WO2020224169A1 - 光引发聚合制备乙烯基醚类聚合物的方法 - Google Patents
光引发聚合制备乙烯基醚类聚合物的方法 Download PDFInfo
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- WO2020224169A1 WO2020224169A1 PCT/CN2019/107807 CN2019107807W WO2020224169A1 WO 2020224169 A1 WO2020224169 A1 WO 2020224169A1 CN 2019107807 W CN2019107807 W CN 2019107807W WO 2020224169 A1 WO2020224169 A1 WO 2020224169A1
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- vinyl ether
- polymerization
- halogenated hydrocarbon
- photo
- alkyl group
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- 238000000034 method Methods 0.000 title claims abstract description 36
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229920000642 polymer Polymers 0.000 title claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 31
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 239000011572 manganese Substances 0.000 claims abstract description 26
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 230000009471 action Effects 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 125000002091 cationic group Chemical group 0.000 abstract description 9
- 238000005286 illumination Methods 0.000 abstract description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 238000010538 cationic polymerization reaction Methods 0.000 description 5
- 238000010828 elution Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 150000001723 carbon free-radicals Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000010550 living polymerization reaction Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- MVFPGBVZPPNHJX-KPKJPENVSA-N CCCCC(C)(CC1)C/C1=C/CC Chemical compound CCCCC(C)(CC1)C/C1=C/CC MVFPGBVZPPNHJX-KPKJPENVSA-N 0.000 description 1
- 0 CC[C@@](C)(CC1)*C2C1CCC(C)CC2 Chemical compound CC[C@@](C)(CC1)*C2C1CCC(C)CC2 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- -1 coatings Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000008266 hair spray Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010551 living anionic polymerization reaction Methods 0.000 description 1
- 238000010552 living cationic polymerization reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- C08F116/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F116/12—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F116/14—Monomers containing only one unsaturated aliphatic radical
- C08F116/16—Monomers containing no hetero atoms other than the ether oxygen
- C08F116/18—Acyclic compounds
- C08F116/20—Monomers containing three or more carbon atoms in the unsaturated aliphatic radical
-
- 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
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F116/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F116/12—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F116/14—Monomers containing only one unsaturated aliphatic radical
-
- 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
- C08F116/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F116/12—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F116/14—Monomers containing only one unsaturated aliphatic radical
- C08F116/16—Monomers containing no hetero atoms other than the ether oxygen
- C08F116/18—Acyclic compounds
-
- 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
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F16/14—Monomers containing only one unsaturated aliphatic radical
-
- 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
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/26—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of manganese, iron group metals or platinum group metals
-
- 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
- C08F2438/00—Living radical polymerisation
Definitions
- the invention relates to the technical field of polymer preparation, in particular to a method for preparing vinyl ether polymers by photo-initiated polymerization.
- Vinyl ether polymers are mainly used to make adhesives, coatings, oil viscosity modifiers, plasticizers, hair sprays, etc. due to their excellent flexibility, solubility and cohesiveness, and non-toxic and harmless. .
- the use of "living" polymerization methods to prepare polymers with controllable molecular weight and molecular weight distribution has always been a hot issue in polymerization methodology. Since the report of living anionic polymerization in 1956, both living cationic polymerization and living free radical polymerization have developed tremendously.
- vinyl ether monomers can only be realized by cationic polymerization due to the particularity of their structure, that is, the oxygen atom in the alkoxy group is directly connected to the double bond.
- the key to realizing living polymerization is to use halogenated hydrocarbons or cationic RAFT reagents to inhibit the increase of the concentration of cationic species, thereby reducing its side reactions to achieve the purpose of preparing controllable polymers.
- these systems are still very sensitive to the magazines in the system such as water.
- visible light has been widely used in various living polymerization systems as a green energy source.
- This stimulation method not only has the advantages of low energy consumption, low price and commercial availability, but more importantly, it can be controlled in time and space.
- the degree of polymerization can be controlled by the length of light, or the polymerization can be realized by switching the light source. The reaction proceeds and stops.
- the object of the present invention is to provide a method for preparing vinyl ether polymers by photo-initiated polymerization.
- the method uses manganese decacarbonyl and organic halogenated hydrocarbons to treat vinyl ether monomers under visible light. Carry out cationic polymerization to prepare vinyl ether polymers with controllable molecular weight and narrow molecular weight distribution.
- the invention provides a method for preparing vinyl ether polymers by photo-initiated polymerization, which comprises the following steps:
- the vinyl ether monomers represented by formula (1) are subjected to the action of organic halogenated hydrocarbons and manganese decacarbonyl (Mn 2 (CO) 10 ) under illumination conditions with a wavelength of 365-550 nm
- Light-initiated polymerization reaction occurs at -25°C to 25°C, and the vinyl ether polymer is obtained after the reaction is completed:
- R is an alkyl group or a halogenated alkyl group, and the number of carbon atoms in the alkyl group or a halogenated alkyl group is 1-10.
- the number of carbon atoms in the alkyl group or haloalkyl group is 2-5.
- the structural formula of the vinyl ether monomer is Wherein X is halogen.
- X in the vinyl ether monomer is chlorine, referred to as Cl-EVE for short.
- X in the organic halogenated hydrocarbon is bromine. That is, the structural formula of organic halogenated hydrocarbon is as follows:
- the molar ratio of vinyl ether monomers, organic halogenated hydrocarbons and manganese decacarbonyl is 100-500:1:0.01-0.5.
- the molar ratio of vinyl ether monomers, organic halogenated hydrocarbons and manganese decacarbonyl is 200-500:1:0.05-0.5.
- the molar ratio of vinyl ether monomers, organic halogenated hydrocarbons and manganese decacarbonyl is 200:1:0.05-0.5 or 200-500:1:0.2.
- the polymerization time is 5min-5h.
- the polymerization time is 10min-60min; more preferably, the polymerization time is 20min-40min.
- the reaction temperature is 0-25°C, more preferably, the reaction temperature is 0-10°C.
- reaction process may not use an organic solvent, or it may be carried out in an organic solvent.
- the organic solvent is one or more of toluene, n-hexane, ethyl acetate and dichloromethane.
- reaction after the reaction is completed, it also includes the steps of dissolving the obtained polymer in tetrahydrofuran, then precipitating in methanol, filtering and drying.
- the protective atmosphere is preferably a nitrogen atmosphere.
- Manganese decacarbonyl and halogenated hydrocarbons can simultaneously generate carbon free radicals and manganese pentacarbonyl bromide under light, while manganese pentacarbonyl bromide can be used as an oxidant to directly oxidize free radicals to carbocations.
- the halogenated hydrocarbons in the system can be catalyzed The process is converted to carbocations to initiate polymerization.
- the present invention has at least the following advantages:
- the present invention provides a light-initiated controllable cationic polymerization method with simple components. Under a specific wavelength of light, a catalyst generated in situ is used to prepare vinyl ether polymers with controllable molecular weight and molecular weight distribution. An effective method.
- the reagents used in this method are all commercially available, do not require additional purification, react under visible light conditions, and have many advantages such as environmental friendliness and simple operation.
- vinyl ether polymers such as polyisobutyl vinyl ether with controllable molecular weight and narrow molecular weight distribution can be prepared.
- Figure 1 is the kinetic curve (A), the monomer conversion curve with time (B) and the molar ratio of [IBVE]:[EBP]:[Mn 2 (CO) 10 ] at 200:1:0.2.
- Figure 2 shows the carbon nuclear magnetic (2A-2B), hydrogen nuclear magnetic (2C-2D) and macromolecular mass spectrum (2E-2F) of the obtained polymer when IBVE is selected as the monomer;
- Figure 3 shows the GPC elution curve of each polymer obtained by selecting different halogenated hydrocarbons
- Figure 4 is the GPC elution curve of each polymer obtained in different solvents
- Figure 5 shows the GPC elution curve of each polymer obtained by selecting different monomers.
- Table 1 shows the polymerization results of different halogenated hydrocarbons under the above conditions for different times.
- the calculation formula of M n,th is as follows: [M] 0 /[halogenated hydrocarbon] 0 ⁇ conversion rate ⁇ M+M EBP ).
- reaction temperature is 0°C; the reaction temperature in Example 12 is 25°C, and the reaction temperature in Example 13 is -25°C.
- Figure 1 is the kinetic curve (A), the monomer conversion curve with time (B) and the molar ratio of [IBVE]:[EBP]:[Mn 2 (CO) 10 ] at 200:1:0.2.
- the GPC elution curve (C) of the obtained polymer In Figure C, from right to left, the reaction time corresponding to the curve increases sequentially.
- Figure 2 shows the carbon nuclear magnetic (2A-2B), hydrogen nuclear magnetic (2C-2D) and macromolecular mass spectra (2E-2F) of the obtained polymer when the monomer is selected as IBVE.
- Figure 2B is a partial enlarged view of 2A
- Figure 2D is a partial enlarged view of 2C
- Figure 2F is an enlarged view of box a in 2E.
Abstract
Description
Claims (10)
- 根据权利要求1所述的方法,其特征在于:所述烷基或卤代烷基中的碳原子数为2-5个。
- 根据权利要求1所述的方法,其特征在于:所述乙烯基醚类单体、有机卤代烃与十羰基锰的摩尔比为100-500:1:0.01-0.5。
- 根据权利要求5所述的方法,其特征在于:所述乙烯基醚类单体、有机卤代烃与十羰基锰的摩尔比为200-500:1:0.05-0.5。
- 根据权利要求6所述的方法,其特征在于:所述乙烯基醚类单体、有机卤代烃与十羰基锰的摩尔比为200:1:0.05-0.5或200-500:1:0.2。
- 根据权利要求1所述的方法,其特征在于:聚合时间为5min–5h。
- 根据权利要求1所述的方法,其特征在于:反应在有机溶剂中进行。
- 根据权利要求9所述的方法,其特征在于:所述有机溶剂为甲苯、正己烷、乙酸乙酯和二氯甲烷中的一种或几种。
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AU2019427990A AU2019427990B2 (en) | 2019-05-05 | 2019-09-25 | Method for preparing vinyl ether polymer by photo-initiated polymerization |
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US20210371556A1 (en) | 2021-12-02 |
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