WO2018145517A1 - Procédé de catalyse de polymérisation de monomères vinyliques au moyen de nanoparticules de métal de transition - Google Patents

Procédé de catalyse de polymérisation de monomères vinyliques au moyen de nanoparticules de métal de transition Download PDF

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WO2018145517A1
WO2018145517A1 PCT/CN2017/116807 CN2017116807W WO2018145517A1 WO 2018145517 A1 WO2018145517 A1 WO 2018145517A1 CN 2017116807 W CN2017116807 W CN 2017116807W WO 2018145517 A1 WO2018145517 A1 WO 2018145517A1
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acrylate
methacrylate
nanoparticles
monomer
vinyl
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PCT/CN2017/116807
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Chinese (zh)
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唐华东
李小年
祝一峰
张攀攀
袁明
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浙江工业大学
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Definitions

  • the invention relates to a novel polymerization method of a vinyl monomer, in particular to a method for polymerizing a vinyl monomer by living polymerization by selecting an appropriate catalyst, an initiator and a solvent, and finally obtaining a molecular weight and a molecular weight.
  • a method of distributing a controllable polymer is a novel polymerization method of a vinyl monomer, in particular to a method for polymerizing a vinyl monomer by living polymerization by selecting an appropriate catalyst, an initiator and a solvent, and finally obtaining a molecular weight and a molecular weight.
  • the production methods of these polymers can be mainly divided into free radical polymerization, anionic (cationic) ion polymerization and coordination polymerization according to different reaction mechanisms.
  • the free radical polymerization has a wide range of suitable monomers, mild reaction conditions, and mature theoretical research, which is convenient for large-scale industrial production (Qiu Kunyuan. Polymer Bulletin, 2008(7): 15 The characteristics of -28), and thus the vinyl polymer produced by radical polymerization accounts for about 70% of the total yield of the vinyl polymer.
  • chain initiation is a key reaction that controls the rate of polymerization and the molecular weight of the polymer, directly affecting the polymerization rate of the monomer and the properties of the polymer.
  • the initiator of free radical polymerization can be divided into azo initiator, peroxide initiator, redox initiation system, etc. (Liu Yong, Huang Zhiyu, Lu Yi, et al. Chemical Journal, 2005, 19(3): 35 -39).
  • the azo initiator has no induced decomposition, is stable at normal temperature, and is convenient for storage and transportation, but its type is small, the applicable temperature range is narrow, and the price is high.
  • the peroxygen initiator is rich in products, low in price and wide in use, but the organic peroxide is generally low in purity, easy to react with other factors such as amines and alcohols in the polymerization system, and sensitive to heat, vibration and friction.
  • Storage and transportation troubles Jin Kegang, Xiao Jinping, Wang Huazhou. Fine Chemical Materials and Intermediates, 2007, (3): 18-20).
  • the redox-initiating system chain has low activation energy and can be polymerized at low temperature or room temperature, but the disadvantage is that the utilization efficiency of the initiator is low and the applicable temperature range is narrow.
  • active radical polymerization such as atom transfer radical polymerization (Wang J, Matyjaszewski K, J. Am. Chem.
  • the present invention does not use a radical polymerization initiator or an anion (cation) polymerization initiator, and does not use a coordination polymerization Zieg-Natta catalyst.
  • the polymerization method provided by the invention uses a transition metal nanoparticle as a catalyst and an organosilicon hydrogen compound as an initiator to initiate polymerization of a plurality of ethylenically unsaturated monomers, and finally obtains a controllable molecular weight and molecular weight distribution, and the terminal group contains Silicon polymer functional polymer.
  • the present invention adopts the following technical solutions:
  • a method for catalyzing a polymerization of a vinyl monomer by a transition metal nanoparticle the method being:
  • the monomer, catalyst, initiator and solvent are uniformly mixed and reacted at 0-130 ° C for 0.2-72 h, after which the reaction system is post-treated to obtain a product.
  • the monomer is an ethylenically unsaturated monomer; the catalyst is a transition metal nanoparticle; and the initiator is an organosilicon hydrogen compound.
  • the ratio of the amount of the monomer, the initiator, the catalyst, and the solvent to be charged is 1.0:0.0002 to 0.3:0.0000003 to 0.01:0 to 20, preferably 1:0.001 to 0.1:0.000001 to 0.001:0 to 1, particularly preferably 1:0.001 to 0.01: 0.0001 to 0.001: 0 to 0.5; wherein when the solvent is supplied at a ratio of 0, the monomer is directly subjected to bulk polymerization in the absence of a solvent.
  • a preferred reaction temperature is from 50 to 100 °C.
  • the preferred reaction time is from 1 to 36 hours.
  • the inert gas is, for example, one or a mixture of two or more of the following gases: nitrogen, argon, helium, neon.
  • the post-treatment of the reaction system may be carried out by conventional means known in the art. For example, after the reaction is completed, the reaction system is returned to normal temperature (20 to 30 ° C), and the reaction liquid is poured out or the solid substance is directly taken out to be a polymerization product. The final product is obtained by centrifuging, precipitating, grading, and conventional processing such as injection molding and molding.
  • the polymerization product obtained by the process of the present invention has a terminal group containing a silicone functional group, and the molecular weight and molecular weight distribution are controllable.
  • the molecular weight of the polymerization product is generally between 1.0 x 10 4 and 1.0 x 10 7 daltons, preferably between 5.0 x 10 4 and 5 x 10 6 daltons.
  • the molecular weight distribution of the polymerization product is generally between 1.2 and 3.0, preferably in the range of 1.3 to 2.0, depending on the molecular weight polydispersity index (PDI).
  • the monomer in the present invention is one of the following monomers, or a mixture of two or more miscible monomers in any ratio:
  • styrene including styrene, p-chloromethylstyrene, ⁇ -methylstyrene, p-fluorostyrene, p-chlorostyrene, p-bromostyrene, p-trifluoromethylstyrene, p-pair Vinylbenzene
  • Methacrylates including methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, methyl Octyl acrylate, isooctyl methacrylate, lauryl methacrylate, phenyl methacrylate, glycidyl methacrylate, triethylene glycol methacrylate, 2-ethyl methacrylate Ester, isobornyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, trifluoroethyl methacrylate, hexafluorobutyl methacrylate, N, N- Dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, 1,4-butylene glycol dimethacrylate;
  • (meth)acrylamides including acrylamide, methacrylamide, N-isopropylacrylamide, N-methylol acrylamide, N-(2-hydroxypropyl)methacrylamide, N-methacrylamide, N,N-dimethylacrylamide, N-tert-butylacrylamide, N-n-butylacrylamide, methylenebisacrylamide;
  • vinyl esters including vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate;
  • the monomer is one of the following monomers, or a mixture of two or more miscible monomers in any ratio:
  • styrenes including styrene, p-chloromethylstyrene, p-chlorostyrene
  • Methacrylates including methyl methacrylate, butyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, methacrylic acid Borneol ester, trifluoroethyl methacrylate, hexafluorobutyl methacrylate;
  • acrylates including methyl acrylate, ethyl acrylate, butyl acrylate, lauryl acrylate, hydroxyethyl acrylate, glycidyl acrylate, hexafluorobutyl acrylate;
  • (meth)acrylamides including acrylamide, methacrylamide, N-isopropylacrylamide, N-methylolacrylamide, N,N-dimethylacrylamide, methylene double Acrylamide;
  • vinyl esters including vinyl acetate, vinyl chloroacetate, vinyl propionate
  • the monomer is one of the following monomers, or a mixture of two or more miscible monomers in any ratio:
  • Styrene p-chloromethylstyrene, methyl methacrylate, butyl methacrylate, lauryl methacrylate, glycidyl methacrylate, isobornyl methacrylate, trifluoroethyl methacrylate , methyl acrylate, butyl acrylate, lauryl acrylate, hydroxyethyl acrylate, glycidyl acrylate, acrylamide, methacrylamide, N-isopropyl acrylamide, vinyl acetate, vinyl chloroacetate, propylene Nitrile, acrylic acid, 4-vinyl pyridine, N-vinyl pyrrolidone, vinyl chloride, isoprene.
  • the catalyst in the present invention is one or a mixture of two or more of the following transition metal nanoparticles: gold nanoparticles, silver nanoparticles, copper nanoparticles, platinum nanoparticles, palladium nanoparticles, nickel nanoparticles, ruthenium Nanoparticles, cerium nanoparticles, cerium nanoparticles, iron nanoparticles, cobalt nanoparticles, cerium nanoparticles, tungsten nanoparticles, titanium nanoparticles, vanadium nanoparticles, manganese nanoparticles, molybdenum nanoparticles, chromium nanoparticles.
  • Preferred catalysts are: gold nanoparticles, silver nanoparticles, copper nanoparticles, platinum nanoparticles, palladium nanoparticles, ruthenium nanoparticles, nickel nanoparticles, cobalt nanoparticles, ruthenium nanoparticles, titanium nanoparticles, molybdenum nanoparticles, chromium nanoparticles Particles, tungsten nanoparticles.
  • catalysts are: gold nanoparticles, silver nanoparticles, copper nanoparticles, platinum nanoparticles, palladium nanoparticles, molybdenum nanoparticles, tungsten nanoparticles.
  • the transition metal nanoparticles have an average particle diameter of between 1 and 100 nm, preferably between 2 and 20 nm.
  • the transition metal nanoparticles may be present in the form of a solid powder, a nanoparticle solution, or a nanoparticle loaded onto the surface of the solid substrate.
  • the solvent in the nanoparticle solution includes, but is not limited to, one or more of the following solvents: a mixture of any solvent in a miscible solvent: petroleum ether, n-hexane, toluene, chloroform, tetrahydrofuran, dioxane, and Phenyl ether, ethyl acetate, methanol, ethanol, water, aqueous PBS.
  • the material of the solid substrate includes, but is not limited to, one or a mixture of two or more of the following materials: activated carbon, aluminum oxide, silica gel, molecular sieve, calcium carbonate, barium sulfate, specifically, for example, palladium nanoparticles are loaded to Activated carbon (Pd/C).
  • the initiator in the present invention is one or a mixture of two or more of the following organosilicon compounds:
  • a trihydrosilane compound including phenylsilane, n-butylsilane, n-hexylsilane, cyclohexylsilane, n-octadecylsilane;
  • Dihydrosilane compounds including diphenylsilane, dipropylsilane, diisopropylsilane, di-n-butylsilane, diisobutylsilane, di-tert-butylsilane, di-n-hexylsilane, and Cyclohexylsilane, methylphenylsilane, phenylchlorosilane;
  • monohydrogen silane compounds including triphenyl silane, triethyl silane, tripropyl silane, triisopropyl silane, tri-n-butyl silane, triisobutyl silane, tri-tert-butyl silane, three N-hexylsilane, tricyclohexylsilane, tri-n-octylsilane, n-butyldimethylsilane, isobutyldimethylsilane, tert-butyldimethylsilane, tris(trimethylsilyl)silane, three (triethylsilyl)silane, trichlorosilane, methyldichlorosilane, ethyldichlorosilane, phenyldichlorosilane, dimethylchlorosilane, diphenylchlorosilane, diisopropylchlorosilane, Di-tert-but
  • the initiator is one or a mixture of two or more of the following organosilicon compounds:
  • a trihydrosilane compound including phenylsilane, n-hexylsilane;
  • dihydrosilane compound including diphenylsilane, diethylsilane, di-n-butylsilane, methylphenylsilane, phenylchlorosilane;
  • monohydrosilane compounds including triphenylsilane, triethylsilane, triisopropylsilane, tri-tert-butylsilane, tris(trimethylsilyl)silane, tris(triethylsilyl) Silane, trichlorosilane, methyldichlorosilane, phenyldichlorosilane, dimethylchlorosilane, diphenylchlorosilane, dimethylallylsilane, trimethoxysilane, triethoxysilane, three Tert-butoxysilane.
  • the initiator is one or a mixture of two or more of the following organosilicon compounds: phenylsilane, n-hexylsilane, diphenylsilane, diethylsilane, phenylchlorosilane, three Phenylsilane, triethylsilane, tri-tert-butylsilane, tris(trimethylsilyl)silane, dimethylallylsilane, triethoxysilane.
  • organosilicon compounds phenylsilane, n-hexylsilane, diphenylsilane, diethylsilane, phenylchlorosilane, three Phenylsilane, triethylsilane, tri-tert-butylsilane, tris(trimethylsilyl)silane, dimethylallylsilane, triethoxysilane.
  • the solvent in the present invention is a mixture of one or more of the following solvents in any ratio: n-hexane, cyclohexane, petroleum ether, heptane, octane, benzene, toluene, p-xylene, ten Hydrogen naphthalene, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, tetrachloroethylene, diethyl ether, n-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol Methyl ether, tetrahydrofuran, dioxane, diphenyl ether, acetone, acetylacetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, methanol, ethanol, isopropanol,
  • the room temperature in the present invention is 20 to 30 °C.
  • styrene vinyl chloride
  • vinyl acetate vinyl acetate
  • (meth) acrylate monomers vinyl acetate
  • (meth) acrylamide monomers 4-vinyl pyridine
  • N-ethylene a variety of monomers such as pyrrolidone
  • the reaction can be carried out at normal pressure, room temperature or near room temperature, and the amount of the catalyst can be as low as 1.0 ppm or less, no special equipment is required, the preparation steps are simple, and the production cost is low;
  • ultra-high molecular weight polymers with a molecular weight of more than 3 million. It is suitable for the production of high-strength and high-modulus polymer materials. It is used in chemical fiber, rubber elastomer, plastics, coatings, adhesives, biomedical polymers, etc. The prospects are very broad.
  • Figure 1a TEM image of gold nanoparticles in Example 1;
  • Figure 3 Example of gold particles in the resultant catalyst of MMA 1 PMMA and PDI- M n versus conversion
  • Figure 4a TEM image of Pd/C nanoparticles in Example 7;
  • Figure 5 Nuclear magnetic resonance ( 1 H-NMR) spectrum of PMMA obtained by catalytic polymerization of gold nanoparticles in Example 18.
  • Gold nanopowder organic solvent dispersible, average particle size 6nm, J&K Chemical
  • gold nanoparticle 0.1 mM PBS solution average particle size 20 nm, optical density value 1, Sigma-Aldrich
  • gold nanoparticle n-hexane solution average particle 4.1 nm, 0.75 mg/mL, reference Robinson I, Tung L D, Maenosono S, et al.
  • Nanoscale, 2010, 2, 2624-2630 platinum carbon (Pt/C, 5%, Aladdin), palladium Carbon (Pd/C, 5%, Aladdin), hydrogen (Ru/C, 5%, Aladdin), hydrogen (Rh/C, 5%, Aladdin), hydrogen (Ir/C, 5%, Macklin) , nano nickel powder (Ni, APS 10-25nm, Alfa Aesar), nano iron powder (Fe, APS 10-30nm, Alfa Aesar), nano copper powder (Cu, 99.9%, 10-30nm, Aladdin), nano silver powder ( Ag, APS 20-40 nm, Alfa Aesar), nano titanium powder (Ti, 99.8%, average particle size 60 nm, Aladdin), nano tungsten powder (W, 99.9%, average particle size 100 nm, Aladdin).
  • Tris(trimethylsilyl)silane TTSS, 97%, Sigma-Aldrich
  • tris(triethylsilyl)silane TTESS, 97%, Sigma-Aldrich
  • phenylsilane PSH, 98%, Alfa Aeser
  • Diphenylsilane DPS, 97%, Alfa Aeser
  • triphenylsilane TPS, 99%, Alfa Aeser
  • diethylsilane DES, 98%, Alfa Aeser
  • di-tert-butylsilane DTBS, 95%, TCI
  • triethylsilane TES, 97%, Alfa Aeser
  • triisopropylsilane TiPS, 99%, Alfa Aeser
  • methylphenylsilane MPS, 98%, Aldrich
  • II Benzylsilane DPMS, 97%, Alfa
  • triethoxysilane TEOS, 97%, Alfa
  • Styrene (St, 99%) and acrylamide (99%) were purchased from Alfa Aeser.
  • the monomers such as N-vinylpyrrolidone and isoprene are all Aladdin analytical reagents, and the column is treated with a basic Al 2 O 3 column before the reaction.
  • M n number average molecular weight
  • M w weight average molecular weight
  • PDI molecular weight distribution polydispersity coefficient
  • M PDI M w / M n
  • the measurement was performed by a permeation chromatography (GPC) system.
  • the system is equipped with Viscotek VE1122 solvent delivery unit, Viscotek VE 3580 refractive index detector, Viscotek 270 laser light scattering-differential viscometer dual detector, Viscotek VE2585 column oven and Viscotek T6000M GPC column.
  • M n , M w and PDI were measured using a Shimadzu Prominence GPC analysis system.
  • the system is equipped with Shimadzu RID-20A refractive index detector, Shimadzu SPD-15C UV visible light detector, Shimadzu LC-16C solvent delivery unit, Shimadzu CTO-16C column oven, and Waters Styragel HR 5E DMF column. .
  • Molecular weight calibration curves were prepared using a series of narrowly dispersed PMMA standards (Polymer Laboratories), data acquisition analysis software: Labsolutions Essentia 5.82.
  • Test conditions mobile phase, N,N-dimethylformamide (containing 0.01 M LiBr); column temperature, 50 ° C; mobile phase flow rate, 0.3 mL/min.
  • the molecular weight of polyacrylamide was determined by the viscosity method in accordance with the national standard GB17514-2008.
  • the molecular weight of polyacrylic acid is determined by the viscosity method by reference to Zhao Chunfeng, Liu Kunyuan, Han Shuzhen. Journal of Beijing University of Chemical Technology, 2002, 29(1): 51-55.
  • the nuclear magnetic resonance spectrum of the polymer material was measured on a Bruker Avance III 500 MHz NMR spectrometer.
  • the particle diameter of the metal nanoparticles was measured by a FEI Tecnai G2F30 high resolution transmission electron microscope (TEM).
  • the gold nanoparticle content in the n-hexane solution was measured by PerkinElmer ELAN DRC-e inductively coupled plasma mass spectrometer (ICP-MS). The conversion of the monomer during the reaction was determined gravimetrically.
  • the gold nanoparticle n-hexane solution prepared according to the reference was tested by transmission electron microscopy (TEM).
  • TEM transmission electron microscopy
  • EDX X-ray energy spectrum
  • Fig. 1 the gold nanoparticles are spherical. It has good dispersibility, a particle size of about 3 to 7 nm, and a statistical average particle diameter of 4.1 nm.
  • the gold content in the n-hexane solution was 0.75 mg/mL as measured by ICP-MS.
  • Fig. 2 It can be seen from Fig. 2 that the rate of polymerization of MMA by gold nanoparticles is very high. As the reaction time increases, the monomer conversion rate increases rapidly. The conversion rate is 13.0% at 50 min and 71.1% at 160 min. PMMA polymer has a number average molecular weight M n linearly increased from 1.6 ⁇ 10 5 5.0 ⁇ 10 5, PDI of the polymer is maintained at 2.7 or less (FIG. 3) increasing with conversion, the polymerization reaction exhibit living polymerization wherein The experimental operator can thereby control the molecular weight and molecular weight distribution of the polymerization product by changing the conversion rate of the polymerization reaction.
  • the 2.0 nm (1.01 ⁇ 10 -5 mol Au) organic solvent was added to the Schlenk reaction flask to disperse the gold nanopowder, vacuumed and filled with nitrogen, and 2 mL (0.019 mol) of pre-nitrogen-deoxygenated MMA monomer was added by syringe to ultrasonically oscillate. 1 min, stirring was started, then 10 ⁇ L (5.38 ⁇ 10 -5 mol) DPS was added with a micro syringe, stirred at room temperature for 5 min, and then heated to 80 ° C for 4.5 h. The reaction was stopped and the monomer conversion was 85.2%.
  • PMMA The weight average molecular weight was 2.96 million, the number average molecular weight was 1.31 million, and PDI was 2.25.
  • the purchased Pd/C powder catalyst was tested by transmission electron microscopy (TEM).
  • TEM transmission electron microscopy
  • EDX X-ray energy spectrum
  • Fig. 4 As can be seen from the figure, the Pd nanoparticles are spherical and uniformly dispersed.
  • the particle diameter was between 1-3 nm, and the statistical average particle diameter was 1.7 nm.
  • the polymer solution after the reaction was precipitated with methanol, and the obtained PMMA had a weight average molecular weight of 32,000, a number average molecular weight of 17,000, and a PDI of 1.88 as measured by GPC.
  • the nuclear magnetic resonance spectrum of the obtained PMMA is shown in Fig. 5.
  • the ratio of the PMMA polymer was calculated to be 16,000, which is consistent with the GPC measurement, indicating that a silicon-containing DPS initiator group is present at the end of each macromolecular chain.
  • This functional group can be further converted into other functional groups to obtain a more valuable functional polymer.
  • the conversion of the monomer was 85.1%
  • the weight average molecular weight of the poly(trifluoroethyl methacrylate) was 990,000
  • the number average molecular weight was 780,000
  • the PDI was 1.27.
  • the reaction was stopped after reacting at 90 ° C for 18 h.
  • the conversion of the monomer was 43.2%
  • the weight average molecular weight of poly(N-vinylpyrrolidone) was 470,000
  • the number average molecular weight was 180,000
  • PDI was 2.61.
  • PSH was stirred at room temperature for 5 min, then heated to 70 ° C for 39.5 h, and the reaction was stopped.
  • the conversion of the monomer was 56.8%
  • the weight average molecular weight of the copolymer was 450,000
  • the number average molecular weight was 154,000
  • PDI was 2.92.
  • Initiator azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptanenitrile, the amount of 0.6-2.0 wt%;
  • Polymer number average molecular weight 2772-14656; molecular weight distribution polydispersity index: 3.66-174.42.
  • the conventional radical polymerization initiator is used in a large amount, the obtained polymer has a low molecular weight, and the molecular weight distribution has a large polydispersity coefficient.
  • Monomer methyl methacrylate, concentration 1.23mol / L;
  • Initiator n-butyl lithium, concentration: 2.55 ⁇ 10 -2 mol / L;
  • reaction temperature -40 ° C
  • reaction in a sealed tube reaction time: 90 minutes
  • the anionic polymerization reaction condition of methyl methacrylate is severe, n-butyl lithium is extremely active, and it is required to carry out the reaction under low temperature conditions under a completely anhydrous condition, and the obtained polymer has a wide molecular weight distribution. , showing a bimodal distribution.
  • Monomer methyl methacrylate, concentration 10vol%
  • Catalyst Zieg-Natta catalyst TiCl 4 + AlEt 3 ;
  • reaction temperature -78 ° C
  • reaction time 18 h
  • the coordination polymerization conditions of methyl methacrylate are severe, and TiCl 4 and AlEt 3 are extremely active, and it is required to carry out the reaction in an extremely low temperature environment under completely anhydrous conditions, and the molecular weight of the obtained polymer is relatively high. low.

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Abstract

La présente invention concerne un procédé de catalyse de la polymérisation de monomères vinyliques au moyen de nanoparticules de métal de transition. Le procédé comprend : le mélange uniforme de monomères à insaturation vinylique, des nanoparticules de métal de transition de catalyseur, d'un composé initiateur organosilicium ayant des atomes d'hydrogène et d'un solvant sous la protection d'un gaz inerte ; la réalisation d'une réaction à 0 à 130 °C pendant 0,2 à 72 h ; puis la réalisation d'un post-traitement du système de réaction, de façon à obtenir un produit. Le procédé de la présente invention est approprié pour une large gamme de monomères, la réaction peut être effectuée à température ambiante ou proche et sous une pression normale, et la quantité d'utilisation du catalyseur peut être inférieure ou égale à 1,0 ppm, sans nécessiter d'équipement spécial, le processus de préparation étant simple, et le coût de production étant faible. Le procédé peut produire des polymères de poids moléculaire ultra-élevé ayant un poids moléculaire supérieur ou égal à 3 millions, étant appropriés pour la production de matériaux polymères à haute résistance et à module élevé, ayant de vastes perspectives d'application dans les domaines des fibres chimiques, des élastomères de caoutchouc, des plastiques, des revêtements, des adhésifs, des polymères biomédicaux et équivalents.
PCT/CN2017/116807 2017-02-09 2017-12-18 Procédé de catalyse de polymérisation de monomères vinyliques au moyen de nanoparticules de métal de transition WO2018145517A1 (fr)

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