-23 | 南开大学 | Surface-functionalized molecularly imprinted polymer microsphere and preparation method thereof |
| CN102977403A (en) * | 2012-12-24 | 2013-03-20 | 重庆大学 | Molecularly imprinted membrane based on porphyrin and acrylic monomers for organophosphorus pesticide and application thereof |
| CN103752237A (en) * | 2014-01-10 | 2014-04-30 | 陕西师范大学 | Preparation method of pH sensitive microgel loaded nanogold |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104190467A (en) | 2014-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liang et al. | Bioconjugation of papain on superparamagnetic nanoparticles decorated with carboxymethylated chitosan | |
| Zhu et al. | Preparation of nickel nanoparticles in spherical polyelectrolyte brush nanoreactor and their catalytic activity | |
| Eyimegwu et al. | Gold-nanoparticle-embedded poly (N-isopropylacrylamide) microparticles for selective quasi-homogeneous catalytic homocoupling reactions | |
| Baran et al. | Green synthesis of a palladium nanocatalyst anchored on magnetic lignin-chitosan beads for synthesis of biaryls and aryl halide cyanation | |
| CN102226029A (en) | Preparation method of temperature responsive nanohydrogel carrying silver nanoparticles | |
| CN107999077B (en) | Tri-metal nano-grade Prussian-like blue material and application thereof | |
| CN105754021A (en) | Method for preparing mean-particle magnetic polymer microsphere | |
| CN105906760A (en) | Preparation method of novel temperature-sensitive nano gel microspheres | |
| Wang et al. | Pt Nanoparticles confined by zirconium metal–organic frameworks with enhanced enzyme-like activity for glucose detection | |
| CN104959163A (en) | Controllable and adjustable metal nanoparticle-loaded polymer catalyst and preparation method thereof | |
| CN102827330A (en) | Preparation method of gel nano particles in thermosensitivie nuclear shell structure and application of product thereof | |
| Xu et al. | Microfluidic preparation of chitosan microspheres with enhanced adsorption performance of copper (II) | |
| CN104262812A (en) | Magnetic fluorescent polymer microsphere with high load stability and preparation method of magnetic fluorescent polymer microsphere | |
| CN104353494A (en) | Preparation method of intelligent nickel-based catalyst with automatic on/off control function | |
| Ashraf et al. | Synthesis and characterization of pH-responsive organic–inorganic hybrid material with excellent catalytic activity | |
| CN104190467B (en) | A kind of preparation method of non-PNIPAm base temperature sensitive intelligence Raney nickel | |
| CN106040307B (en) | One step hydro thermal method synthesizes Fe3O4(PAA) preparation method of@C-Au core-shell structure microballoon | |
| Ahn et al. | Single-step synthesis of alginate microgels enveloped with a covalent polymeric shell: a simple way to protect encapsulated cells | |
| CN104387712A (en) | Nano composite carrier with superparamagnetism and preparation method thereof | |
| Fan et al. | Cost-effective screening of antimicrobial performance of multiple metal–organic frameworks via a droplet-based batch synthesis platform | |
| Tatykhanova et al. | Metal complexes of amphoteric cryogels based on allylamine and methacrylic acid | |
| Xu et al. | Microfluidic preparation of chitosan–poly (acrylic acid) composite microspheres with a porous surface structure | |
| Häring et al. | Non-enzyme entrapping biohydrogels in catalysis | |
| Žuža et al. | Hydrolysis of penicillin G by penicillin G acylase immobilized on chitosan microbeads in different reactor systems | |
| CN102558581B (en) | Method for preparing high-strength solid chitosan microcarriers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |