CN103263916A - Preparation method and use of crosslinked polyethylene-loaded metal nanoparticles - Google Patents
Preparation method and use of crosslinked polyethylene-loaded metal nanoparticles Download PDFInfo
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Abstract
The invention discloses a preparation method and a use of crosslinked polyethylene-loaded metal nanoparticles. The preparation method comprises that ethylene and a crosslinking monomer undergo a chain walking copolymerization reaction in the presence of a palladium-diimine catalyst to produce a crosslinked polyethylene carrier for loading metal nanoparticles; through a one-step loading or two-step loading technology, a metal compound is fixedly loaded on the crosslinked polyethylene carrier; and the metal compound loaded by the crosslinked polyethylene carrier undergoes a reduction reaction and is transformed into metal nanoparticles so that the crosslinked polyethylene-loaded metal nanoparticle catalyst is obtained. The crosslinked polyethylene-loaded metal nanoparticles are used for catalysis of a carbon-carbon cross-coupling reaction, has high catalytic activity and good stability, and can be recovered and recycled easily.
Description
Technical field
The present invention relates to a kind of metal nanoparticle, relate in particular to the application of the metal nanoparticles loaded preparation method of a kind of crosslinked polyethylene and the efficient recyclable catalyst of the metal nanoparticles loaded conduct of crosslinked polyethylene.
Background technology
Metal nanoparticle has very large specific area and special skin effect, make it there is very high surface-active, can effectively avoid the side reaction produced to the inside particles diffusion due to reactant, there is high activity and selective, therefore, be widely used as the organic-matter chemical catalysts.
Due to metal, particularly the noble metal cost is high, remains in product and can bring metallic pollution, therefore, after catalytic reaction finishes, needs separation, recovery and reuse metal nano catalyst.For separation, the recovery and reuse that facilitate catalyst, usually form heterogeneous catalysis by metal nanoparticle is immobilized on inorganic or organic carrier.In these carriers, cross-linked polymer has following advantage: the supported catalyst in (1) reaction system can be realized reclaiming by easy filter operation; (2) good chemical stability; (3) can change by the physical/chemical of regulation and control polymer support the activity and selectivity of catalyst, and that this is inorganic carrier is not available.
At present, the catalyst with metal nanoparticles of relevant cross-linked polymer load, Chinese patent 200910008897.1 has been reported a kind of method of using the Pd nano particle in-situ suspension polymerization to prepare the supported palladium resin catalyst; Chinese patent 200580007594.8 has been announced a kind of macromolecule-supported palladium metal cluster compositions, and to be that the macromolecule of the hydrophilic side-chains by having hydrophobic side chains and containing bridging property functional group is crosslinked form this cross-linked polymer; Chinese patent CN101890367A has reported preparation and the application in the Heck cross-coupling reaction thereof of interpenetrating net polymer supported palladium nano-particle catalyst, used polyvinyl alcohol and polyacrylamide for the interpenetrating networks base material, by five steps, reacted and make corresponding supported catalyst; CN201110404836.4 has reported a kind of temperature-sensitive polymer/gold nanoparticle hybrid microspheres, wherein hybrid polymer micro-sphere is comprised of polymer inner layer and the temperature sensitive polymeric outer layer of pH sensitivity, and golden nanometer particle is positioned at the responsive internal layer of hybrid polymer micro-sphere pH; Patent CN200910067031.8 has announced that a kind of to prepare metal nanoparticle by in-situ polymerization be the core-shell particles that core, polymer are shell.
All there is loaded down with trivial details, synthetic difficult, the high in cost of production problem of preparation process in the cross-linked polymer catalyst with metal nanoparticles loaded preparation method of existing report, limited as the cross-linked polymer patent report of carrier.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, the metal nanoparticles loaded preparation method of a kind of crosslinked polyethylene and application are provided.
The objective of the invention is to be achieved through the following technical solutions: the preparation method that a kind of crosslinked polyethylene is metal nanoparticles loaded comprises the following steps:
(1) crosslinked polyethylene of load palladium metal nano particle load is synthetic: utilize palladium-diimine catalysts, carry out " one pot " copolymerization of ethene and dienes monomer and/or function monomer in the organic solvent of crossing in drying under-30 ~ 50 ℃, wherein, palladium-diimine catalysts concentration is 0.001-1 mol/L, the dienes monomer concentration is 0.01-2mol/L, function monomer concentration is 0.01-2mol/L, and ethylene pressure is 0.1-100atm, reaction time 0.5-48h; In polymerization process, before polyethylene gel forms, add palladium salt, the palladium salinity of adding is 0-5mol/L; Reaction adds reaction terminating agent after finishing, and the volume ratio of reaction terminating agent and organic solvent is 1-100:1, obtains the crosslinked polyethylene of load palladium metal;
(2) the metal nanoparticles loaded post processing of crosslinked polyethylene: methyl alcohol, ethanol, propyl alcohol or other alcohols solvent for crosslinked polyethylene of step 1 gained load palladium metal are washed 3 times, the 1-10 that each alcohols solvent consumption is the organic solvent volume doubly, and then with oxolane or the fragmentation of carrene swelling, the 1-10 that its consumption is the organic solvent volume doubly, again with methyl alcohol or ethanol washing, the 1-10 that its consumption is the organic solvent volume doubly, product after processing, at 30-100 ℃ of vacuum drying, can prepare the metal nanoparticle of crosslinked polyethylene load.
The preparation method that a kind of crosslinked polyethylene is metal nanoparticles loaded comprises the following steps:
(1) crosslinked polyethylene of load palladium metal nano particle load is synthetic: utilize palladium-diimine catalysts, carry out " one pot " copolymerization of ethene and dienes monomer and/or function monomer in the organic solvent of crossing in drying under-30 ~ 50 ℃, wherein, palladium-diimine catalysts concentration is 0.001-1 mol/L, the dienes monomer concentration is 0.01-2mol/L, function monomer concentration is 0.01-2mol/L, and ethylene pressure is 0.1-100atm, reaction time 0.5-48h; In polymerization process, before polyethylene gel forms, add palladium salt, the palladium salinity of adding is 0-5mol/L; Reaction adds reaction terminating agent after finishing, and the volume ratio of reaction terminating agent and organic solvent is 1-100:1, obtains the crosslinked polyethylene of load palladium metal;
(2) secondary load of other metal nanoparticle: the crosslinked polyethylene of the load palladium metal that obtains in step 1 is scattered in the organic solvent of equal volume again, add other slaine that need to carry out load, the concentration of slaine is 0.001-5mol/L, utilize functional group in crosslinked polyethylene and the charge effect between ionizable metal salt, the load of realization to slaine, load time 0.5-24h; Then, add reducing agent, the concentration of reducing agent is 0-5 mol/L, reaction time 0.5-10h, and reducing loaded slaine, obtain the metal nanoparticle of crosslinked polyethylene load;
(3) the metal nanoparticles loaded post processing of crosslinked polyethylene: step 2 products therefrom further washs 3 times with methyl alcohol, ethanol, propyl alcohol or other alcohols solvent, the 1-10 that each alcohols solvent consumption is the organic solvent volume doubly, and then with oxolane or the fragmentation of carrene swelling, the 1-10 that its consumption is the organic solvent volume doubly, again with methyl alcohol or ethanol washing, the 1-10 that its consumption is the organic solvent volume doubly, product after processing, at 30-100 ℃ of vacuum drying, can prepare the metal nanoparticle of crosslinked polyethylene load.
The invention has the beneficial effects as follows, the catalyst with metal nanoparticles of crosslinked polyethylene load prepared by the present invention in contrast to other supported catalyst of the same type, itself and preparation method thereof there is advantage and the feature of following uniqueness: (1) polyethylene support has good chemical stability, applicable to the differential responses system; (2) catalyst with metal nanoparticles of crosslinked polyethylene load is easy to prepare and cost is low, utilize palladium-diimine catalysts catalyzed ethylene and dienes monomer/monomer's copolymerzation with cross-linking by " one pot " method, can obtain being applicable to the crosslinked polyethylene of metal nanoparticle load; (3) catalyst with metal nanoparticles of crosslinked polyethylene load catalysis different chemical reaction efficiently, its catalytic activity can compare favourably with the nanocatalyst of homogeneous polymer load, is better than the nanocatalyst of other cross-linked polymer load of great majority; (4) the catalyst with metal nanoparticles good stability of crosslinked polyethylene load, be easy to separate, and can repeatedly reclaim and repeat.
The specific embodiment
The present invention utilizes the copolymerization of palladium-diimine catalysts catalyzed ethylene and dienes monomer and/or function monomer, and by following two kinds of methods: two-step method (load) or three-step approach (secondary load) prepare.
The preparation method that a kind of crosslinked polyethylene is metal nanoparticles loaded, the method is a load, comprises the following steps:
1, the crosslinked polyethylene of load palladium metal nano particle load is synthetic: utilize palladium-diimine catalysts, carry out " one pot " copolymerization of ethene and dienes monomer and/or function monomer in the organic solvent of crossing in drying under-30 ~ 50 ℃, wherein, palladium-diimine catalysts concentration is 0.001-1 mol/L, the dienes monomer concentration is 0.01-2mol/L, function monomer concentration is 0.01-2mol/L, and ethylene pressure is 0.1-100atm, reaction time 0.5-48h; In polymerization process, before polyethylene gel forms, add palladium salt, the palladium salinity of adding is 0-5mol/L.Reaction adds reaction terminating agent after finishing, and the volume ratio of reaction terminating agent and organic solvent is 1-100:1, obtains the crosslinked polyethylene of load palladium metal.
2, the metal nanoparticles loaded post processing of crosslinked polyethylene: methyl alcohol, ethanol, propyl alcohol or other alcohols solvent for crosslinked polyethylene of step 1 gained load palladium metal are washed 3 times, the 1-10 that each alcohols solvent consumption is the organic solvent volume doubly, and then with oxolane or the fragmentation of carrene swelling, the 1-10 that its consumption is the organic solvent volume doubly, again with methyl alcohol or ethanol washing, the 1-10 that its consumption is the organic solvent volume doubly, product after processing, at 30-100 ℃ of vacuum drying, can prepare the metal nanoparticle of crosslinked polyethylene load.
The metal nanoparticles loaded preparation method of another kind of crosslinked polyethylene, the method is secondary load, comprises the following steps:
1, the crosslinked polyethylene of load palladium metal nano particle load is synthetic: utilize palladium-diimine catalysts, carry out " one pot " copolymerization of ethene and dienes monomer and/or function monomer in the organic solvent of crossing in drying under-30 ~ 50 ℃, wherein, palladium-diimine catalysts concentration is 0.001-1 mol/L, the dienes monomer concentration is 0.01-2mol/L, function monomer concentration is 0.01-2mol/L, and ethylene pressure is 0.1-100atm, reaction time 0.5-48h; In polymerization process, before polyethylene gel forms, add palladium salt, the palladium salinity of adding is 0-5mol/L.Reaction adds reaction terminating agent after finishing, and the volume ratio of reaction terminating agent and organic solvent is 1-100:1, obtains the crosslinked polyethylene of load palladium metal.
2, the secondary load of other metal nanoparticle: the crosslinked polyethylene of the load palladium metal that obtains in step 1 is scattered in the organic solvent of equal volume again, add other slaine that need to carry out load, the concentration of slaine is 0.001-5mol/L, utilize functional group in crosslinked polyethylene and the charge effect between ionizable metal salt, the load of realization to slaine, load time 0.5-24h.Then, add reducing agent, the concentration of reducing agent is 0-5 mol/L, reaction time 0.5-10h, and reducing loaded slaine, obtain the metal nanoparticle of crosslinked polyethylene load.
3, the metal nanoparticles loaded post processing of crosslinked polyethylene: step 2 products therefrom further washs 3 times with methyl alcohol, ethanol, propyl alcohol or other alcohols solvent, the 1-10 that each alcohols solvent consumption is the organic solvent volume doubly, and then with oxolane or the fragmentation of carrene swelling, the 1-10 that its consumption is the organic solvent volume doubly, again with methyl alcohol or ethanol washing, the 1-10 that its consumption is the organic solvent volume doubly, product after processing, at 30-100 ℃ of vacuum drying, can prepare the metal nanoparticle of crosslinked polyethylene load.
Palladium-diimine catalysts described in above-mentioned steps 1, their polymerization property is known in the art, referring to Ittel, S. D. etc., M., Late-metal catalysts for ethylene homo-and copolymerization. Chem. Rev. 2000,100,1169-1203.First-selected palladium-diimine catalysts comprises [(ArN=C (Me)-(Me) C=NAr) Pd (CH
3) (N ≡ CMe)]
+sbF
6 ?(Ar=2,6-(iPr)
2c
6h
3or 2,6-(Me)
2c
6h
3), [(ArN=C (Me)-(Me) C=NAr) Pd (CH
3) (OEt
2)]
+sbF
6 ?, [(ArN=C (Me) – (Me) C=NAr) Pd (CH
2)
3c (O) OCH
3]
+sbF
6 --, [(ArN=C (Me) – (Me) C=NAr) Pd (CH
2)
3c (O) O (CH
2)
2oC (O) C (CH
3)
2br]
+sbF
6 ?, [(ArN=C (Me)-(Me) C=NAr) Pd (CH
3) (N ≡ CMe)]
+b (Ar ')
4 ?, [(ArN=C (Me) – (Me) C=NAr) Pd-(CH
3) (OEt
2)]
+b (Ar ')
4 ?, [(ArN=C (Me) – (Me) C=NAr) Pd (CH
2)
3c (O) OCH
3]
+b (Ar ')
4 ?, [(ArN=C (Me) – (Me) C=NAr) Pd (CH
2)
3c (O) O (CH
2)
2oC (O) C (CH
3)
2br]
+b (Ar ')
4 ?, [(ArN=CH-HC=NAr) Pd (CH
3) (N ≡ CMe)]
+sbF
6 ?, [(ArN=CH-HC=NAr) Pd (CH
3) (OEt
2)]
+sbF
6 ?, [(ArN=CH-HC=NAr) Pd (CH
2)
3c (O) OCH
3]
+sbF
6 --, [(ArN=CH-HC=NAr) Pd (CH
2)
3c (O) O (CH
2)
2oC (O) C (CH
3)
2br]
+sbF
6 ?, [(ArN=CH-HC=NAr) Pd (CH
3) (N ≡ CMe)]
+b (Ar ')
4 ?, [(ArN=CH-HC=NAr) Pd-(CH
3) (OEt
2)]
+b (Ar ')
4 ?, [(ArN=CH-HC=NAr) Pd (CH
2)
3c (O) OCH
3]
+b (Ar ')
4 ?and [(ArN=CH-HC=NAr) Pd (CH
2)
3c (O) O (CH
2)
2oC (O) C (CH
3)
2br]
+b (Ar ')
4 ?, [(ArN=An=NAr) Pd (CH
3) (N ≡ CMe)]
+sbF
6 ?(An=), [(ArN=An=NAr) Pd (CH
3) (OEt
2)]
+sbF
6 ?, [(ArN=An=NAr) Pd (CH
2)
3c (O) OCH
3]
+sbF
6 --, [(ArN=An=NAr) Pd (CH
2)
3c (O) O (CH
2)
2oC (O) C (CH
3)
2br]
+sbF
6 ?, [(ArN=An=NAr) Pd (CH
3) (N ≡ CMe)]
+b (Ar ')
4 ?, [(ArN=An=NAr) Pd-(CH
3) (OEt
2)]+B (Ar ')
4 ?, [(ArN=An=NAr) Pd (CH
2)
3c (O) OCH
3]
+b (Ar ')
4 ?, [(ArN=An=NAr) Pd (CH
2)
3c (O) O (CH
2)
2oC (O) C (CH
3)
2br]
+b (Ar ')
4 ?deng.Synthesizing of they is known in this area, can be referring to the document of having reported " Johnson, L. K.; Killian, C. M.; Brookhart; M.; New Pd (II)-and Ni (II)-Based Catalysts for Polymerization of Ethylene and .alpha.-Olefins. Journal of the American Chemical Society 1995; 117 (23); 6414-6415 " and document " Zhang, K.; Ye, Z.; Subramanian, R., Synthesis of block copolymers of ethylene with styrene and n-butyl acrylate via a tandem strategy combining ethylene " Living " polymerization catalyzed by a functionalized Pd-diimine catalyst with atom transfer radical polymerization. Macromolecules 2008,41 (3), 640-649 ".
The dienes monomer related in above-mentioned steps 1 of the present invention be can with esters of acrylic acid or the olefin monomer of ethene generation copolymerization, comprise that two acrylic acid diol esters are (as 1, the 6-hexanediyl ester, 1, the 4-butanediol diacrylate, 1, 3-butanediol diacrylate etc.), diethylene glycol diacrylate, four (ethylene glycol) diacrylate, the diacrylate macrogol ester, N, N'-di-2-ethylhexylphosphine oxide acrylate, two (2-acryloyl) ethyoxyl two sulphur, Allyl disulfide, allyl sulfide, alkadienes is (as 1, the 3-butadiene, 1, the 4-pentadiene, 1, the 5-hexadiene, 1, 7-octadiene etc.).
The function monomer related in above-mentioned steps 1 of the present invention is can be with ethylene copolymer, with olefines or the acrylic ester monomer of specific functional groups; comprise N; N'-di-2-ethylhexylphosphine oxide acrylate, two (2-acryloyl) ethyoxyl two sulphur, Allyl disulfide, allyl sulfide, 2-(2'-bromo isobutyl acyloxy) ethyl-2 "-the acrylyl oxy-ethyl disulfide (it is synthetic sees Liu, P.; Ye, Macromolecules 2013,46,72 – 82 such as Z. B.), 2-(2-bromine isobutoxy) (it is synthetic sees document Matyjaszewski, K. to ethyl acrylate; Gaynor, S. G.; Kulfan, A.; Podwika, M. Macromolecules 1997,30 (17), 5192-5194.), acrylic acid-2,3-epoxy propyl ester, 2 (acryloyl-oxy base oxethyl) trimethyl silane, acrylyl oxy-ethyl-trimethyl salmiac, 2-(dimethylamino) ethyl acrylate, 2-(lignocaine) ethyl acrylate, tert-butyl acrylate, 2 (1,1-dimethyl butyrate-3-thiazolinyl) oxirane (Journal of the American Chemical Society (2003), 125 (22), the monomer such as 6697-6704.).
The palladium salt related in above-mentioned steps 1 of the present invention comprises palladium, palladium chloride, two (ethylenediamine) chlorine Palladium of tetrachloro-palladium potassium chlorate, six potassium chloropalladates, palladium bromide, hydration palladium bichloride (II), palladium iodide, ammonium chloropalladate, six ammonium chloropalladates, tetrachloro-palladium acid sodium, palladium sulfate, dichloro four ammonia palladiums, tetrabromo palladium acid potassium, tetramino palladium, palladium trifluoroacetate, dichloro four ammonia palladiums, dichloro diamino palladium, palladium nitrate, (1,5-cyclo-octadiene) palladium chloride, palladium nitrate etc.
The organic solvent related in above-mentioned steps 1 of the present invention comprises: carrene, chlorobenzene, dichloro benzene,toluene,xylene, acetone, dimethyl formamide (DMF), dimethyl formamide, oxolane, chloroform etc.The reaction terminating agent used in the present invention is comprised of one or both mixing of methyl alcohol and ethanol.
Other slaine that in the present invention, step 2 relates to is platinum salt, golden salt, rhodium salt, ruthenium salt etc.; The platinum salt wherein related to comprises: platinous chloride, platinum tetrachloride, ammonium chloroplatinate, potassium chloroplatinite, potassium chloroplatinate, diphenyl (1,5-cyclo-octadiene) platinum (II), dichloro two ammino platinum, dichloro four ammino platinum, two (acetylacetone,2,4-pentanedione) platinum, the acid of chlordene platinum, sulfurous acid platinum, platinic sodium chloride, platinum nitrate, potassium trichloroaminoplatinate, platinum dioxide hydrate, the two chloro cyclohexene platinum of dichloro, sodium chloroplatinite, six hydroxide platinic acid potassium etc.; The golden salt related to comprises: the sour potassium of gold cyanide (III), tetra chlorauric acid, sodium chloraurate, two water thing potassium chloroaurates, tetra chlorauric acid trihydrate, tetra chlorauric acid ammonium, tetrachloro gold (III) sour potassium hydrate, chlorauride, sodium chloraurate, sodium chloraurate two water things, aurous cyanide, gold bromide, auric iodide, aurosulfo etc.; The rhodium salt related to comprises: rhodium hydroxide III, rhodium oxide, sulfurous acid rhodium, rhodium nitrate, two (norbornadiene) dichloro rhodium, trichlorine six ammonia rhodiums, dicarbapentaborane radium chloride, hydration chlorine rhodium acid sodium, chlorine rhodium acid ammonium, chlorine rhodium acid potassium, chlorine rhodium acid sodium, acetic acid rhodium, three hydration radium chlorides, three (ethylenediamine) rhodium chloride, radium chloride, iodate rhodium etc.; The ruthenium salt related to comprises: trinitro-nitrosyl ruthenium, two (the 4-isopropyl methyl phenyl) rutheniums (II) of dichloro, two hydration eight chlorine time sour three ammoniums of nitrogen two Ruthenium (IV), ruthenium hydrochloride ammonium, the carbonyl hydrogenated ruthenium of praseodynium ruthenium, three (triphenylphosphine), (1,5-cyclo-octadiene) ruthenic chloride, three (triphenylphosphine) ruthenous chloride, acetic acid ruthenium etc.
The reducing agent that in the present invention, step 2 relates to, comprise the NaBH of strong reductant
4, KBH
4, LiAlH
4, hydrogen etc., also comprise methyl alcohol, ethanol of weak reductant etc.
At the crosslinked polyethylene prepared in metal nanoparticles loaded process, the kind that can use by the control catalyst, catalyst concn, dienes monomer concentration and dropping strategy, reaction temperature, pressure etc., effectively regulate and control poly crosslink density, the metal nanoparticle of load can stably be present in the spatial network of polyethylene crosslinking.
The preparation method of the metal nanoparticle of above-mentioned crosslinked polyethylene load is by controlling kind and the concentration of function monomer, introduce once functional group and realize functional group densities and the regulation and control of kind in the ethylene copolymer process, making this crosslinked polyethylene loading metal-salt effectively.
By regulating polymerization process, ((step 2) other metal salt concentrations during secondary load after adding the concentration of palladium salt or polymerisation in step 1) and finishing, realize the Effective Regulation to carried metal kind and amount to the preparation method of the metal nanoparticle of above-mentioned crosslinked polyethylene load effectively.
The metal nanoparticle product of the crosslinked polyethylene load prepared by said method, carrier crosslinked polyethylene chemical stability is good, crosslink density (0.1-10 mol.%) is suitable, when guaranteeing that reaction substrate can be diffused into surfaces of metal nanoparticles, can also make metal nanoparticle that good stability is in use arranged, be difficult for loss and reveal.
The metal nanoparticles loaded product of the crosslinked polyethylene prepared by said method, described metal nanoparticle comprises palladium, gold, platinum, rhodium, ruthenium and series metal thereof, its metal nanoparticle load capacity is 1*10
-4the every gram crosslinked polyethylene of-100 mmol metal, the metal nanoparticle particle diameter is in 1-500 nm scope.
The catalytic applications of the metal nanoparticles loaded product of above-mentioned crosslinked polyethylene, it is efficient that this product can be used as a class, heterogeneous catalysis stable and that easily reclaim, be applied in the middle of the corresponding organic catalytic reaction of different loads metal, for example, the Pd nano particle of crosslinked polyethylene load can be used for catalyzed carbon carbon cross-coupling reaction, the golden nanometer particle of crosslinked polyethylene load can be used for the epoxidation of catalyzing propone, unsaturated hydrocarbon hydrogenation etc., the nano platinum particle of crosslinked polyethylene load can be used for catalytic hydrogenation, the rhodium nano particle of crosslinked polyethylene load can be used for catalysis asymmetric hydroformylation reaction etc.
The catalytic applications of the metal nanoparticles loaded product of above-mentioned crosslinked polyethylene, the total moles that the metal nanoparticles loaded use amount of course of reaction crosslinked polyethylene is controlled at its metal is the 0.001-10% of the mole of reaction substrate.Above-mentioned catalyst is after reaction finishes, and supported catalyst can be realized by the mode of decant or filtration and the separating of product solution.The catalyst of separating can directly utilize, and the reaction of catalysis new reaction substrate realizes reclaiming and repeatedly recycling easily.
Below in conjunction with the specific embodiment, the invention will be further described:
Embodiment 1: a step load method of crosslinked polyethylene supported palladium nano particle is synthetic
The 50mL round-bottomed flask that dewaters dry, by application of vacuum and use the ethene balance, under 25 ℃, add the palladium of 5mL-diimine catalysts solution (0.1 mmol [(ArN=C (Me)-(Me) C=NAr) Pd (CH
3) (N ≡ CMe)]
+sbF
6 --be dissolved in the dry methylene chloride of 5 mL), 5 mL are added fast containing the dichloromethane solution of 1,6-hexylene glycol double methacrylate (0.10 g) simultaneously, start reaction.Course of reaction keeps the ethene continuous feed, after reacting 24 h, the methyl alcohol cessation reaction that adds 40mL in system, obtain the crosslinked polyethylene product, with 40mL methyl alcohol, to this crosslinked polyethylene product washing three times, then with 40 mL oxolanes, this crosslinked polyethylene product is carried out to the swelling fragmentation, crosslinked polyethylene product after fragmentation is used respectively 40 mL methanol wash three times again, vacuum drying under 70oC, obtain 3.3 g crosslinked polyethylene supported palladium nano particles, and wherein the content of palladium metal is 1.9*10
-2mmol Pd/g polyethylene, the Pd nano particle particle diameter is 9-29.5 nm.
Embodiment 2: two step load methods of crosslinked polyethylene supported platinum nano particle are synthetic
The 100 dry mL round-bottomed flasks that dewater, by application of vacuum and use the ethene balance, under 25 ℃, add the palladium of 10mL-diimine catalysts solution (0.2 mmol (ArN=C (Me)-(Me) C=NAr) Pd (CH
3) (N ≡ CMe)]
+sbF
6 --be dissolved in the dry methylene chloride of 10 mL), 10 mL are added fast containing the dichloromethane solution of two (2-acryloyl) ethyoxyl two sulphur (0.19 g) of dienes monomer simultaneously, start reaction.Course of reaction keeps the ethene continuous feed, after reacting 24 h, adds the methyl alcohol cessation reaction of 50 mL in system, obtains the crosslinked polyethylene product.Crosslinked polyethylene product is scattered in the carrene of 20 mL, adds diphenyl (1, the 5-cyclo-octadiene) platinum (II) of 0.4 mmol, stir load, reaction 12h.Then with 50mL methyl alcohol, this crosslinked polyethylene product is washed three times, then with 50 mL oxolanes, this crosslinked polyethylene product is carried out to the swelling fragmentation, crosslinked polyethylene product after fragmentation is used respectively 50 mL methanol wash three times again, 70 ℃ of lower vacuum dryings, obtain 11.23 g crosslinked polyethylene supported platinum nano particles, wherein the content of platinum is 3.3*10
-2mmol Pt/g polyethylene, the nano platinum particle particle diameter is 5 – 30 nm.
Comparative Examples 1: polyethylene supported palladium nano particle synthetic
The 100mL round-bottomed flask that dewaters dry, by application of vacuum and use the ethene balance, under 25 ℃, add the palladium of 10 mL-diimine catalysts solution (0.15 mmol [(ArN=C (Me)-(Me) C=NAr) Pd (CH
3) (N ≡ CMe)]
+sbF
6 --be dissolved in the dry methylene chloride of 5 mL), simultaneously by 10 mL containing 2-2-(bromo isobutyl acyl-oxygen) dichloromethane solution of ethyl propylene acid esters (0.21 g) adds fast, starts reaction.Course of reaction keeps the ethene continuous feed, after reacting 24 h, the methyl alcohol cessation reaction that adds 50 mL in system, obtain the crosslinked polyethylene product, with 50 mL methyl alcohol, to this crosslinked polyethylene product washing three times, then with 50 mL oxolanes, this crosslinked polyethylene product is carried out to the swelling fragmentation, crosslinked polyethylene product after fragmentation is used respectively 50 mL methanol wash three times again, 70 ℃ of lower vacuum dryings, obtain 6.3 g crosslinked polyethylene supported palladium nano particles, and wherein the content of palladium metal is 0.9*10
-2mmol Pd/g polyethylene, the Pd nano particle particle diameter is 3 – 10 nm.
Catalytic applications and the recycling of the crosslinked polyethylene supported palladium nano particle of embodiment 1 in the Heck reaction:
0.183 g crosslinked polyethylene supported palladium nano particle is (containing 3.5*10
-3mmol Pd), 0.5 g iodobenzene (2.4 mmol, [Pd]/[IB]=0.15 %), 0.47 g n-butyl acrylate (3.6 mmol), 0.37 g triethylamine (3.6 mmol), 3mL dimethyl formamide join the Schlenck reaction bulb of 20mL, through vacuum nitrogen filling, 100 ℃ are reacted 2 hours, the reactant conversion ratio is 99%, and the palladium amount of leakage is 0.5% of total load amount.
Reaction can be isolated crosslinked polyethylene supported palladium nano particle by decant after finishing from reaction system, it is isolated after for catalyst, dimethyl formamide (each 4 mL) washs three times, this catalyst is joined in new Schlenck reaction bulb, add the new reaction substrate (iodobenzene of 0.5 g simultaneously, 0.46 g n-butyl acrylate, 0.37 g triethylamine and 3 mL dimethyl formamides), through vacuum nitrogen filling, 100 oC reactions 2 hours, the reactant conversion ratio is 99%, complete the catalytic applications of a circulation, the palladium amount of leakage is 1.2% of total load amount.Repeat ten catalytic reactions of circulation once, each circulation catalytic reaction 2 h, reaction-ure conversion-age all reaches 99%, the ten total amount of leakage of palladium in process that recycles once and is about 15% of total load amount.The catalyst average activity is 460 h
-1, be better than most of loaded palladium catalyst of reporting.
Catalytic applications and the recycling of the crosslinked polyethylene supported palladium nano particle of embodiment 1 in the Heck reaction:
0.183 g crosslinked polyethylene supported palladium nano particle is (containing 3.5 * 10
-3mmol Pd), 0.5 g iodobenzene (2.4 mmol, [Pd]/[IB]=0.15 %), 0.37 g styrene (3.6 mmol), 0.37 g triethylamine (3.6 mmol), 3 mL dimethyl formamides join the Schlenck reaction bulb of 20mL, through vacuum nitrogen filling, 100 ℃ of reaction 6 h, carry out the catalytic reaction of six circulations, the average conversion ratio of reactant is to recycle total amount of leakage of palladium in process for 82%, six time to be less than 10% of total load amount.The catalyst average activity is 87 h
-1, be better than most of loaded palladium catalyst of reporting.
Catalytic applications and the recycling of the crosslinked polyethylene supported palladium nano particle of embodiment 1 in the Suzuki reaction:
0.183 g crosslinked polyethylene supported palladium nano particle is (containing 3.5 * 10
-3mmol Pd), 0.5 g iodobenzene (2.4 mmol, [Pd]/[IB]=0.15 %), 0.44 g phenyl boric acid (3.6 mmol), 0.66 g Anhydrous potassium carbonate (4.8 mmol), 3 mL dimethyl formamides and 3 mL water join the Schlenck reaction bulb of 20mL, through vacuum nitrogen filling, 100 oC reactions 4 hours, carry out the catalytic reaction of five circulations, it is 10.3% of total load amount that the conversion ratio of reactant all recycles total amount of leakage of palladium in process over 96%, five time.The catalyst average activity is 150 h
-1, be better than most of loaded palladium catalyst of reporting.
Catalytic applications and the recycling of the polyethylene supported palladium nano particle of Comparative Examples 1 in the Heck reaction:
Polyethylene supported palladium nano particle is for the Heck reaction, and the stability of its Pd nano particle is very poor, in course of reaction, very easily leaks, and catalyst loss is serious, through primary first-order equation, substantially runs off totally, can't realize recycling.
above-described embodiment is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change that the present invention is made, all fall into protection scope of the present invention.
Claims (9)
1. the preparation method that crosslinked polyethylene is metal nanoparticles loaded, is characterized in that, comprises the following steps:
(1) crosslinked polyethylene of load palladium metal nano particle load is synthetic: utilize palladium-diimine catalysts, carry out " one pot " copolymerization of ethene and dienes monomer and/or function monomer in the organic solvent of crossing in drying under-30 ~ 50 ℃, wherein, palladium-diimine catalysts concentration is 0.001-1 mol/L, the dienes monomer concentration is 0.01-2mol/L, function monomer concentration is 0.01-2mol/L, and ethylene pressure is 0.1-100atm, reaction time 0.5-48h; In polymerization process, before polyethylene gel forms, add palladium salt, the palladium salinity of adding is 0-5mol/L; Reaction adds reaction terminating agent after finishing, and the volume ratio of reaction terminating agent and organic solvent is 1-100:1, obtains the crosslinked polyethylene of load palladium metal;
(2) the metal nanoparticles loaded post processing of crosslinked polyethylene: methyl alcohol, ethanol, propyl alcohol or other alcohols solvent for crosslinked polyethylene of step 1 gained load palladium metal are washed 3 times, the 1-10 that each alcohols solvent consumption is the organic solvent volume doubly, and then with oxolane or the fragmentation of carrene swelling, the 1-10 that its consumption is the organic solvent volume doubly, again with methyl alcohol or ethanol washing, the 1-10 that its consumption is the organic solvent volume doubly, product after processing, at 30-100 ℃ of vacuum drying, can prepare the metal nanoparticle of crosslinked polyethylene load.
2. the preparation method that crosslinked polyethylene is metal nanoparticles loaded, is characterized in that, comprises the following steps:
(1) crosslinked polyethylene of load palladium metal nano particle load is synthetic: utilize palladium-diimine catalysts, carry out " one pot " copolymerization of ethene and dienes monomer and/or function monomer in the organic solvent of crossing in drying under-30 ~ 50 ℃, wherein, palladium-diimine catalysts concentration is 0.001-1 mol/L, the dienes monomer concentration is 0.01-2mol/L, function monomer concentration is 0.01-2mol/L, and ethylene pressure is 0.1-100atm, reaction time 0.5-48h; In polymerization process, before polyethylene gel forms, add palladium salt, the palladium salinity of adding is 0-5mol/L; Reaction adds reaction terminating agent after finishing, and the volume ratio of reaction terminating agent and organic solvent is 1-100:1, obtains the crosslinked polyethylene of load palladium metal;
(2) secondary load of other metal nanoparticle: the crosslinked polyethylene of the load palladium metal that obtains in step 1 is scattered in the organic solvent of equal volume again, add other slaine that need to carry out load, the concentration of slaine is 0.001-5mol/L, utilize functional group in crosslinked polyethylene and the charge effect between ionizable metal salt, the load of realization to slaine, load time 0.5-24h; Then, add reducing agent, the concentration of reducing agent is 0-5 mol/L, reaction time 0.5-10h, and reducing loaded slaine, obtain the metal nanoparticle of crosslinked polyethylene load;
(3) the metal nanoparticles loaded post processing of crosslinked polyethylene: step 2 products therefrom further washs 3 times with methyl alcohol, ethanol, propyl alcohol or other alcohols solvent, the 1-10 that each alcohols solvent consumption is the organic solvent volume doubly, and then with oxolane or the fragmentation of carrene swelling, the 1-10 that its consumption is the organic solvent volume doubly, again with methyl alcohol or ethanol washing, the 1-10 that its consumption is the organic solvent volume doubly, product after processing, at 30-100 ℃ of vacuum drying, can prepare the metal nanoparticle of crosslinked polyethylene load.
3. according to the metal nanoparticles loaded preparation method of the described crosslinked polyethylene of claim 1 or 2, it is characterized in that, described dienes monomer be can with esters of acrylic acid or the olefin monomer of ethene generation copolymerization, comprise two acrylic acid diol esters, diethylene glycol diacrylate, four (ethylene glycol) diacrylate, diacrylate macrogol ester, N, N'-di-2-ethylhexylphosphine oxide acrylate, two (2-acryloyl) ethyoxyl two sulphur, Allyl disulfide, allyl sulfide and alkadienes etc.
4. according to the metal nanoparticles loaded preparation method of the described crosslinked polyethylene of claim 1 or 2, it is characterized in that, described function monomer is energy and ethylene copolymer, olefines or acrylic ester monomer with specific functional groups, comprise N, N'-di-2-ethylhexylphosphine oxide acrylate, two (2-acryloyl) ethyoxyl two sulphur, Allyl disulfide, allyl sulfide, 2-(2'-bromo isobutyl acyloxy) ethyl-2 "-the acrylyl oxy-ethyl disulfide, 2-(2-bromine isobutoxy) ethyl acrylate, acrylic acid-2, 3-epoxy propyl ester, 2 (acryloyl-oxy base oxethyl) trimethyl silane, acrylyl oxy-ethyl-trimethyl salmiac, 2-(dimethylamino) ethyl acrylate, 2-(lignocaine) ethyl acrylate, tert-butyl acrylate, 2 (1, 1-dimethyl butyrate-3-thiazolinyl) monomer such as oxirane.
5. according to the metal nanoparticles loaded preparation method of the described crosslinked polyethylene of claim 1 or 2, it is characterized in that, described organic solvent comprises: carrene, chlorobenzene, dichloro benzene,toluene,xylene, acetone, dimethyl formamide, dimethyl formamide, oxolane, chloroform.
6. according to the metal nanoparticles loaded preparation method of the described crosslinked polyethylene of claim 1 or 2, it is characterized in that, described reaction terminating agent is comprised of one or both mixing of methyl alcohol and ethanol.
7. according to the metal nanoparticles loaded preparation method of the described crosslinked polyethylene of claim 1 or 2, it is characterized in that, described other slaine is platinum salt, golden salt, rhodium salt or ruthenium salt.
8. according to the metal nanoparticles loaded preparation method of the described crosslinked polyethylene of claim 1 or 2, it is characterized in that, described reducing agent comprises NaBH
4, KBH
4, LiAlH
4, hydrogen, methyl alcohol, ethanol.
9. the metal nanoparticles loaded purposes as catalyst of crosslinked polyethylene, it is characterized in that, described crosslinked polyethylene is metal nanoparticles loaded as heterogeneous catalysis, be applied in the corresponding organic catalytic reaction of its carried metal, the metal nanoparticles loaded use amount of crosslinked polyethylene is controlled at the 0.001-10% that its metal molar number is the mole of reaction substrate.
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