WO2018145517A1 - Method for catalyzing polymerization of vinyl monomers by means of transition metal nanoparticle - Google Patents

Abstract

The present invention provides a method for catalyzing polymerization of vinyl monomers by means of transition metal nanoparticles. The method comprises: uniformly mixing vinyl unsaturated monomers, the catalyst transition metal nanoparticles, an initiator organosilicon hydrogen compound and a solvent under the protection of an inert gas; performing reaction at 0 to 130 °C for 0.2 to 72 h; and then performing post-treatment of the reaction system, so as to obtain a product. The method of the present invention is suitable for a wide range of monomers, the reaction can be performed at or near room temperature and under a normal pressure, and the usage amount of the catalyst can be as low as 1.0 ppm or less, without the need for special equipment, the preparation process being simple, and the production cost being low. The method can produce ultra-high molecular weight polymers having a molecular weight of 3 million or more, being suitable for the production of high strength and high modulus polymer materials, having wide application prospects in the fields of chemical fibers, rubber elastomers, plastics, coatings, adhesives, biomedical polymers and the like.

Description

Method for catalyzing polymerization of vinyl monomer by transition metal nanoparticles (1) Technical field

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.

(2) Background technology

The world produces more than 200 million tons of vinyl polymer per year. 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. Compared with the cation (cationic) ion polymerization and coordination polymerization, 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.

In free radical polymerization, 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). Among them, 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. In recent years, active radical polymerization such as atom transfer radical polymerization (Wang J, Matyjaszewski K, J. Am. Chem. Soc., 1995, 117: 5614-5615.), reversible addition fragmentation chain transfer polymerization (Le T P, Moad G, Rizzardo E, PCT Int. Appl., WO 9801478A1, 980115, 1998) have been widely used in the laboratory, but due to the large amount of transition metal complexes and dithioester chain transfer agents. The cost is high, and the problem of transition metal complexes and dithioester fragments remaining in the polymer needs to be solved, and it is difficult to realize large-scale industrial production applications.

(3) Invention content

It is an object of the present invention to provide a novel polymerization process for vinyl monomers. Different from the conventional radical polymerization, anion (cation) polymerization or coordination polymerization method, 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.

To achieve the above object, 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:

Under the protection of inert gas, 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:

(1) styrene, including styrene, p-chloromethylstyrene, α-methylstyrene, p-fluorostyrene, p-chlorostyrene, p-bromostyrene, p-trifluoromethylstyrene, p-pair Vinylbenzene

(2) 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;

(3) Acrylates, including methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, octyl acrylate, isooctyl acrylate, lauryl acrylate, hydroxyethyl acrylate Ester, hydroxypropyl acrylate and hydroxybutyl acrylate, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, trifluoroethyl acrylate, glycidyl acrylate , triethylene glycol acrylate, hexafluorobutyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, 1,4-butylene glycol diacrylate, isobornyl acrylate;

(4) (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;

(5) vinyl esters, including vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate;

(6) Other types of monomers, including acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, 4-vinylpyridine, N-vinylpyrrolidone, vinyl chloride, isoprene, butadiene.

Preferably, the monomer is one of the following monomers, or a mixture of two or more miscible monomers in any ratio:

(1) styrenes, including styrene, p-chloromethylstyrene, p-chlorostyrene;

(2) Methacrylates, including methyl methacrylate, butyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, methacrylic acid Borneol ester, trifluoroethyl methacrylate, hexafluorobutyl methacrylate;

(3) acrylates, including methyl acrylate, ethyl acrylate, butyl acrylate, lauryl acrylate, hydroxyethyl acrylate, glycidyl acrylate, hexafluorobutyl acrylate;

(4) (meth)acrylamides, including acrylamide, methacrylamide, N-isopropylacrylamide, N-methylolacrylamide, N,N-dimethylacrylamide, methylene double Acrylamide;

(5) vinyl esters, including vinyl acetate, vinyl chloroacetate, vinyl propionate;

(6) Other types of monomers, including acrylonitrile, acrylic acid, 4-vinylpyridine, N-vinylpyrrolidone, vinyl chloride, isoprene.

Particularly preferably, 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.

Particularly preferred 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:

(1) a trihydrosilane compound, including phenylsilane, n-butylsilane, n-hexylsilane, cyclohexylsilane, n-octadecylsilane;

(2) Dihydrosilane compounds, including diphenylsilane, dipropylsilane, diisopropylsilane, di-n-butylsilane, diisobutylsilane, di-tert-butylsilane, di-n-hexylsilane, and Cyclohexylsilane, methylphenylsilane, phenylchlorosilane;

(3) 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-butylchlorosilane, methylphenylchlorosilane, dimethylallylsilane, methyldiphenylsilane, dimethylphenylsilane, dimethyl-n-hexylsilane, dimethyl-n-butylsilane , n-octadecyldiethoxysilane, trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, tri-tert-butoxysilane, A Dimethoxysilane, methyldiethoxysilane, phenyldimethoxysilane, phenyldiethoxysilane.

Preferably, the initiator is one or a mixture of two or more of the following organosilicon compounds:

(1) a trihydrosilane compound, including phenylsilane, n-hexylsilane;

(2) a dihydrosilane compound, including diphenylsilane, diethylsilane, di-n-butylsilane, methylphenylsilane, phenylchlorosilane;

(3) 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.

Particularly preferably, 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.

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, n-butanol, Isobutanol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, water, N,N-dimethylformamide, N-methylformamide, N-methyl Amide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, γ-butyrolactone.

The room temperature in the present invention is 20 to 30 °C.

The invention has three distinct advantages:

First, a wide range of suitable monomers, including styrene, vinyl chloride, vinyl acetate, (meth) acrylate monomers, (meth) acrylamide monomers, 4-vinyl pyridine, N-ethylene a variety of monomers such as pyrrolidone;

Secondly, 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;

Third, it can prepare 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.

(4) Description of the drawings

Figure 1a: TEM image of gold nanoparticles in Example 1;

Figure 1b: EDX spectrum of gold nanoparticles in Example 1;

Figure 2: Conversion rate-time curve of gold nanoparticle catalyzed MMA polymerization 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 4b: EDX spectrum 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.

(5) Specific implementation methods

The details of the objects, advantages and technical solutions of the present invention are further illustrated by the specific embodiments. Due to the similar nature of similar monomers or similar initiators, only typical examples of such monomers or initiators are used in the examples (eg, in styrene, methacrylate monomers in styrenic monomers). Methyl methacrylate and isobornyl methacrylate, methyl acrylate and butyl acrylate in acrylate monomers, phenyl silane in a trihydrosilane initiator, and the like are exemplified. The specific materials and amounts and other details set forth in the examples are not intended to limit the invention. Many other modifications and embodiments can be devised by those skilled in the art in light of the present invention. These modifications and embodiments are also within the scope of the invention.

The raw materials, equipment, and test characterization methods used in the specific example process are as follows.

Reagent material

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 Aeser), other silanes were purchased from J&K Chemical.

Styrene (St, 99%) and acrylamide (99%) were purchased from Alfa Aeser. Methyl methacrylate (MMA), methyl acrylate (MA), butyl acrylate (BA), vinyl acetate (VAc), trifluoroethyl methacrylate, isobornyl methacrylate, 4-vinyl pyridine 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.

testing method

For tetrahydrofuran (THF) soluble polymers, the number average molecular weight (M _n ), weight average molecular weight (M _w ) and molecular weight distribution polydispersity coefficient PDI (PDI = M _w / M _n ) with Malvern Viscotek 270Max gel 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. The system was calibrated with polystyrene standard polymer PS 105k (Malvern, PolyCAL PS Std) according to the instrument manufacturer's operating manual and further verified with polystyrene standard polymer PS 9290k (Polymer Standard Service USA, Inc). Data acquisition and analysis software: OmniSEC 5.02. Test conditions: mobile phase, tetrahydrofuran; column temperature, 35 ° C; mobile phase flow rate: 1.0 mL / min.

For THF-insoluble polyvinylpyridine and polyvinylpyrrolidone, 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.

Example 1

The gold nanoparticle n-hexane solution prepared according to the reference was tested by transmission electron microscopy (TEM). The obtained TEM image and X-ray energy spectrum (EDX) are shown in Fig. 1. As can be seen from the figure, 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.

Add 100 μL of the above-mentioned 100 μL (3.81×10 ^-7 mol Au) gold nanoparticle n-hexane solution to the centrifuge tube, centrifuge at 16000 g for 30 min, remove the supernatant, add 2 mL (0.019 mol) of MMA monomer, shake for 30 s, and purge with nitrogen. Oxygen for 5 min, then the monomer solution was added to a nitrogen-desulfurized Schlenk reaction bottle with a syringe, stirring was started, 10 μL (5.38×10 ^-5 mol) DPS was added with a micro syringe, stirred at room temperature for 5 min, and then heated to 70 ° C. At 6 min, 50 min, 90 min, 130 min, and 160 min, an oxygen scavenging syringe and a long needle were used to sample from the reaction flask. The conversion rate of the monomer at each reaction time point was determined by gravimetric method, and the weight average of each point polymer was determined by GPC. molecular weight M _n, weight average molecular weight M _w and _{PDI (PDI = M w / M} n), rendering the conversion - time curve, number average molecular weight - as well as the conversion curve PDI- conversion curve, results as shown in FIG. 2 and FIG. 3 is shown.

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.

Example 2

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 μL (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.

Example 3

2 mL (1.32 × 10 ^-6 mol Au) gold nanoparticles 0.1 mM PBS solution was added to the centrifuge tube, centrifuged at 10,000 g for 20 min, the supernatant was removed, 2 mL of tetrahydrofuran was added, ultrasonically shaken for 30 s, centrifuged at 10000 g for 20 min, the supernatant was removed, and 5 mL was added ( 0.047mol) MMA monomer, ultrasonically shaken for 30s, degassed by nitrogen for 5min, then the monomer solution was added to the nitrogen and deoxidation Schlenk reaction bottle by syringe, and the mixture was stirred, and 10μL (8.10×10) was added with a micro syringe. ^-5 mol) PSH, stirred at room temperature for 5 min, then heated to 70 ° C for 10 h and then stopped. The conversion of the monomer was 59.0%, the weight average molecular weight of PMMA was 2.12 million, the number average molecular weight was 1.02 million, and PDI was 2.07.

Example 4

Add 30 μL (1.15×10 ^-7 mol Au) gold nanoparticles to n-hexane solution to the centrifuge tube, centrifuge at 16000 g for 30 min, remove the supernatant, add 15 mL (0.142 mol) of MMA monomer, ultrasonically shake for 30 s, and deaerator with nitrogen for 5 min. Then, the monomer solution was added to a nitrogen-desulfurized Schlenk reaction bottle by a syringe, and stirring was started. 5 μL (4.05×10 ^-5 mol) of PSH was added by a micro syringe, stirred at room temperature for 5 minutes, and then heated to 70 ° C for 22.5 hours. After the reaction was stopped, the conversion of the monomer was 83.1%, the weight average molecular weight of the polymer PMMA was 7.79 million, the number average molecular weight was 5.82 million, and the PDI was 1.34.

Example 5

Add 100 μL (3.81×10 ^-7 mol Au) gold nanoparticles to n-hexane solution to the centrifuge tube, centrifuge at 16000 g for 30 min, remove the supernatant, add 10 mL (0.094 mol) of MMA monomer and 10 mL (0.094 mol) of toluene solvent, and shake for 30 s. Nitrogen was bubbled and deaerated for 5 min. Then, the monomer solution was added to a nitrogen-desulfurized Schlenk reaction bottle with a syringe, and stirring was started. 10 μL (5.38×10 ^-5 mol) of DPS was added using a micro syringe, and the mixture was stirred at room temperature for 5 min. After the temperature was raised to 70 ° C for 11.5 h, the reaction was stopped. The conversion of the monomer was 35.0%, the weight average molecular weight of PMMA was 1.57 million, the number average molecular weight was 840,000, and PDI was 1.87.

Example 6

Add 1 mL (3.81×10 ^-6 mol Au) gold nanoparticle n-hexane solution to the centrifuge tube, centrifuge at 16000 g for 30 min, remove the supernatant, add 0.5 mL (0.0047 mol) MMA monomer and 9.5 mL (0.090 mol) toluene solvent, and sonicate. After shaking for 30 s, deaerator with nitrogen for 5 min, then add the monomer solution to a nitrogen-desulfurized Schlenk reaction bottle with a syringe, start stirring, add 20 μL (1.08×10 ^-4 mol) DPS with a micro syringe, at room temperature. After stirring for 5 min, the temperature was raised to 70 ° C for 17 h, and the reaction was stopped. The conversion of the monomer was 62.9%, the weight average molecular weight of PMMA was 110,000, the number average molecular weight was 64,000, and PDI was 1.72.

Example 7

The purchased Pd/C powder catalyst was tested by transmission electron microscopy (TEM). The obtained TEM image and X-ray energy spectrum (EDX) are shown in Fig. 4. As can be seen from the figure, the Pd nanoparticles are spherical and uniformly dispersed. On the activated carbon powder, the particle diameter was between 1-3 nm, and the statistical average particle diameter was 1.7 nm.

Add 20 mg Pd/C (9.40×10 ^-6 mol Pd) to the Schlenk reaction flask, vacuum-fill nitrogen three times, add 2 mL (0.019 mol) of pre-deoxygenated MMA monomer with a syringe, shake it for 30 s, and start stirring. 10 μL (8.10×10 ^-5 mol) PSH was added in a micro-syringe, stirred at room temperature for 5 min, and then heated to 80 ° C for 16.5 h. The reaction was stopped. The conversion of the monomer was 53.0%, and the weight average molecular weight of PMMA was 2.69 million. The number average molecular weight was 1.49 million, and PDI was 1.81.

Example 8

Add 20 mg Ru/C (9.90×10 ^-6 mol Ru) to the Schlenk reaction flask, vacuum-fill nitrogen three times, add 2 mL (0.019 mol) of pre-deoxygenated MMA monomer with a syringe, shake it for 30 s, and start stirring. 10 μL (8.10×10 ^-5 mol) PSH was added in a micro-syringe, stirred at room temperature for 5 min, and then heated to 80 ° C for 25 h. The reaction was stopped. The conversion of the monomer was 31.1%, and the weight average molecular weight of PMMA was 4.49 million. The average molecular weight was 1.91 million, and PDI was 2.35.

Example 9

Add 40 mg of Rh/C (1.94×10 ^-5 mol Rh) to the Schlenk reaction flask, evacuate it under vacuum for three times, add 2 mL (0.019 mol) of pre-deoxygenated MMA monomer with a syringe, shake it for 30 s, and start stirring. 10 μL (5.38×10 ^-5 mol) of DPS was added in a micro-syringe, stirred at room temperature for 5 min, and then heated to 70 ° C for 24 h. The reaction was stopped. The conversion of the monomer was 47.4%, and the weight average molecular weight of PMMA was 4.75 million. The average molecular weight was 2.62 million, and PDI was 1.81.

Example 10

Add 40 mg of Pt/C (1.03×10 ^-5 mol Pt) to the Schlenk reaction flask, evacuate it under vacuum for three times, add 2 mL (0.019 mol) of pre-deoxygenated MMA monomer with a syringe, shake it for 30 s, and start stirring. 10 μL (5.38×10 ^-5 mol) of DPS was added in a micro-syringe, stirred at room temperature for 5 min, and then heated to 70 ° C for 13 h. The reaction was stopped. The conversion of the monomer was 24%, and the weight average molecular weight of the polymer PMMA was 2.1 million. , the number average molecular weight of 780,000, PDI = 2.69.

Example 11

Add 20 mg Ir/C (5.21×10 ^-6 mol Ir) to the Schlenk reaction flask, vacuum-fill nitrogen three times, add 2 mL (0.019 mol) of pre-deoxygenated MMA monomer with a syringe, shake it for 30 s, and start stirring. 10 μL (8.10×10 ^-5 mol) PSH was added in a micro-syringe, stirred at room temperature for 5 min, and then heated to 80 ° C for 34 h. The reaction was stopped. The conversion of the monomer was 25.6%, and the weight average molecular weight of PMMA was 3.6 million. The average molecular weight was 1.95 million, and PDI was 1.85.

Example 12

Add 10 mg (1.79×10 ^-4 mol) of nano-iron powder to the Schlenk reaction flask, vacuum-fill nitrogen three times, add 5 mL (0.047 mol) of pre-deoxygenated MMA monomer with a syringe, shake it for 1 min, stir vigorously. 10μL (5.38×10 ^-5 mol) DPS was added to the micro-syringe, stirred at room temperature for 5 min, and then heated to 70 ° C for 22.5 h. The reaction was stopped. The conversion of the monomer was 23.4%, and the weight average molecular weight of PMMA was 2.8 million. The average molecular weight was 1.71 million and PDI=1.63.

Example 13

Add 10 mg (1.70×10 ^-4 mol) of nano-nickel powder to the Schlenk reaction flask, vacuum-fill nitrogen three times, add 5 mL (0.047 mol) of pre-deoxygenated MMA monomer with a syringe, shake it for 1 min, stir vigorously. 10μL (5.38×10 ^-5 mol) DPS was added to the micro-syringe, stirred at room temperature for 5 min, then heated to 80 ° C for 30 h and then stopped. The sample was found to have a conversion of 25.2%. The weight average molecular weight of PMMA was 1.97 million. , the number average molecular weight of 920,000, PDI = 2.14.

Example 14

Add 10mg (1.57×10 ^-4 mol) of nano copper powder to the Schlenk reaction bottle, vacuum and nitrogen three times, add 5mL (0.047mol) of pre-oxygenated MMA monomer with syringe, ultrasonically shake for 1min, use with vigorous stirring 10μL (8.10×10 ^-5 mol) PSH was added to the micro-syringe, stirred at room temperature for 5 min, and then heated to 80 ° C for 26 h. The reaction was stopped. The conversion of the monomer was 26.7%, and the weight average molecular weight of PMMA was 3.01 million. The number average molecular weight was 1.61 million, and PDI=1.87.

Example 15

Add 15mg (1.39×10 ^-4 mol) of nano silver powder to the Schlenk reaction bottle, vacuum and nitrogen gas three times, add 5mL (0.047mol) pre-deoxygenated MMA monomer with syringe, ultrasonically shake for 1min, stir with trace 10 μL (8.10×10 ^-5 mol) PSH was added to the syringe, stirred at room temperature for 5 min, and then heated to 80 ° C for 21 h. The reaction was stopped. The conversion of the monomer was 35.5%, and the weight average molecular weight of PMMA was 7.43 million. The number average molecular weight was 5.58 million, and PDI=1.33.

Example 16

Add 20 mg (4.18×10 ^-4 mol) of nano titanium powder to the Schlenk reaction flask, vacuum-fill nitrogen three times, add 5 mL (0.047 mol) of pre-deoxygenated MMA monomer with a syringe, shake it for 1 min, stir vigorously. 10μL (8.10×10 ^-5 mol) PSH was added to the micro-syringe, stirred at room temperature for 5 min, and then heated to 90 ° C for 30 h. The reaction was stopped. The conversion of the monomer was 32.2%, and the weight average molecular weight of PMMA was 2.27 million. , the number average molecular weight of 1.27 million, PDI = 1.79.

Example 17

Add 25mg (1.36×10 ^-4 mol) of nano-tungsten powder to Schlenk reaction flask, vacuum-fill nitrogen three times, add 5mL (0.047mol) pre-deoxygenated MMA monomer with syringe, ultrasonically shake for 1min, use with vigorous stirring 10μL (8.10×10 ^-5 mol) PSH was added to the micro-syringe, stirred at room temperature for 5 min, and then heated to 80 ° C for 24 h. The reaction was stopped. The conversion of the monomer was 28.8%, and the weight average molecular weight of PMMA was 2.07 million. , the number average molecular weight of 830,000, PDI = 2.49.

Example 18

Add 10 mL (3.81×10 ^-5 mol Au) gold nanoparticle n-hexane solution to the centrifuge tube, centrifuge at 16000 g for 30 min, remove the supernatant, add 1 mL (0.0094 mol) of MMA monomer, shake for 30 s, and deaerate with nitrogen. 5 min, then the monomer solution was added to a nitrogen-desulfurized Schlenk reaction bottle with a syringe, stirring was started, 500 μL (2.69×10 ^-3 mol) DPS was added with a micro syringe, stirred at room temperature for 5 min, and then heated to 70 ° C. The reaction was stopped after a minute, and the conversion of the monomer was measured to be 5.0%.

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 three sets of multiple peaks between δ=7.2-7.8 ppm in the figure correspond to the protons on the benzene ring of the initiator DPS, and the strong peak of δ=3.6 ppm corresponds to the protons on the methoxy group of the long chain of PMMA, according to the two. 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.

Example 19

Add 5 mL (1.90×10 ^-5 mol Au) gold nanoparticle n-hexane solution to the centrifuge tube, centrifuge at 16000 g for 30 min, remove the supernatant, add 1 mL (0.0094 mol) of MMA monomer, ultrasonically shake for 30 s, and deaerator with nitrogen for 5 min. Then, the monomer solution was added to a nitrogen-desulfurized Schlenk reaction bottle by a syringe, and the stirring was started. 50 μL (2.69×10 ^-4 mol) of DPS was added by a micro syringe, and the reaction system was cooled to 0 ° C for reaction, after 24 hours. The reaction was stopped, and the conversion of the monomer was 51.1%, the weight average molecular weight of PMMA was 550,000, the number average molecular weight was 190,000, and PDI was 2.89.

Example 20

250 μL (9.52×10 ^-7 mol Au) gold nanoparticles in n-hexane solution was added to the centrifuge tube, centrifuged at 16000 g for 30 min, the supernatant was removed, 20 mL (0.189 mol) of MMA monomer was added, ultrasonically shaken for 30 s, and oxygen was bubbled for 5 min. Then, the monomer solution was added to a nitrogen-desulfurized Schlenk reaction bottle by a syringe, and the stirring was started. 10 μL (6.26×10 ^-5 mol) of TES was added by a micro syringe, and the reaction system was cooled to 70 ° C for reaction, after 34 hours. The reaction was stopped, and the conversion of the monomer was 30.8%, the weight average molecular weight of PMMA was 6.36 million, the number average molecular weight was 4.48 million, and PDI=1.42.

Example 21

Add 200 μL (7.62×10 ^-7 mol Au) gold nanoparticles to n-hexane solution to the centrifuge tube, centrifuge at 16000 g for 30 min, remove the supernatant, add 10 mL (0.108 mol) of vinyl acetate monomer, shake for 30 s, and purge with nitrogen. Oxygen for 5 min, then the monomer solution was added to a nitrogen-desulfurized high-pressure reaction tube (Ace pressure tubes, #15 Ace-Thred) by a syringe, and the stirring was started. 10 μL (8.10×10 ^-5 mol) PSH was added with a micro syringe, and the temperature was increased. After stirring for 5 min, the temperature was raised to 80 ° C for 72 h, and the reaction was stopped. The conversion of the monomer was 54.9%, the weight average molecular weight of polyvinyl acetate was 260,000, the number average molecular weight was 120,000, and the PDI was 2.17.

Example 22

Add 0.5 mL (1.90×10 ^-6 mol Au) gold nanoparticle n-hexane solution to the centrifuge tube, centrifuge at 16000 g for 30 min, remove the supernatant, add 2 mL (0.020 mol) of isoprene monomer, ultrasonically shake for 30 s, and pass the nitrogen drum. The bubble was deaerated for 5 min, then the monomer solution was added to a nitrogen-desulfurized high-pressure reaction tube (Ace pressure tubes, #15 Ace-Thred) by a syringe, and the stirring was started, and 50 μL (3.86×10 ^-4 mol) was added using a micro syringe. DES, after stirring at room temperature for 5 min, the temperature was raised to 130 ° C for 23 h, and the reaction was stopped. The conversion of the monomer was 32.4%, the weight average molecular weight of polyisoprene was 90,000, the number average molecular weight was 45,000, and PDI was 2.0.

Example 23

100 μL of gold nanoparticle n-hexane solution (3.81×10 ^-7 mol Au) was added to the centrifuge tube, centrifuged at 16000 g for 30 min, the supernatant was removed, 20 mL of butyl acrylate monomer (0.138 mol) was added, ultrasonically shaken for 30 s, and nitrogen gas was bubbled. Oxygen for 5 min, then the monomer solution was added to a nitrogen-desulfurized Schlenk reaction bottle with a syringe, stirring was started, 10 μL of DES (7.72×10 ^-5 mol) was added with a micro syringe, stirred at room temperature for 5 min, and then heated to 60 ° C. After 16 h, the reaction was stopped. The conversion of the monomer was 54.4%, the weight average molecular weight of polybutyl acrylate was 9.81 million, the number average molecular weight was 6.48 million, and PDI=1.51.

Example 24

Add 20 μL of gold nanoparticle n-hexane solution (7.61×10 ^-8 mol Au) to the centrifuge tube, centrifuge at 16000 g for 30 min, remove the supernatant, add 20 mL of methyl acrylate monomer (0.222 mol), ultrasonically shake for 30 s, and purge with nitrogen. Oxygen for 5 min, then the monomer solution was added to a nitrogen-desulfurized Schlenk reaction bottle with a syringe, stirring was started, 6 μL of DES (4.63×10 ^-5 mol) was added with a micro syringe, stirred at room temperature for 5 min, and then heated to 50 ° C. After 16 h, the reaction was stopped. The conversion of the monomer was 53.5%, the weight average molecular weight of polymethyl acrylate was 8.27 million, the number average molecular weight was 6.11 million, and PDI=1.35.

Example 25

Add 1.0 mL of gold nanoparticle n-hexane solution (3.81×10 ^-6 mol Au) to the centrifuge tube, centrifuge at 16000 g for 30 min, remove the supernatant, and add 4 mL (0.061 mol) of acrylonitrile monomer and 1 mL (0.013 mol) of N, N- Dimethylformamide solvent, ultrasonic vibration for 30 s, bubbling oxygen for 5 min, then adding the monomer solution to a nitrogen-desulfurized Schlenk reaction bottle with a syringe, stirring, and adding 10 μL (8.10×10) with a micro syringe. ^-5 mol) PSH, stirred at room temperature for 5 min, then heated to 60 ° C for 30 h and then stopped. The conversion of monomer was 18.0%, the weight average molecular weight of polyacrylonitrile was 1.07 million, and the number average molecular weight was 370,000. PDI=2.89 .

Example 26

Add 1g (0.014mol) of acrylamide monomer to Schlenk reaction flask, vacuum-fill nitrogen, add 1.0mL (6.60×10 ^-7 mol Au) gold nanoparticles 0.1 mM PBS solution with syringe, ultrasonically shake for 30s, pass nitrogen drum The bubble was deoxidized for 10 min, the stirring was started, 20 μL (1.62×10 ^-4 mol) PSH was added with a micro syringe, and the reaction was stopped after 1.5 h at room temperature. The conversion of the monomer was determined by sampling, and the polyacrylamide was measured by the viscosity method. The molecular weight is 970,000.

Example 27

1.0 mL (6.60×10 ^-7 mol Au) gold nanoparticles 0.1 mM PBS solution, 4 g (0.056 mol) of acrylic acid monomer and 1 mL (0.056 mol) of distilled water solvent were added to the Schlenk reaction flask, and ultrasonically shaken for 30 s. After deaeration for 10 min, stir stirring, add 10 μL (8.10×10 ^-5 mol) PSH with a micro-syringe, stir the reaction at room temperature for 2 h, then stop the reaction. The sample was found to have a conversion of 44.7%. The viscosity of the polyacrylic acid was determined by viscosity method. It is 5.52 million.

Example 28

Add 0.5 mL (1.90×10 ^-6 mol Au) gold nanoparticle n-hexane solution to the centrifuge tube, centrifuge at 16000 g for 30 min, remove the supernatant, add 2 mL (0.017 mol) of styrene monomer, ultrasonically shake for 30 s, and purge with nitrogen. Oxygen for 5 min, then the monomer solution was added to a nitrogen-desulfurized Schlenk reaction bottle with a syringe, stirring was started, 10 μL (8.10×10 ^-5 mol) PSH was added with a micro syringe, stirred at room temperature for 5 min, and then heated to 80 ° C. After 14h, the reaction was stopped. The conversion of the monomer was 59.4%, the weight average molecular weight of polystyrene was 750,000, and the number average molecular weight was 260,000. PDI=2.88

Example 29

Add 50 μL (1.90×10 ^-7 mol Au) gold nanoparticles to n-hexane solution to the centrifuge tube, centrifuge at 16000 g for 30 min, remove the supernatant, add 2 mL (0.035 mol) of trifluoroethyl methacrylate monomer, and shake for 30 s. Nitrogen was bubbled and deaerated for 5 min. Then, the monomer solution was added to a nitrogen-desulfurized Schlenk reaction bottle with a syringe, and stirring was started. 10 μL (5.38×10 ^-5 mol) of DPS was added with a micro syringe, and the mixture was stirred at room temperature for 5 minutes. After the reaction was carried out at 80 ° C for 11.5 h, the reaction was stopped. 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, and the PDI was 1.27.

Example 30

10.0 mg (3.84 x 10 ^-5 mol) of TPS was added to the Schlenk reaction flask, and the mixture was evacuated under nitrogen. Add 1.0 mL of gold nanoparticle n-hexane solution (3.81×10 ^-6 mol Au) to the centrifuge tube, centrifuge at 16000 g for 30 min, remove the supernatant, and add 10 mL (0.044 mol) of isobornyl methacrylate monomer and 3 mL (0.035 mol). Dioxane solvent, ultrasonic vibration for 30s, bubbling oxygen for 5min, then adding the monomer solution to the nitrogen and deoxidation Schlenk reaction bottle with a syringe, stirring, stirring at room temperature for 5min, then heating to 70 °C reaction After 6 h, the reaction was stopped, and the conversion of the monomer was 52.7%. The weight average molecular weight of polyisobornyl methacrylate was 6.28 million, the number average molecular weight was 4.41 million, and PDI=1.42.

Example 31

Add 100 μL (3.81×10 ^-7 mol Au) gold nanoparticles to n-hexane solution to the centrifuge tube, centrifuge at 16000 g for 30 min, remove the supernatant, add 5 mL (0.047 mol) of N-vinylpyridine monomer, shake for 30 s, and pass the nitrogen drum. The bubble was deaerated for 5 min, then the monomer solution was added to a pre-nitrogen-deoxygenated Schlenk reaction bottle, and stirring was started. 10 μL (8.10×10 ^-5 mol) PSH was added with a micro syringe, stirred at room temperature for 5 min, and then heated to 80 ° C. After 20.5 h, the reaction was stopped. The conversion of the monomer was 46.8%, the weight average molecular weight of poly(N-vinylpyridine) was 758,000, the number average molecular weight was 311,000, and PDI was 2.45.

Example 32

Add 0.5 mL (3.30×10 ^-7 mol Au) gold nanoparticles 0.1 mM PBS solution to the centrifuge tube, centrifuge at 10,000 g for 20 min, remove the supernatant, add 2 mL (0.019 mol) N-vinylpyrrolidone monomer, and shake for 30 s. Nitrogen was bubbled and deaerated for 5 min. Then, the monomer solution was added to a nitrogen-desulfurized Schlenk reaction bottle with a syringe, and stirring was started. 20 μL (1.62×10 ^-4 mol) of PSH was added by a micro syringe, and the mixture was stirred at room temperature for 5 minutes. 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, and PDI was 2.61.

Example 33

Add 200 μL (7.62×10 ^-7 mol Au) gold nanoparticle n-hexane solution to the centrifuge tube, centrifuge at 16000 g for 30 min, remove the supernatant, add 10 mL (0.094 mol) MMA and 10 mL (0.069 mol) butyl acrylate monomer, ultrasonic. After shaking for 30 s, deaerator with nitrogen for 5 min, then add the mixed monomer solution to the pre-nitrogen and deoxidation Schlenk reaction bottle, start stirring, add 20 μL (1.08×10 ^-4 mol) DPS with a micro syringe, stir at room temperature. After 5 minutes, the temperature was raised to 70 ° C for 36 h, and the reaction was stopped. The conversion of the monomer was 34.9%, the weight average molecular weight of the copolymer was 3.7 million, the number average molecular weight was 2.61 million, and PDI=1.42.

Example 34

Add 50 μL (1.90×10 ^-7 mol Au) gold nanoparticles to n-hexane solution to the centrifuge tube, centrifuge at 16000 g for 30 min, remove the supernatant, and add 2.3 mL (0.022 mol) of MMA and 2.3 mL (0.022 mol) of N-vinylpyridine. The monomer was ultrasonically shaken for 30 s, and degassed by nitrogen for 5 min. Then, the mixed monomer solution was added into a nitrogen-desulfurized Schlenk reaction bottle with a syringe, and the mixture was stirred, and 10 μL (8.10×10 ^-5 mol) was added using a micro syringe. 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, and PDI was 2.92.

Comparative example 1

According to the literature (He Wei, Guo Wenxun, Peng Dang, et al. Applied Chemicals, 2011, 40(2): 210-214), a typical example of free radical polymerization is as follows:

Monomer: methyl methacrylate: methacrylic acid: butyl acrylate = 50:25:25;

Initiator: azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptanenitrile, the amount of 0.6-2.0 wt%;

Reaction temperature: 70-85 ° C;

Polymer number average molecular weight: 2772-14656; molecular weight distribution polydispersity index: 3.66-174.42.

Compared with the method of the present invention, 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.

Comparative example 2

According to the literature (Yan Deyue, Wu Bangyuan, Qi Zuwen, et al. Journal of Tongji University, 1980, 4: 34-43), a typical example of anionic polymerization is as follows:

Monomer: methyl methacrylate, concentration 1.23mol / L;

Solvent: toluene;

Initiator: n-butyl lithium, concentration: 2.55 × 10 ^-2 mol / L;

Reaction temperature: -40 ° C; reaction in a sealed tube, reaction time: 90 minutes;

Molecular weight (expressed as the intrinsic viscosity of the polymer): [η] = 164.1 ml/g; the molecular weight distribution is broad and exhibits a bimodal distribution.

Compared with the method of the present invention, 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.

Comparative example 3

According to the literature (Hitoshi Abe, Kiyokazu Imai, Masakazu Matsumoto. Journal of Polymer Science Part B: Polymer Letters, 1965, 3, 1053-1058), a typical example of coordination polymerization is as follows:

Monomer: methyl methacrylate, concentration 10vol%;

Solvent: toluene;

Catalyst: Zieg-Natta catalyst TiCl ₄ + AlEt ₃ ;

Reaction temperature: -78 ° C; reaction time: 18 h;

Conversion rate: 88.5%; molecular weight: 255,000.

Compared with the method of the present invention, 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.

Claims (10)

1. A method for catalyzing a polymerization of a vinyl monomer by a transition metal nanoparticle, characterized in that the method is:

   Under the protection of inert gas, 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; 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.
2. The method of claim 1, wherein the ratio of the amount of the monomer, the initiator, the catalyst, and the solvent to be charged is 1:0.001 to 0.1: 0.000001 to 0.001: 0 to 1.
3. A method of catalyzing a polymerization of a vinyl monomer by transition metal nanoparticles according to claim 1, wherein the temperature of the reaction is from 50 to 100 °C.
4. The method of claim 1, wherein the reaction is carried out for a period of from 1 to 36 hours.
5. A method of catalyzing a polymerization of a vinyl monomer by transition metal nanoparticles according to claim 1, wherein the monomer is one of the following monomers, or a mixture of two or more miscible monomers in any ratio:

   Styrene, p-chloromethylstyrene, α-methylstyrene, p-fluorostyrene, p-chlorostyrene, p-bromostyrene, p-trifluoromethylstyrene, p-divinylbenzene, methacrylic acid Ester, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, octyl methacrylate, isooctyl methacrylate, methacrylic acid Lauryl ester, phenyl methacrylate, glycidyl methacrylate, triethylene glycol methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate Ester, hydroxypropyl methacrylate, hydroxybutyl methacrylate, trifluoroethyl methacrylate, hexafluorobutyl methacrylate, N,N-dimethylaminoethyl methacrylate, N, N -diethylaminoethyl methacrylate, 1,4-butylene glycol dimethacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate , octyl acrylate, isooctyl acrylate, lauryl acrylate, hydroxy acrylate Ester, hydroxypropyl acrylate and hydroxybutyl acrylate, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, trifluoroethyl acrylate, glycidyl acrylate , Triethylene glycol acrylate, hexafluorobutyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, 1,4-butylene glycol diacrylate, isobornyl acrylate, acrylamide, methacryl Amide, N-isopropylacrylamide, N-methylol acrylamide, N-(2-hydroxypropyl)methacrylamide, N-methyl acrylamide, N,N-dimethyl acrylamide, N -tert-butyl acrylamide, N-n-butyl acrylamide, methylene bis acrylamide, vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, acrylonitrile, methacrylonitrile, acrylic acid , methacrylic acid, 4-vinyl pyridine, N-vinyl pyrrolidone, vinyl chloride, isoprene or butadiene.
6. A method of catalyzing a polymerization of a vinyl monomer by a transition metal nanoparticle according to claim 5, wherein the monomer is one of the following monomers, or a mixture of two or more miscible monomers in any ratio:

   Styrene, p-chloromethylstyrene, p-chlorostyrene, methyl methacrylate, butyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate , isobornyl methacrylate, trifluoroethyl methacrylate, hexafluorobutyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, lauryl acrylate, hydroxyethyl acrylate, glycidyl acrylate , hexafluorobutyl acrylate, acrylamide, methacrylamide, N-isopropyl acrylamide, N-methylol acrylamide, N,N-dimethyl acrylamide, methylene bis acrylamide, vinyl acetate Ester, vinyl chloroacetate, vinyl propionate, acrylonitrile, acrylic acid, 4-vinyl pyridine, N-vinyl pyrrolidone, vinyl chloride or isoprene.
7. The method of claim 1, wherein the catalyst 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, ruthenium nanoparticles, ruthenium nanoparticles, iron nanoparticles, cobalt nanoparticles, ruthenium nanoparticles, tungsten nanoparticles Particles, titanium nanoparticles, vanadium nanoparticles, manganese nanoparticles, molybdenum nanoparticles or chromium nanoparticles.
8. The method of claim 7, wherein the transition metal nanoparticles have an average particle diameter of between 1 and 100 nm; and the transition metal nanoparticles are present. The form is a solid powder, a nanoparticle solution or a form of nanoparticles loaded onto the surface of a solid substrate.
9. The method of claim 1, wherein the initiator is one or a mixture of two or more of the following organosilicon compounds:

   Benzylsilane, n-butylsilane, n-hexylsilane, cyclohexylsilane, n-octadecylsilane, diphenylsilane, dipropylsilane, diisopropylsilane, di-n-butylsilane, diisobutylsilane , di-tert-butylsilane, di-n-hexylsilane, dicyclohexylsilane, methylphenylsilane, phenylchlorosilane, triphenylsilane, triethylsilane, tripropylsilane, triisopropylsilane, three n-Butylsilane, triisobutylsilane, tri-tert-butylsilane, tri-n-hexylsilane, tricyclohexylsilane, tri-n-octylsilane, n-butyldimethylsilane, isobutyldimethylsilane, uncle Butyldimethylsilane, tris(trimethylsilyl)silane, tris(triethylsilyl)silane, trichlorosilane, methyldichlorosilane, ethyldichlorosilane, phenyldichlorosilane, two Methylchlorosilane, diphenylchlorosilane, diisopropylchlorosilane, di-tert-butylchlorosilane, methylphenylchlorosilane, dimethylallylsilane, methyldiphenylsilane, dimethyl Phenylsilane, dimethyl-n-hexylsilane, dimethyl-n-butylsilane, n-octadecyldiethoxysilane, trimethoxy Silane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, tri-tert-butoxysilane, methyldimethoxysilane, methyldiethoxysilane, Phenyldimethoxysilane or phenyldiethoxysilane.
10. The method for catalyzing the polymerization of a vinyl monomer by the transition metal nanoparticles according to claim 1, wherein the solvent is one or a mixture of two or more miscible solvents in any ratio of the following solvents:

    Hexane, cyclohexane, petroleum ether, heptane, octane, benzene, toluene, p-xylene, decahydronaphthalene, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, tetrachloroethylene, diethyl ether , n-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetrahydrofuran, dioxane, diphenyl ether, acetone, acetylacetone, methyl ethyl ketone, cyclohexanone , ethyl acetate, propyl acetate, butyl acetate, methanol, ethanol, isopropanol, n-butanol, isobutanol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol , water, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone or γ-butyrolactone.

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