CN102489331A - Preparation of super-molecular intelligent hydrogel palladium-supported catalyst and application thereof in Heck reaction - Google Patents
Preparation of super-molecular intelligent hydrogel palladium-supported catalyst and application thereof in Heck reaction Download PDFInfo
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- CN102489331A CN102489331A CN201110403006XA CN201110403006A CN102489331A CN 102489331 A CN102489331 A CN 102489331A CN 201110403006X A CN201110403006X A CN 201110403006XA CN 201110403006 A CN201110403006 A CN 201110403006A CN 102489331 A CN102489331 A CN 102489331A
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Abstract
The invention provides a method for carrying out palladium-supported catalytic Heck reaction on a calixarene super-molecular intelligent gel material. The method mainly comprises the following three steps of: 1, utilizing a calixarene derivative and N-isopropyl acrylamide to copolymerize to obtain a super-molecular intelligent gel P[NIPA-co-Calix]; 2, preparing a P[NIPA-co-Calix] hydrogel palladium-supported catalyst; and 3, carrying out the catalytic Heck reaction on the P[NIPA-co-Calix] hydrogel palladium-supported catalyst. An organic reaction carried in the P[NIPA-co-Calix] hydrogel has three advantages that: (1) a reaction material and Pd<2+> ions of the reversible shrinkage/swelling of the intelligent hydrogel are highly enriched in a gel so that the organic reaction is efficient; (2) a solvent or a cosolvent is not additionally added into the organic reaction in the hydrogel; and (3) the P[NIPA-co-Calix] hydrogel palladium-supported catalyst is easy to recycle and reutilize.
Description
Technical field
The present invention relates to the technology that a kind of progress in Intelligent Hydrogel is used for loaded palladium catalyst catalysis Heck reaction.Be specially a kind of temperature sensitive type intelligent aqueous gel capable, shrink when above when temperature rises to a certain critical-temperature with calixarenes structure, material recoverys of expanding again when temperature is recovered, but and load P d catalysis Heck react.
Background technology
Heck reaction is the reaction of the new C-C key that links to each other with unsaturated double-bond of one type of important formation; This reaction has very high trans stereoselectivity; And reaction condition is gentle, easy and simple to handle, has bigger choice at aspects such as substrate kind, reaction condition, catalyst types; Be a kind of increasingly extensive methodology of organic synthesis of using, be widely used in the synthetic of fine chemistry, agrochemicals and bio-pharmaceuticals intermediate.
Palladium salt homogeneous catalysis C-C coupling reaction has active high, reaction characteristic of simple.But palladium salt homogeneous catalyst is difficult for Separation and Recovery, and use cost is high, and is unfavorable to environment.In order to overcome the shortcoming of homogeneous catalytic reaction, exploitation out-phase palladium catalyst becomes the research focus, has obtained in recent years developing rapidly.Wherein, macromolecule comprises natural polymer carrier and synthetic high polymer carrier as immobilized material.Palladium catalyst is carried on the organic polymer carrier, not only can keeps its catalytic activity, and catalyst is separable through means such as suction filtrations and reclaims that the three-dimensional effect of support materials can also influence the product configuration.Generally speaking, macromolecule carrier should have three characteristics: (1) is carried out chemical modification easily, carries out functionalization again after utilizing monomer polymerization with functional functional group or polymerization to accomplish, make palladium catalyst part can with macromolecule carrier on-OH ,-NH
2, functional groups such as-COOH combine; (2) specific area is bigger, can increase the decentralization of palladium catalyst like this, thereby can improve the catalytic efficiency of catalyst; (3) have certain intensity and chemical stability, can prolong catalyst service life and make it be easy to separate and reclaim.
It is a kind of typical environment-responsive hydrogel that temperature sensitive property is gathered (N-NIPA) hydrogel; Bigger Volume Changes can take place when lower critical solution temperature (LCST); When being heated to LCST when above; Gather (N-NIPA) hydrogel and in water, demonstrate a kind of hydrophilic/hydrophobic and change, water is extruded from gel network and becomes partially hydrophobic, thereby a kind of hydrophobic environment is provided for lyophobic dust.When temperature drops to LCST when following, the hydrogel water absorption and swelling.With the rising and the reduction of temperature, reversible swelling and contraction process can take place in hydrogel.The swelling of this hydrogel depends on temperature consumingly with contraction.
Summary of the invention
The technical problem that quasi-solution of the present invention is determined is to provide a kind of intelligent supramolecular hydrogel to react by load palladium catalysis Heck.This responsive to temperature type supramolecular hydrogel can adsorb Pd
2+Ion is then to Heck reaction carrying out catalysis.A kind of responsive to temperature type supramolecular hydrogel according to the invention is got with (NIPA) copolymerization of N-NIPA by cup [4] arene derivatives (the etherificate product of cup [4] aromatic hydrocarbons and 6-bromo-1-hexene).Its structural formula is following:
The intelligent aqueous gel capable Preparation of catalysts and the application in the Heck coupling reaction thereof of a kind of supported palladium according to the invention comprise:
(1) preparation hydrogel: press Calixarene Derivatives: (Calix: mass ratio NIPA)=0.1 adds NIPA, dissolving behind the 10mlDMF dissolving Calix to the N-NIPA.In above-mentioned mixed solution, add 0.2313g N, N '-methylene-bisacrylamide (MBAA) crosslinking agent and 0.04926g azodiisobutyronitrile (AIBN) initator, the logical nitrogen in dissolving back.Solution is put into 60 ℃ of isoperibols, reaction a period of time, promptly get Calixarene Derivatives and NIPA copolymer hydrogel.
Hydrogel post processing: the copolymer hydrogel of gained was at room temperature soaked 7 days with distilled water,, promptly get described responsive to temperature type intelligent macromolecule hydrogel to remove unreacted small molecule monomer and solvent.
(2) preparation of P [NIPA-co-Calix] hydrogel loaded palladium catalyst: the PdCl that puts into 0.5mL in 40 ℃ of water-baths of the P of 2g [NIPA-co-Calix] hydrogel behind the about 1h of deswelling
2(0.1mmol/L) in the aqueous solution, stir 30min under the room temperature, orange solution becomes colourless transparent solution, promptly obtains P [NIPA-co-Calix] hydrogel loaded palladium catalyst.
(3) hydrogel loaded palladium catalyst catalysis Heck reaction: get the hydrogel catalyst of above-mentioned preparation, add the 2.0mmol iodobenzene, 3.0mmol acrylic acid, the 6.0mmol triethylamine is made acid binding agent.Get the rubber stopper that has two holes and be equipped with two glass tubes (vacuumizing and logical nitrogen) and seal the test tube mouth, vacuumize under the room temperature, logical N
2, vacuumize/fill N three times
2After the circulation.N
2Under the protection, 100 ℃ of oil bath pans reactions were reacted 15 hours.
Post processing: use the 1mol/L hcl acidifying, produce white precipitate, add the dissolving of 20ml ether postprecipitation, ultrasonic extraction 5min room temperature suction filtration; Add product in the 20ml extracted with diethyl ether gel again, suction filtration merges ether solution twice; Ethyl acetate 20ml carries out last ultrasonic extraction to gel, and suction filtration merges in the ether solution.Saturated common salt moisture three times is washed ether and ethyl acetate mixed liquor, and each consumption is about 3 times of mixeding liquid volume.Mixed liquor after the washing merges in the beaker, and add an amount of anhydrous magnesium sulfate and dewater, the room temperature suction filtration, filtrating is poured at the bottom of the roundlet in the flask, and preservative film seals, and on film, pricks several apertures, so that solvent volatilizes at ambient temperature naturally.
Product purification: after solvent volatilizes, use column chromatography silica gel, benzinum: ethyl acetate=20: 1 is solvent, and product is carried out purifying, obtains solid product.
The supramolecular hydrogel of the present invention's design is that product structure is stable by Calixarene Derivatives (the etherificate product of cup [4] aromatic hydrocarbons and 6-bromo-1-hexene) and N-NIPA crosslinking copolymerization gained.This gel has a certain proportion of hydrophobic grouping (CH (CH
3)
2-) and hydrophilic radical (NHCO-), variation of temperature can influence the hydrophobic effect of these groups and the hydrogen bond action between macromolecular chain, thereby gel structure is changed, and volume takes place change mutually.When ambient temperature was lower than lower critical solution temperature (LCST), the hydrophilic radical in the gel network on the macromolecular chain caused the hydrogel water absorption and swelling through hydrogen bond and water molecules.When temperature rose, this hydrogen bond action weakened, and the interaction between hydrophobic grouping is able to strengthen in the macromolecular chain.Temperature rises to LCST when above, and hydrophobic effect plays a leading role between macromolecular chain, and macromolecular chain is assembled mutually through hydrophobic effect.This moment, hydrogel took place to change mutually, and its swelling ratio is violent suddenly to descend.On the contrary, when temperature is reduced to LCST again when following, hydrogel swelling again recovers, and has good invertibity.Because hydrogel of the present invention is to be made by chemical method, and molecular structure stabilized, so the temperature-responsive characteristic has continuation and durability.
Responsive to temperature type supermolecule intelligent aqueous gel capable load palladium catalysis Heck of the present invention reaction is applicable to common electrophilic reagent in the Heck coupling reactions such as bromo or iodo aromatic hydrocarbons, can hold in the reaction multiple functional group (like CHO, COCH
3, COOC
2H
5, OCH
3, CN, NO
2Deng), another reactant is an olefin(e) compound.
Invention responsive to temperature type supermolecule intelligent aqueous gel capable load palladium catalysis Heck course of reaction is the heterogeneous catalytic reaction that need not to use any organic solvent, can the recycle-water gel catalyst after reaction is accomplished, can reuse, and use productive rate higher first.
Preparation method's of the present invention key is: the prescription of design hydrogel and Calixarene Derivatives and NIPA copolymerization process and the reaction unit that is used for catalysis Heck course of reaction, condition control and experiment aftertreatment technology.It is innovative design that preparation method of the present invention utilizes said Calixarene Derivatives and NIPA copolymerzation with cross-linking to prepare hydrogel material; Next is to utilize the hydrogel load palladium catalysis Heck reaction for preparing, and the reaction unit in the course of reaction, condition control, experiment processing method all belong to innovative design.
One week of distilled water immersion is adopted in the post processing of preparation hydrogel process, to remove unreacted small molecule monomer and solvent, get final product described responsive to temperature type intelligent macromolecule hydrogel.
The prepared supermolecule intelligent aqueous gel capable of preparation method of the present invention material, this gel copolymer has response to variations in temperature, and swelling ratio is undergone mutation when temperature rises to 31-33 ℃, and swelling ratio reduces, gel shrinks; When temperature was reduced to below 32 ℃, swelling ratio raise again gradually, and when temperature returned to former temperature, swelling ratio was tending towards initial value.Hydrogel of the present invention is a kind of novel temperature sensitive type water gel material; Soft moistening because of it; Can be used for absorption, thereby be used in industrial treatment fields such as sewage disposal and desalinization heavy metal ion, transition metal ions, rare earth element ion, alkali metal ion etc.
The intelligent aqueous gel capable catalyst of supported palladium of the present invention is applicable to common electrophilic reagent in the Heck coupling reactions such as bromo or iodo aromatic hydrocarbons.Invention responsive to temperature type supermolecule intelligent aqueous gel capable load palladium catalysis Heck course of reaction is the heterogeneous catalytic reaction that need not to use any organic solvent, can the recycle-water gel catalyst after reaction is accomplished, can reuse.
The specific embodiment
Following embodiment can make those skilled in the art more fully understand the present invention, but does not limit the present invention in any way.
Embodiment 1:
(1) by Calixarene Derivatives: (Calix: mass ratio NIPA)=0.1 adds NIPA, dissolving behind the 10ml DMF dissolving Calix to the N-NIPA.In above-mentioned mixed solution, add 0.2313g N, N '-methylene-bisacrylamide (MBAA) crosslinking agent and 0.04926g azodiisobutyronitrile (AIBN) initator, the logical nitrogen in dissolving back.Solution is put into 60 ℃ of isoperibols, reaction a period of time, promptly get Calixarene Derivatives and NIPA copolymer hydrogel.
Hydrogel post processing: the copolymer hydrogel of gained was at room temperature soaked 7 days with distilled water,, promptly get described responsive to temperature type intelligent macromolecule hydrogel to remove unreacted small molecule monomer and solvent.
(2) preparation of P [NIPA-co-Calix] hydrogel loaded palladium catalyst: the reaction tube of water-setting adhesive tape vacuum pumping opening; P [NIPA-co-Calix] hydrogel (R=0.100) of getting 2g is put into 40 ℃ the about 1h of water-bath deswelling, subsequently P [NIPA-co-Calix] hydrogel is added the PdCl of 0.5mL
2(0.01～0.1mmol/L) aqueous solution at room temperature stirs 30min, and orange solution becomes colourless transparent solution, promptly obtains P [NIPA-co-Calix] hydrogel loaded palladium catalyst.
(3) hydrogel loaded palladium catalyst catalysis Heck reaction (iodobenzene and acrylic acid Heck reaction): get P [NIPA-co-Calix] the hydrogel catalyst of above-mentioned preparation, add the 2.0mmol iodobenzene, 3.0mmol acrylic acid, the 6.0mmol triethylamine is made acid binding agent.Get the rubber stopper that has two holes and be equipped with two glass tubes (vacuumizing and logical nitrogen) and seal the test tube mouth, room temperature vacuumizes, and fills nitrogen, vacuumize for three times/fill nitrogen cycle after.N
2Under the protection, 100 ℃ of oil bath pans reactions were reacted 15 hours.
Post processing: use the 1mol/L hcl acidifying, produce white precipitate, add the dissolving of 20ml ether postprecipitation, ultrasonic extraction 5min room temperature suction filtration; Add product in the 20ml extracted with diethyl ether gel again, suction filtration merges ether solution twice; Ethyl acetate 20ml carries out last ultrasonic extraction to gel, and suction filtration merges in the ether solution.Saturated common salt moisture three times is washed ether and ethyl acetate mixed liquor, and each consumption is about 3 times of mixeding liquid volume.Mixed liquor after the washing merges in the beaker, and add an amount of anhydrous magnesium sulfate and dewater, the room temperature suction filtration, filtrating is poured at the bottom of the roundlet in the flask, and preservative film seals, and on film, pricks several apertures, so that solvent volatilizes at ambient temperature naturally.
Product purification: after solvent volatilizes, use column chromatography silica gel, benzinum: ethyl acetate=20: 1 is solvent, and product is carried out purifying, obtains solid product.
Embodiment 2:
(1) with embodiment 1.
(2) preparation of P [NIPA-co-Calix] hydrogel loaded palladium catalyst: the reaction tube of water-setting adhesive tape vacuum pumping opening; P [NIPA-co-Calix] hydrogel (R=0.100) of getting 2g is put into 40 ℃ the about 1h of water-bath deswelling, subsequently P [NIPA-co-Calix] hydrogel is added the PdCl of 1.0mL
2(0.01～0.1mmol/L) aqueous solution at room temperature stirs 30min, and orange solution becomes colourless transparent solution, promptly obtains P [NIPA-co-Calix] hydrogel loaded palladium catalyst.
(3) with embodiment 1.
Embodiment 3:
(1) with embodiment 1.
(2) preparation of P [NIPA-co-Calix] hydrogel loaded palladium catalyst: the reaction tube of water-setting adhesive tape vacuum pumping opening; P [NIPA-co-Calix] hydrogel (R=0.100) of getting 2g is put into 40 ℃ the about 1h of water-bath deswelling, subsequently P [NIPA-co-Calix] hydrogel is added the PdCl of 0.25mL
2(0.01～0.1mmol/L) aqueous solution at room temperature stirs 30min, and orange solution becomes colourless transparent solution, promptly obtains P [NIPA-co-Calix] hydrogel loaded palladium catalyst.
(3) with embodiment 1.
Embodiment 4:
(1) with embodiment 1.
(2) with embodiment 1.
(3) hydrogel loaded palladium catalyst catalysis Heck reaction (bromobenzene and acrylic acid Heck reaction): get P [NIPA-co-Calix] the hydrogel catalyst of above-mentioned preparation, add the 2.0mmol bromobenzene, 3.0mmol acrylic acid, the 6.0mmol triethylamine is made acid binding agent.Get the rubber stopper that has two holes and be equipped with two glass tubes (vacuumizing and logical nitrogen) and seal the test tube mouth, room temperature vacuumizes, and fills N
2, vacuumize/fill N three times
2After the circulation.N
2Under the protection, 100 ℃ of oil bath pans reactions were reacted 15 hours.
Post processing: use the 1mol/L hcl acidifying, produce white precipitate, add the dissolving of 20ml ether postprecipitation, ultrasonic extraction 5min room temperature suction filtration; Add product in the 20ml extracted with diethyl ether gel again, suction filtration merges ether solution twice; Ethyl acetate 20ml carries out last ultrasonic extraction to gel, and suction filtration merges in the ether solution.Saturated common salt moisture three times is washed ether and ethyl acetate mixed liquor, and each consumption is about 3 times of mixeding liquid volume.Mixed liquor after the washing merges in the beaker, and add an amount of anhydrous magnesium sulfate and dewater, the room temperature suction filtration, filtrating is poured at the bottom of the roundlet in the flask, and preservative film seals, and on film, pricks several apertures, so that solvent volatilizes at ambient temperature naturally.
Product purification: after solvent volatilizes, use column chromatography silica gel, benzinum: ethyl acetate=20: 1 is solvent, and product is carried out purifying, obtains solid product.
Embodiment 5:
(1) with embodiment 1.
(2) with embodiment 2.
(3) hydrogel loaded palladium catalyst catalysis Heck reaction (bromobenzene and acrylic acid Heck reaction): get P [NIPA-co-Calix] the hydrogel catalyst of above-mentioned preparation, add the 2.0mmol bromobenzene, 3.0mmol acrylic acid, the 6.0mmol triethylamine is made acid binding agent.Get the rubber stopper that has two holes and be equipped with two glass tubes (vacuumizing and logical nitrogen) and seal the test tube mouth, room temperature vacuumizes, and fills nitrogen, vacuumize for three times/fill nitrogen cycle after.N
2Under the protection, 100 ℃ of oil bath pans reactions were reacted 15 hours.
Post processing: use the 1mol/L hcl acidifying, produce white precipitate, add the dissolving of 20ml ether postprecipitation, ultrasonic extraction 5min room temperature suction filtration; Add product in the 20ml extracted with diethyl ether gel again, suction filtration merges ether solution twice; Ethyl acetate 20ml carries out last ultrasonic extraction to gel, and suction filtration merges in the ether solution.Saturated common salt moisture three times is washed ether and ethyl acetate mixed liquor, and each consumption is about 3 times of mixeding liquid volume.Mixed liquor after the washing merges in the beaker, and add an amount of anhydrous magnesium sulfate and dewater, the room temperature suction filtration, filtrating is poured at the bottom of the roundlet in the flask, and preservative film seals, and on film, pricks several apertures, so that solvent volatilizes at ambient temperature naturally.
Product purification: after solvent volatilizes, use column chromatography silica gel, benzinum: ethyl acetate=20: 1 is solvent, and product is carried out purifying, obtains solid product.
Embodiment 6:
(1) with embodiment 1.
(2) with embodiment 3.
(3) hydrogel loaded palladium catalyst catalysis Heck reaction (bromobenzene and acrylic acid Heck reaction): get P [NIPA-co-Calix] the hydrogel catalyst of above-mentioned preparation, add the 2.0mmol bromobenzene, 3.0mmol acrylic acid, the 6.0mmol triethylamine is made acid binding agent.Get the rubber stopper that has two holes and be equipped with two glass tubes (vacuumizing and logical nitrogen) and seal the test tube mouth, room temperature vacuumizes, and fills nitrogen, vacuumize for three times/fill nitrogen cycle after.N
2Under the protection, 100 ℃ of oil bath pans reactions were reacted 15 hours.
Post processing: use the 1mol/L hcl acidifying, produce white precipitate, add the dissolving of 20ml ether postprecipitation, ultrasonic extraction 5min room temperature suction filtration; Add product in the 20ml extracted with diethyl ether gel again, suction filtration merges ether solution twice; Ethyl acetate 20ml carries out last ultrasonic extraction to gel, and suction filtration merges in the ether solution.Saturated common salt moisture three times is washed ether and ethyl acetate mixed liquor, and each consumption is about 3 times of mixeding liquid volume.Mixed liquor after the washing merges in the beaker, and add an amount of anhydrous magnesium sulfate and dewater, the room temperature suction filtration, filtrating is poured at the bottom of the roundlet in the flask, and preservative film seals, and on film, pricks several apertures, so that solvent volatilizes at ambient temperature naturally.
Product purification: after solvent volatilizes, use column chromatography silica gel, benzinum: ethyl acetate=20: 1 is solvent, and product is carried out purifying, obtains solid product.
Claims (5)
1. a heterogeneous catalysis that adopts P [NIPA-co-Calix] temperature sensitive type supramolecular hydrogel supported palladium ion is applicable to catalysis Heck reaction, and method may further comprise the steps: the preparation of hydrogel; The preparation of P [NIPA-co-Calix] hydrogel loaded palladium catalyst; Hydrogel load palladium catalysis Heck reaction.
2. the method for narrating according to claim 1 for preparing the hydrogel catalyst; It is characterized in that: used hydrogel is that the 6-bromo-1-hexene etherification derivative with cup [4] aromatic hydrocarbons is a function monomer; Obtain with N-NIPA (NIPA) copolymerization, Calixarene Derivatives and N-NIPA mass ratio are 0.1; N, N '-methylene-bisacrylamide (MBAA) is a crosslinking agent, addition is 0.2313g; Azodiisobutyronitrile (AIBN) is an initator, and addition is 0.04926g.
3. the method for narrating according to claim 1 for preparing the hydrogel catalyst is characterized in that: earlier hydrogel is put into 40 ℃ the about 1h of water-bath deswelling.
4. the hydrogel loaded palladium catalyst catalysis Heck reaction of narrating according to claim 1, it is characterized in that: iodobenzene (bromobenzene): acrylic acid: the mol ratio of triethylamine is 2: 3: 6.
5. the hydrogel load palladium catalysis Heck reaction of narrating according to claim 1, it is characterized in that: reaction temperature is constant to be 100 ℃.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103861479A (en) * | 2012-12-18 | 2014-06-18 | 天津工业大学 | Polyvinylidene fluoride/gold nanoparticle hybrid hollow fiber membrane and preparation method thereof |
| CN103861478A (en) * | 2012-12-18 | 2014-06-18 | 天津工业大学 | Polyvinylidene fluoride/silver nanoparticle hybrid hollow fiber membrane and preparation method thereof |
| CN106830259A (en) * | 2017-02-28 | 2017-06-13 | 华南理工大学 | A kind of biodegrading process of chlorinatedorganic |
| CN108467497A (en) * | 2018-04-23 | 2018-08-31 | 佛山市功能高分子材料与精细化学品专业中心 | A kind of cup [8] aromatic hydrocarbons hydrophobically modified poly-N-isopropyl acrylamide temperature-sensitive hydrogel and its synthetic method and application |
| CN108467454A (en) * | 2018-04-23 | 2018-08-31 | 佛山市功能高分子材料与精细化学品专业中心 | A kind of cup [8] aromatic hydrocarbons hydrophobically modified temperature-sensitive hydrogel and its synthetic method and application |
| CN108586659A (en) * | 2018-04-23 | 2018-09-28 | 佛山市功能高分子材料与精细化学品专业中心 | A kind of aromatic modified temperature-sensitive hydrogel of cup [6] and its synthetic method and application |
| CN108586661A (en) * | 2018-04-23 | 2018-09-28 | 佛山市功能高分子材料与精细化学品专业中心 | A kind of cup [4] aromatic hydrocarbons hydrophobically modified temperature-sensitive hydrogel and the preparation method and application thereof |
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| CN103861479A (en) * | 2012-12-18 | 2014-06-18 | 天津工业大学 | Polyvinylidene fluoride/gold nanoparticle hybrid hollow fiber membrane and preparation method thereof |
| CN103861478A (en) * | 2012-12-18 | 2014-06-18 | 天津工业大学 | Polyvinylidene fluoride/silver nanoparticle hybrid hollow fiber membrane and preparation method thereof |
| CN103861478B (en) * | 2012-12-18 | 2016-03-30 | 天津工业大学 | A kind of Kynoar/Nano silver grain hydridization hollow-fibre membrane and preparation method thereof |
| CN103861479B (en) * | 2012-12-18 | 2016-04-13 | 天津工业大学 | A kind of Kynoar/golden nanometer particle hydridization hollow-fibre membrane and preparation method thereof |
| CN106830259A (en) * | 2017-02-28 | 2017-06-13 | 华南理工大学 | A kind of biodegrading process of chlorinatedorganic |
| CN106830259B (en) * | 2017-02-28 | 2019-04-09 | 华南理工大学 | A kind of biodegrading process of chlorinatedorganic |
| CN108467497A (en) * | 2018-04-23 | 2018-08-31 | 佛山市功能高分子材料与精细化学品专业中心 | A kind of cup [8] aromatic hydrocarbons hydrophobically modified poly-N-isopropyl acrylamide temperature-sensitive hydrogel and its synthetic method and application |
| CN108467454A (en) * | 2018-04-23 | 2018-08-31 | 佛山市功能高分子材料与精细化学品专业中心 | A kind of cup [8] aromatic hydrocarbons hydrophobically modified temperature-sensitive hydrogel and its synthetic method and application |
| CN108586659A (en) * | 2018-04-23 | 2018-09-28 | 佛山市功能高分子材料与精细化学品专业中心 | A kind of aromatic modified temperature-sensitive hydrogel of cup [6] and its synthetic method and application |
| CN108586661A (en) * | 2018-04-23 | 2018-09-28 | 佛山市功能高分子材料与精细化学品专业中心 | A kind of cup [4] aromatic hydrocarbons hydrophobically modified temperature-sensitive hydrogel and the preparation method and application thereof |
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