CN112778444A - Method for preparing polyolefin by photoinduced organic catalysis - Google Patents
Method for preparing polyolefin by photoinduced organic catalysis Download PDFInfo
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- CN112778444A CN112778444A CN202110095950.7A CN202110095950A CN112778444A CN 112778444 A CN112778444 A CN 112778444A CN 202110095950 A CN202110095950 A CN 202110095950A CN 112778444 A CN112778444 A CN 112778444A
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 58
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 150000001336 alkenes Chemical class 0.000 claims abstract description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 alkyl halogen Chemical class 0.000 claims abstract description 14
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- 239000011941 photocatalyst Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 73
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 17
- 238000005286 illumination Methods 0.000 claims description 17
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 16
- BKTKLDMYHTUESO-UHFFFAOYSA-N ethyl 2-bromo-2-phenylacetate Chemical compound CCOC(=O)C(Br)C1=CC=CC=C1 BKTKLDMYHTUESO-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- PQUSVJVVRXWKDG-UHFFFAOYSA-N methyl 2-bromo-2-methylpropanoate Chemical compound COC(=O)C(C)(C)Br PQUSVJVVRXWKDG-UHFFFAOYSA-N 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- VBHXIMACZBQHPX-UHFFFAOYSA-N 2,2,2-trifluoroethyl prop-2-enoate Chemical compound FC(F)(F)COC(=O)C=C VBHXIMACZBQHPX-UHFFFAOYSA-N 0.000 claims description 2
- PYNYHMRMZOGVML-UHFFFAOYSA-N 2-bromopropanenitrile Chemical compound CC(Br)C#N PYNYHMRMZOGVML-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- XXRLJXZVZZXDPP-UHFFFAOYSA-N ethyl 2-chloro-2-phenylacetate Chemical compound CCOC(=O)C(Cl)C1=CC=CC=C1 XXRLJXZVZZXDPP-UHFFFAOYSA-N 0.000 claims description 2
- ACEONLNNWKIPTM-UHFFFAOYSA-N methyl 2-bromopropanoate Chemical compound COC(=O)C(C)Br ACEONLNNWKIPTM-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012947 alkyl halide initiator Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 24
- 239000003054 catalyst Substances 0.000 abstract description 12
- 238000006116 polymerization reaction Methods 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 230000036632 reaction speed Effects 0.000 abstract description 4
- 239000012620 biological material Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000000977 initiatory effect Effects 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000005281 excited state Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 84
- 238000005227 gel permeation chromatography Methods 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 230000001376 precipitating effect Effects 0.000 description 12
- 238000005070 sampling Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- RCBSZGSHSLQLBI-UHFFFAOYSA-N 5,10-diphenylphenazine Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N(C=2C=CC=CC=2)C2=CC=CC=C21 RCBSZGSHSLQLBI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- WAKFRZBXTKUFIW-UHFFFAOYSA-M 2-bromo-2-phenylacetate Chemical compound [O-]C(=O)C(Br)C1=CC=CC=C1 WAKFRZBXTKUFIW-UHFFFAOYSA-M 0.000 description 1
- QKSGIGXOKHZCQZ-UHFFFAOYSA-M 2-chloro-2-phenylacetate Chemical compound [O-]C(=O)C(Cl)C1=CC=CC=C1 QKSGIGXOKHZCQZ-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a method for preparing polyolefin by photoinduced organic catalysis, which comprises the step of reacting an olefin monomer, an alkyl halogen initiator and a 5, 10-diaryl-5, 10-dihydrophenazine organic photocatalyst under the irradiation of light. The visible light catalyst is utilized to efficiently catalyze the alkyl halogen initiator to initiate the polymerization of the olefin monomer by utilizing the characteristics of low photon absorption energy, good solubility, stable catalyst structure, wide absorption wavelength, strong excited state reduction potential, high catalytic polymerization reaction speed and the like, so that the problem of metal residue in the polymer is effectively avoided, the efficient preparation of the polyolefin polymer without metal residue is realized, the polymerization reaction speed is high, the polymer molecular weight is controllable, the molecular weight distribution is narrow, the obtained polymer has great advantages as an electrical material or a biological material, and the defects of high energy using light source, unstable catalyst structure, low catalytic activity of the catalyst, low polymerization initiation efficiency, metal residue and the like in the prior art are overcome.
Description
Technical Field
The invention belongs to the field of photochemistry and high polymer material synthesis, and particularly relates to a method for preparing polyolefin by photoinduced organic catalysis.
Background
The polyolefin has small relative density, good chemical resistance and water resistance; the composite material has the characteristics of good mechanical strength, electrical insulation and the like, can be used for films, pipes, plates, various molded products, wires and cables and the like, and also has wide application in the aspects of agriculture, packaging, electronics, electricity, automobiles, machinery, daily sundries and the like. The polymerization method is studied more, and living radical polymerization is an important method for producing polyolefin, and atom transfer radical polymerization is one of the most widely studied living radical polymerization. Atom transfer radical polymerization is generally carried out using a redox process regulated by metal catalysts [ Cu (I), Ru (II), Fe (II) ]. However, the use of metal catalysts inevitably results in metal residues in the product, thereby limiting the applications of the polyolefin polymer prepared in electrical materials, biomaterials, etc. Therefore, the present invention provides a method for preparing polyolefin by photoinduced organic catalysis, so as to effectively solve the technical problems.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of providing a method for preparing polyolefin by photoinduced organic catalysis aiming at the defects of the prior art.
In order to solve the technical problems, the invention discloses a method for preparing polyolefin by photoinduced organic catalysis, which comprises the step of reacting an olefin monomer, an alkyl halogen initiator and a 5, 10-diaryl-5, 10-dihydrophenazine organic photocatalyst under the irradiation of light, wherein the reaction formula is shown in figure 1.
The reaction can be carried out in a reaction device together with a mixed solution composed of an olefin monomer, an alkyl halogen initiator, a 5, 10-diaryl-5, 10-dihydrophenazine organic photocatalyst and a solvent under the illumination, or can be carried out in a manner that the olefin monomer, the alkyl halogen initiator, the 5, 10-diaryl-5, 10-dihydrophenazine organic photocatalyst and the solvent are respectively singly or randomly combined and are respectively and simultaneously pumped into the reaction device to react under the illumination.
Preferably, the reaction is carried out by reacting the olefin monomer, the alkyl halogen initiator, the 5, 10-diaryl-5, 10-dihydrophenazine organic photocatalyst and a mixed solution of the solvent together in a reaction device under the irradiation of light.
Further preferably, the 5, 10-diaryl-5, 10-dihydrophenazine organic photocatalyst is firstly dissolved in a solvent, then the olefin monomer and the alkyl halogen initiator are respectively added, and then the reaction is carried out in a reaction device under the irradiation of light.
The olefin monomer is an ethylene monomer, preferably any one or a combination of methyl methacrylate, methyl acrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, trifluoroethyl acrylate, styrene and acrylonitrile, and more preferably methyl methacrylate.
Wherein the alkyl halogen initiator is any one or combination of 2-bromo-2-phenylacetate, 2-chloro-2-phenylacetate, 2-bromoisobutyric acid methyl ester, 2-bromopropionic acid methyl ester and 2-bromopropionitrile, preferably 2-bromo-2-phenylacetate ethyl ester.
Wherein, the 5, 10-diaryl-5, 10-dihydrophenazine organic photocatalyst is any one or combination of more of formulas PC-1 to PC-16; preferably any one or two combination of formulas PC-1 and PC-4;
wherein the solvent for the reaction is any one or combination of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, 1, 4-dioxane, toluene and tetrahydrofuran.
Wherein the molar ratio of the olefin monomer to the alkyl halogen initiator is 5-2000: 1, preferably 20 to 1500: 1, more preferably 50 to 1000: 1, more preferably 70 to 500: 1, more preferably 100 to 200: 1.
wherein the mol ratio of the olefin monomer to the 5, 10-diaryl-5, 10-dihydrophenazine organic photocatalyst is 1: 0.0002 to 0.01, preferably 1: 0.0008 to 0.002, and more preferably 1: 0.001.
wherein the concentration of the olefin monomer is 7-12 mmol/mL, preferably 9.35 mmol/mL.
Wherein the light source for illumination is a light source with the wavelength of 280-550 nm or sunlight.
Wherein the temperature of the reaction is room temperature.
Wherein the reaction device is a microchannel reaction device or other conventional reactors such as glass bottles.
Preferably, the reaction device is a microchannel reaction device, i.e. a microchannel reactor is used for reaction.
Further preferably, a mixed solution consisting of an olefin monomer, an alkyl halogen initiator, a 5, 10-diaryl-5, 10-dihydrophenazine organic photocatalyst and a solvent is pumped into the microchannel reaction device together, and the reaction is carried out under the irradiation of light.
As shown in fig. 2, the microchannel reactor includes an injector, a microchannel reactor, a receiver, and a light source.
The sample injector, the microchannel reactor and the receiver are sequentially connected in series through pipelines; the light source is positioned outside the microchannel reactor, and the illumination range of the light source covers the microchannel reactor.
Preferably, the microchannel reactor is made of quartz glass.
Wherein, the retention volume of the microchannel reactor is 1-20 mL, and the tube diameter is 0.2-2 mm.
Wherein the flow rate of the mixed solution pumped into the microchannel reaction device is 0.02-2 mL/min.
Wherein, when the reaction device is a microchannel reaction device, the reaction time is 30 min-4 h.
When the reaction device is other conventional reactors, the reaction time is 6-20 h.
Has the advantages that: compared with the prior art, the invention has the following advantages:
the invention adopts visible light catalyst (5, 10-diaryl-5, 10-dihydrophenazine organic photocatalyst), utilizes the characteristics of the catalyst such as low photon absorption energy, good solubility, stable catalyst structure, wide absorption wavelength, strong excited reduction potential, fast catalytic polymerization reaction speed and the like to efficiently catalyze alkyl halogen initiator to initiate olefin monomer for polymerization, not only effectively avoids the problem of metal residue in the polymer, realizes the efficient preparation of the polyolefin polymer without metal residue, the polymerization reaction speed is high, the molecular weight of the polymer is controllable, the molecular weight distribution is narrow, the obtained polymer has great advantages as an electrical material or a biological material, and the defects of high energy of a used light source, unstable catalyst structure, low catalytic activity of the catalyst, low polymerization initiation efficiency, metal residue and the like in the prior art are overcome.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 shows the reaction formula of initiating agent to initiate the polymerization of ethylene monomer.
FIG. 2 is a schematic structural diagram of a microchannel reactor according to the present invention.
Detailed Description
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
In the following examples, the abbreviation Mn stands for polymer number average molecular weight, PDI for polymer molecular weight distribution, GPC for gel permeation chromatography, and HNMR for nuclear magnetic hydrogen spectroscopy.
Example 1:
PC-1 (9.35. mu. mol) was dissolved in the solvent N, N-dimethylacetamide (1mL) at room temperature, and then the monomer methyl methacrylate (1mL, 9.35mmol) and the initiator ethyl 2-bromo-2-phenylacetate (93.5. mu. mol) were added to the solution separately and stirred well, sucked into a syringe and pumped into a microreactor with a quartz glass tube hold-up volume of 1.61mL at a flow rate of 0.054 mL/min. And then placing the reaction under the condition of illumination (420-430 nm), fully reacting, collecting effluent liquid, sampling and measuring the monomer conversion rate of HNMR, precipitating a polymer by using methanol, washing by using excessive methanol, and repeating for three times. Then, the product was measured for Mn and PDI by GPC, and the monomer conversion of the obtained product was 98.14%, PDI was 1.13, and Mn was 11.92 kDa.
Example 2:
PC-1 (9.35. mu. mol) was dissolved in the solvent N, N-dimethylacetamide (1mL) at room temperature, and then the monomer methyl methacrylate (1mL, 9.35mmol) and the initiator ethyl 2-chloro-2-phenylacetate (93.5. mu. mol) were added to the solution separately and stirred well, sucked into a syringe and pumped into a microreactor with a quartz glass tube holding volume of 1.61mL at a flow rate of 0.054 mL/min. And then placing the reaction under the condition of illumination (420-430 nm), fully reacting, collecting effluent liquid, sampling and measuring the monomer conversion rate of HNMR, precipitating a polymer by using methanol, washing by using excessive methanol, and repeating for three times. Then, the product was measured for Mn and PDI by GPC, and the monomer conversion of the obtained product was 97.68%, PDI was 1.26, and Mn was 10.05 kDa.
Example 3:
PC-1 (9.35. mu. mol) was dissolved in solvent N, N-dimethylacetamide (1mL) at room temperature, and then monomeric methyl methacrylate (1mL, 9.35mmol) and initiator methyl 2-bromoisobutyrate (93.5. mu. mol) were added to the solution separately and stirred well, drawn into a syringe and pumped into a microreactor with a quartz glass tube hold-up volume of 1.61mL at a flow rate of 0.054 mL/min. And then placing the reaction under the condition of illumination (420-430 nm), fully reacting, collecting effluent liquid, sampling and measuring the monomer conversion rate of HNMR, precipitating a polymer by using methanol, washing by using excessive methanol, and repeating for three times. Then, the product was measured for Mn and PDI by GPC, and the monomer conversion of the obtained product was 97.50%, PDI was 1.25, and Mn was 10.61 kDa.
Example 4:
PC-2 (9.35. mu. mol) was dissolved in the solvent N, N-dimethylacetamide (1mL) at room temperature, and then the monomer methyl methacrylate (1mL, 9.35mmol) and the initiator ethyl 2-bromo-2-phenylacetate (93.5. mu. mol) were added to the solution separately and stirred well, sucked into a syringe and pumped into a microreactor with a quartz glass tube hold-up volume of 1.61mL at a flow rate of 0.054 mL/min. And then placing the reaction under the condition of illumination (420-430 nm), fully reacting, collecting effluent liquid, sampling and measuring the monomer conversion rate of HNMR, precipitating a polymer by using methanol, washing by using excessive methanol, and repeating for three times. Then, the product was measured for Mn and PDI by GPC, and the monomer conversion of the obtained product was 97.56%, PDI was 1.15, and Mn was 13.32 kDa.
Example 5:
PC-3 (9.35. mu. mol) was dissolved in N, N-dimethylacetamide (1mL) at room temperature, and then the monomers methyl methacrylate (1mL, 9.35mmol) and ethyl 2-bromo-2-phenylacetate (93.5. mu. mol) as initiator were added to the solution separately and stirred well, sucked into a syringe and pumped into a microreactor with a quartz glass tube holding volume of 1.61mL at a flow rate of 0.054 mL/min. And then placing the reaction under the condition of illumination (420-430 nm), fully reacting, collecting effluent liquid, taking out the reaction, sampling, measuring the conversion rate of monomers by using HNMR, precipitating a polymer by using methanol, washing by using excessive methanol, and repeating for three times. Then, the product was measured for Mn and PDI by GPC, and the monomer conversion of the obtained product was 97.40%, PDI was 1.23, and Mn was 13.48 kDa.
Example 6:
PC-4 (9.35. mu. mol) was dissolved in N, N-dimethylacetamide (1mL) at room temperature, and then the monomer methyl methacrylate (1mL, 9.35mmol) and the initiator ethyl 2-bromo-2-phenylacetate (93.5. mu. mol) were added to the solution separately and stirred well, sucked into a syringe and pumped into a microreactor with a quartz glass tube holding volume of 1.61mL at a flow rate of 0.027 mL/min. And then placing the reaction under the condition of illumination (420-430 nm), fully reacting, collecting effluent liquid, sampling and measuring the monomer conversion rate of HNMR, precipitating a polymer by using methanol, washing by using excessive methanol, and repeating for three times. Then, the product was measured for Mn and PDI by GPC, and the monomer conversion of the obtained product was 98.39%, PDI was 1.17, and Mn was 12.642 kDa.
Example 7:
PC-1 (9.35. mu. mol) was dissolved in N, N-dimethylacetamide (1mL) at room temperature, and then the monomer methyl methacrylate (1mL, 9.35mmol) and the initiator ethyl 2-bromo-2-phenylacetate (187. mu. mol) were added to the solution separately and stirred well, sucked into a syringe and pumped into a microreactor with a quartz glass tube hold up volume of 1.61mL at a flow rate of 0.027 mL/min. And then placing the reaction under the condition of illumination (420-430 nm), fully reacting, collecting effluent liquid, sampling and measuring the monomer conversion rate of HNMR, precipitating a polymer by using methanol, washing by using excessive methanol, and repeating for three times. Then, the product was measured for Mn and PDI by GPC, and the monomer conversion of the obtained product was 97.14%, PDI was 1.10, and Mn was 5.92 kDa.
Example 8: PC-1 (9.35. mu. mol) was dissolved in N, N-dimethylacetamide (1mL) at room temperature, and then the monomer methyl methacrylate (1mL, 9.35mmol) and the initiator ethyl 2-bromo-2-phenylacetate (46.8. mu. mol) were added to the solution separately and stirred well, sucked into a syringe and pumped into a microreactor with a quartz glass tube holding volume of 1.61mL at a flow rate of 0.027 mL/min. And then placing the reaction under the condition of illumination (420-430 nm), fully reacting, collecting effluent liquid, sampling and measuring the monomer conversion rate of HNMR, precipitating a polymer by using methanol, washing by using excessive methanol, and repeating for three times. Then, the product was measured for Mn and PDI by GPC, and the monomer conversion of the obtained product was 96.64%, PDI was 1.21, and Mn was 19.27 kDa.
Example 9:
PC-1 (9.35. mu. mol) was dissolved in N, N-dimethylacetamide (1mL) at room temperature, and then the monomer methyl methacrylate (1mL, 9.35mmol) and the initiator ethyl 2-bromo-2-phenylacetate (93.5. mu. mol) were added to the solution separately and stirred well, sucked into a syringe and pumped into a microreactor with a quartz glass tube holding volume of 1.61mL at a flow rate of 0.027 mL/min. And then placing the reaction under the condition of illumination (420-430 nm), fully reacting, collecting effluent liquid, sampling and measuring the monomer conversion rate of HNMR, precipitating a polymer by using methanol, washing by using excessive methanol, and repeating for three times. Then, the product was measured for Mn and PDI by GPC, and the monomer conversion of the obtained product was 97.13%, PDI was 1.09, and Mn was 10.53 kDa.
Example 10:
PC-1 (9.35. mu. mol) was dissolved in N, N-dimethylacetamide (1mL) at room temperature, and then the monomer methyl methacrylate (1mL, 9.35mmol) and the initiator ethyl 2-bromo-2-phenylacetate (93.5. mu. mol) were added to the solution separately and stirred well, sucked into a syringe and pumped into a microreactor with a quartz glass tube holding volume of 1.61mL at a flow rate of 0.027 mL/min. Then the reaction is put under the sunlight for full reaction, effluent liquid is collected, the sample is taken for HNMR to obtain the monomer conversion rate, the polymer is precipitated by methanol, and the reaction is washed by excessive methanol and repeated for three times. Then, the product was measured for Mn and PDI by GPC, and the monomer conversion of the obtained product was 99.09%, PDI was 1.23, and Mn was 14.21 kDa.
Comparative example 1:
a20 mL clear glass sample vial was charged sequentially with Teflon magnetic stirrer, 5, 10-dihydro-5, 10-diphenylphenazine (9.35. mu. mol), stoppered and sealed at room temperature, and then the vial was degassed three times using a double calandria. N, N-dimethylacetamide (1mL), methyl methacrylate (1mL, 9.35mmol) and ethyl 2-bromo-2-phenylacetate (93.5. mu. mol) were injected in this order. And then placing the reaction under the condition of illumination (420-430 nm), reacting for 12h, taking out the reaction, sampling, measuring the monomer conversion rate by using HNMR, precipitating a polymer by using methanol, washing by using excessive methanol, and repeating for three times. Then, the product was measured for Mn and PDI by GPC, and the monomer conversion of the obtained product was 80.14%, PDI was 1.31, and Mn was 10.92 kDa. (the organic photocatalyst 5, 10-dihydro-5, 10-diphenylphenazine is unstable and is consumed in the system).
Comparative example 2:
at room temperature, a polytetrafluoroethylene magnetic stirrer was sequentially added to a 20mL clear glass sample bottle, and Cu powder (9.35. mu. mol), Me were added6TREN ligand (9.35. mu. mol) was stoppered and sealed, and then the bottle was deaerated three times using a double-calandria pump. N, N-dimethylacetamide (1mL) and methyl methacrylate (1mL, 9.35mmol) were sequentially injected,ethyl 2-bromo-2-phenylacetate (93.5 μmol), reacted at 60 ℃ for 10h, the reaction was taken out, sample taken for HNMR to determine monomer conversion, the product was precipitated with methanol, washed with excess methanol and repeated three times. The product was then used to determine Mn and PDI. The monomer conversion of the product was 91.2%, PDI 1.12 and Mn 9.27 kDa. (since Cu is used as a catalyst, there is metal residue in the resulting polymerization).
Example 11:
a Teflon magnetic stirrer was sequentially added to a 20mL transparent glass sample bottle at room temperature, and PC-1 (9.35. mu. mol), a rubber stopper was stoppered and sealed under nitrogen, followed by removing the air from the bottle three times using a double-row tube. N, N-dimethylacetamide (1mL), methyl methacrylate (1mL, 9.35mmol) and ethyl 2-bromo-2-phenylacetate (93.5. mu. mol) were injected in this order. And then placing the reaction under the condition of illumination (420-430 nm), reacting for 12h, taking out the reaction, sampling, measuring the monomer conversion rate by using HNMR, precipitating a polymer by using methanol, washing by using excessive methanol, and repeating for three times. Then, the product was measured for Mn and PDI by GPC, and the monomer conversion of the obtained product was 90.14%, PDI was 1.13, and Mn was 11.92 kDa.
Example 12
PC-1 (9.35. mu. mol) was dissolved in solvent N, N-dimethylacetamide (1mL) at room temperature, and then monomeric ethyl methacrylate (1.5mL, 9.35mmol) and initiator methyl 2-bromoisobutyrate (93.5. mu. mol) were added to the solution separately and stirred well, drawn into a syringe and pumped into a microreactor with a quartz glass tube hold up volume of 1.61mL at a flow rate of 0.054 mL/min. And then placing the reaction under the condition of illumination (420-430 nm), fully reacting, collecting effluent liquid, sampling and measuring the monomer conversion rate of HNMR, precipitating a polymer by using methanol, washing by using excessive methanol, and repeating for three times. Then, the product was measured for Mn and PDI by GPC, and the monomer conversion of the obtained product was 97.81%, PDI was 1.23, and Mn was 10.78 kDa.
TABLE 1
Note: in the table, example 12 differs from example 3 in that the monomers are different, example 3 being methyl methacrylate; example 12 is ethyl methacrylate.
The present invention provides a method and a concept for preparing polyolefin by photo-induced organic catalysis, and a method and a way for implementing the technical scheme are numerous, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of modifications and embellishments can be made without departing from the principle of the present invention, and these modifications and embellishments should also be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (10)
1. A method for preparing polyolefin by photoinduced organic catalysis is characterized in that an olefin monomer, an alkyl halogen initiator and a 5, 10-diaryl-5, 10-dihydrophenazine organic photocatalyst react under the irradiation of light.
2. The method according to claim 1, wherein the olefin monomer is any one or a combination of methyl methacrylate, methyl acrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, trifluoroethyl acrylate, styrene and acrylonitrile.
3. The method according to claim 1, wherein the alkyl halogen initiator is any one or a combination of 2-bromo-2-phenylacetic acid ethyl ester, 2-chloro-2-phenylacetic acid ethyl ester, 2-bromoisobutyric acid methyl ester, 2-bromopropionic acid methyl ester and 2-bromopropionitrile.
4. The method according to claim 1, wherein the solvent for the reaction is any one or a combination of several of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, 1, 4-dioxane, toluene and tetrahydrofuran.
5. The process of claim 1, wherein the molar ratio of olefin monomer to alkyl halide initiator is from 5 to 2000: 1.
6. the method of claim 1, wherein the molar ratio of the olefin monomer to the 5, 10-diaryl-5, 10-dihydrophenazine-based organic photocatalyst is from 1: 0.0002 to 0.01.
7. The method of claim 1, wherein the olefin monomer concentration is 7 to 12 mmol/mL.
8. The method according to claim 1, wherein the light source for the illumination is a light source with a wavelength of 280-550 nm or sunlight.
9. The method of claim 1, wherein the temperature of the reaction is room temperature.
10. The process of claim 1 wherein the reaction is carried out using a microchannel reaction device.
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| CN115894773A (en) * | 2022-12-07 | 2023-04-04 | 郑州德派医疗器械有限公司 | Light-cured 3D printing resin for dentistry and preparation method thereof |
| CN115894773B (en) * | 2022-12-07 | 2024-05-14 | 郑州德派医疗器械有限公司 | Photo-curing 3D printing resin for dentistry and preparation method thereof |
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