CN115612002A - Preparation method of vinyl polymer - Google Patents
Preparation method of vinyl polymer Download PDFInfo
- Publication number
- CN115612002A CN115612002A CN202110797190.4A CN202110797190A CN115612002A CN 115612002 A CN115612002 A CN 115612002A CN 202110797190 A CN202110797190 A CN 202110797190A CN 115612002 A CN115612002 A CN 115612002A
- Authority
- CN
- China
- Prior art keywords
- initiator
- vinyl
- vinyl polymer
- alkyl
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000000178 monomer Substances 0.000 claims abstract description 42
- 239000003999 initiator Substances 0.000 claims abstract description 32
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 26
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 26
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 22
- 239000011777 magnesium Substances 0.000 claims abstract description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005977 Ethylene Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 58
- -1 grignard reagent lithium chloride Chemical class 0.000 claims description 31
- 238000010791 quenching Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 230000000171 quenching effect Effects 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 238000009826 distribution Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000012716 precipitator Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 150000004795 grignard reagents Chemical group 0.000 abstract description 11
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 40
- 239000004793 Polystyrene Substances 0.000 description 29
- 229920002223 polystyrene Polymers 0.000 description 29
- 239000003153 chemical reaction reagent Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 22
- 238000006116 polymerization reaction Methods 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- 239000012043 crude product Substances 0.000 description 14
- 229920001971 elastomer Polymers 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 11
- 230000001376 precipitating effect Effects 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000000746 purification Methods 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 description 6
- 238000007184 Barbier reaction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000005580 one pot reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- 229920000738 poly(p-divinylbenzene) polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 150000005826 halohydrocarbons Chemical class 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- DBTNVRCCIDISMV-UHFFFAOYSA-L lithium;magnesium;propane;dichloride Chemical compound [Li+].[Mg+2].[Cl-].[Cl-].C[CH-]C DBTNVRCCIDISMV-UHFFFAOYSA-L 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- 229920000779 poly(divinylbenzene) Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- YYTSGNJTASLUOY-UHFFFAOYSA-N 1-chloropropan-2-ol Chemical compound CC(O)CCl YYTSGNJTASLUOY-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- HSOOVEKLGOIEFF-UHFFFAOYSA-N ethenyl nitrate Chemical compound [O-][N+](=O)OC=C HSOOVEKLGOIEFF-UHFFFAOYSA-N 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000002284 excitation--emission spectrum Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 229920001109 fluorescent polymer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- 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
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
-
- 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
- C08F112/00—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 aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- 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
- C08F112/00—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 aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F112/16—Halogens
- C08F112/18—Chlorine
-
- 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
- C08F112/00—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 aromatic carbocyclic ring
- C08F112/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F112/36—Divinylbenzene
-
- 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
- C08F8/00—Chemical modification by after-treatment
Abstract
Disclosed herein is a method for preparing an ethylene-based polymer, the method comprising: reacting a material containing a vinyl monomer and an initiator in the presence of an inert gas to obtain the vinyl polymer; the initiator includes two types, one is a co-initiator containing a halogenated hydrocarbon and magnesium, and the other is a Grignard reagent lithium chloride complex. The preparation method is simple and easy to operate, and the reaction conditions are mild. The initiator is cheap and easy to obtain, and the reaction efficiency is high. And various functional groups on the polymer enable the polymer to have greater application potential in the field of vinyl polymer materials.
Description
Technical Field
The application relates to a preparation method of a vinyl polymer, belonging to the field of chemistry.
Background
The Barbier reaction is an organic reaction in which halohydrocarbon and electrophilic reagents are added in a one-pot mode under the action of metal, and is an important mark for the development of metal organic chemistry. In 1900, inspired by the Barbier reaction, the french chemist Grignard (Francois dust vector Grignard) found that the reaction of magnesium metal with organic halide can obtain an organic magnesium halide reagent, and the reagent can perform nucleophilic addition on some functional groups to synthesize a target product stably and efficiently, so the method can be regarded as a step method of the Barbier reaction. Over the past one hundred years, such organic magnesium halide reagents have gained tremendous value in the construction of carbon-carbon and carbon-halogen bonds, and are referred to as Grignard reagents (Grignard reagents). Although grignard reagents are organometallic reagents that are very commonly used in organic synthesis, there are still some limitations on the preparation process and the synthesis for a particular compound. The development of the Barbier reaction and further optimization of the grignard reagent is therefore still of great importance. In 2004, professor Knochel reported Grignard reagent lithium chloride complex reagents (Grignard reagents and lithium chloride exist in the form of complex, for example, grignard reagent lithium chloride complex reagents represented by i-PrMgCl. LiCl). The Grignard reagent lithium chloride complex reagent not only utilizes halogen-magnesium exchange to successfully prepare various novel functionalized Grignard reagents, but also solves the problem of compatibility of various functional groups, and is widely applied to synthesis and production of organic small molecules at present. The complex reagent is simple to prepare and has been commercialized as a grignard reagent lithium chloride complex.
In the polymer field, grignard reagents are frequently used as anionic polymerization initiators. However, since the reactivity is relatively low, it can only be used for polymerization of highly reactive olefin monomers containing electron-withdrawing groups, such as methyl methacrylate, acrylonitrile, methyl vinyl ketone, and vinyl nitrate, but it is difficult to initiate polymerization of styrene monomers having low reactivity. The grignard reagent lithium chloride complex reagent is a grignard reagent containing LiCl, and the activity of the grignard reagent lithium chloride complex reagent is greatly improved due to the presence of LiCl, so that it is very important to search for the application of the grignard reagent lithium chloride complex reagent in olefin polymerization. In addition, the Barbier reaction utilizes the same raw materials, changes the reaction mode and changes the step method into the one-pot method so as to realize the polymerization of olefin, which has great driving force on the development of the polymerization mode of high molecules and organic metal compounds.
Disclosure of Invention
The application provides a preparation method of a vinyl polymer, which can be used for preparing the vinyl polymer very efficiently under mild conditions by initiating the polymerization of a vinyl monomer by using a halogenated hydrocarbon and a magnesium or Grignard reagent lithium chloride complex reagent. The prepared vinyl polymer has large molecular weight and narrow molecular weight distribution range. Meanwhile, the functional polymer at the tail end can be prepared by a one-pot method by adding the additive. The method is simple and convenient to operate and efficient in reaction. The method has a relatively large application potential in industrial application, and can be further applied to the synthesis of block polymers.
According to an aspect of the present application, there is provided a method of preparing an ethylene-based polymer, the method comprising: reacting I a material containing a vinyl monomer and an initiator in the presence of an inert gas to obtain the vinyl polymer; the initiator includes a co-initiator of a halohydrocarbon and magnesium or a grignard reagent lithium chloride complex initiator.
Alternatively, the process of reaction I is represented by formula I:
wherein the value range of n is 8-50000.
Alternatively, the vinyl polymer has a molecular weight of 1000 to 5000000; the molecular weight distribution range is 1-30.
Alternatively, the vinyl polymer has a molecular weight of 1000, 5000, 10000, 15000, 20000, 30000, 40000, 45000, 50000, 60000, 70000, 80000, 90000, 100000, 150000, 200000, 250000, 300000, 350000, 400000, 450000, 500000, 1000000, 1500000, 2000000, 2500000, 3000000, 3500000, 4000000, 4500000, or 5000000.
Optionally, the molecular weight distribution is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30.
Optionally, the vinyl monomer is selected from one or more compounds having a formula as shown in formula II:
wherein Y is selected from one of Br, cl and F;
R 1 is selected from C 6 ～C 30 Aryl of, C 1 ～C 30 One of alkyl, carbonyl, nitrile, nitro, methoxy and vinyl;
R 2 is selected from C 6 ～C 30 Aryl of (C) 1 ～C 30 Alkyl and carbonyl.
Optionally, the vinyl polymer is selected from at least one of compounds having a formula as shown in formula II-1:
wherein Y is selected from one of Br, cl and F;
R 1 is selected from C 6 ～C 30 Aryl of (C) 1 ～C 30 One of alkyl, carbonyl, nitrile, nitro, methoxy and vinyl;
R 2 is selected from C 6 ～C 30 Aryl of (C) 1 ～C 30 One of an alkyl group and a carbonyl group;
the value range of n is 8-50000.
Optionally, the vinyl polymer is selected from the group consisting of class D structural polymers in formula II-1 as shown.
Optionally, the grignard reagent lithium chloride complex is selected from at least one of the compounds having the structural formula shown in formula III:
wherein X is selected from one of Cl and Br;
R 3 is selected from C 1 ～C 30 Alkyl radical, C 6 ～C 30 One of aryl groups;
the value range of m is 1-20.
Optionally, m ranges from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.
Optionally, the halogenated hydrocarbon is at least one selected from compounds having a structural formula shown in formula IV:
wherein Z is selected from one of F, cl, br and I;
R 4 is selected from C 1 ～C 30 Alkyl of (C) 6 ～C 30 One of the aryl groups of (a);
the value range of r is 1-20.
Optionally, r ranges from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.
Alternatively, the polymerization reaction comprises homopolymerization of one monomer and copolymerization of multiple monomers.
Optionally, an additive shown in formula V can be added in the reaction to prepare the terminal functional polymer.
Optionally, the material further comprises an additive; the additive is selected from at least one of compounds with a structural formula shown in formula V:
wherein, X' is selected from one of F, cl, br and I;
R 5 is selected from C 1 ～C 30 Alkyl of (C) 6 ～C 30 One of the aryl groups of (a);
R 6 is selected from C 1 ～C 30 Alkyl of (C) 6 ～C 30 One of aryl groups of (a);
R 7 is selected from C 1 ～C 30 Alkyl of (C) 6 ～C 30 One of aryl groups of (1).
Alternatively, the molar ratio of the initiator to the additive is 10.
Alternatively, the molar ratio of the initiator to the additive is 10.
Alternatively, the molar ratio of the initiator to the vinyl monomer is 1.
Alternatively, the molar ratio of the initiator to the vinyl monomer is 1, 1.
Optionally, the conditions of reaction I are: the reaction temperature is-78-100 ℃, and the reaction time is 5 min-48 h.
Alternatively, the reaction temperature is-78 ℃, -70 ℃, -60 ℃, -50 ℃, -40 ℃, -30 ℃, -20 ℃, -10 ℃,0 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃.
Optionally, the reaction time is 5min, 10min, 20min, 30min, 40min, 50min, 60min, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 20h, 30h, 40h, or 48h.
Optionally, the material containing the vinyl monomer and the initiator further comprises a solvent; the solvent is at least one selected from tetrahydrofuran, diethyl ether, benzene, toluene and n-hexane.
Optionally, the amount of the solvent added is 0.1-2.0 mL/mmol of the monomer.
Alternatively, the solvent is added in an amount of 0.1mL/mmol, 0.2mL/mmol, 0.3mL/mmol, 0.4mL/mmol, 0.5mL/mmol, 0.6mL/mmol, 0.7mL/mmol, 0.8mL/mmol, 0.9mL/mmol, 1.0mL/mmol, 1.1mL/mmol, 1.2mL/mmol, 1.3mL/mmol, 1.4mL/mmol, 1.5mL/mmol, 1.6mL/mmol, 1.7mL/mmol, 1.8mL/mmol, 1.9mL/mmol, or 2.0mL/mmol of the monomer.
Optionally, the reactive monomer is dispersed in a solvent.
Optionally, the preparation method further comprises a post-treatment step; the post-processing step comprises: (1) Mixing the reacted mixed system with a quenching agent, quenching and extracting to obtain a mixture containing the vinyl polymer; (2) And (3) mixing the mixture containing the vinyl polymer with a precipitator, and reacting II to obtain the vinyl polymer.
Optionally, the quenching agent is selected from at least one of methanol, ethanol, isopropanol, water, saturated aqueous ammonium chloride solution.
Preferably, the quenching agent comprises degassed methanol.
Optionally, the volume ratio of the quencher to the initiator is 1 to 10.
Optionally, the quenching comprises: adding a quenching agent under the protection of nitrogen and stirring.
Optionally, the extractant used for the extraction is selected from at least one of tetrahydrofuran and dichloromethane.
Optionally, the precipitant is at least one selected from petroleum ether, n-hexane, cyclohexane, methanol and ethanol.
Alternatively, the step (2) comprises mixing the mixture containing the vinyl polymer with an organic solvent, and then mixing with a precipitant.
Optionally, the purification comprises precipitation purification.
The precipitation purification comprises: dissolving a mixture containing the vinyl polymer in an organic solvent, precipitating and purifying in a precipitator, filtering, and drying in vacuum to obtain the vinyl polymer.
Optionally, the volume of the precipitant and the organic solvent is 15 to 20.
As an embodiment, the post-processing step includes: adding quenching agent, quenching, stirring, extracting with organic solvent and water, collecting organic layer extractive solution, adding desiccant, drying, and removing water.
Optionally, the inert gas is at least one selected from inert gases such as nitrogen and argon.
Optionally, the preparation method is a one-pot method.
Optionally, the preparation method comprises:
the first scheme is as follows: halogenated hydrocarbons and magnesium as co-initiators.
Step 1: synthesis of mixtures containing vinyl polymers
Under the protection of inert environment, adding halogenated hydrocarbon into a reaction solvent containing magnesium and vinyl monomers to react I to prepare a mixture containing a vinyl polymer;
step 2: post-treatment of mixtures containing vinyl polymers
And (3) mixing the mixture containing the vinyl polymer obtained in the step (1) with a quenching agent, quenching, extracting, precipitating in a precipitating agent, and purifying to obtain the vinyl polymer.
The reaction conditions are determined according to the vinyl monomer activity.
Preferably, the solvent in step 1 is tetrahydrofuran.
Preferably, the vinyl monomer in step 1 is one of styrene, naphthylethylene, o-m-p-chlorostyrene, o-m-p-bromostyrene, o-m-p-fluorostyrene, p-vinyl trityl alcohol and divinylbenzene.
Preferably, the reaction time of the step 1 is 5 min-48 h.
Preferably, the precipitant in step 2 is methanol.
Scheme II: grignard reagent lithium chloride complex reagent is used as an initiator.
Step 1: synthesis of mixtures containing vinyl polymers
Under the protection of inert environment, adding an initiator Grignard reagent lithium chloride complex reagent into a reaction solvent containing a vinyl monomer, and reacting I to prepare a mixture containing a vinyl polymer;
step 2: post-treatment of mixtures containing vinyl polymers
And (3) mixing the mixture containing the vinyl polymer obtained in the step (1) with a quenching agent, quenching, extracting, precipitating in a precipitating agent, and purifying to obtain the vinyl polymer.
The reaction conditions are determined according to the vinyl monomer activity.
Preferably, the solvent in step 1 is tetrahydrofuran.
Preferably, the vinyl monomer in step 1 is one of styrene, naphthylene, o-m-p-chlorostyrene, o-m-p-bromostyrene, o-m-p-fluorostyrene, p-vinyltrityl alcohol and divinylbenzene.
Preferably, the reaction time of the step 1 is 5 min-48 h.
Preferably, the precipitant in step 2 is methanol.
In the present application, "mild conditions" means a temperature of 0 ℃ to 45 ℃ which is in the range of approximately room temperature, and it is not necessarily required to use low temperatures or high temperatures, but it may be carried out at low temperatures or high temperatures.
In the present application, "very high efficiency" means that the conversion of the monomer can reach more than 99%.
In the present application, "narrow distribution" means that the molecular weight distribution obtained is narrow and polystyrene PDI (polymer dispersibility index) can be 1.1 or less.
In the present application, tetrahydrofuran is abbreviated as THF.
In the present application, the grignard reagent lithium chloride complex reagent acts as an initiator in the process.
In the present application, the term "vinyl monomer" refers to a compound in which one hydrogen atom on an ethylene molecule is replaced with another structure; for example, styrene is obtained by substituting one of the hydrogens of ethylene with benzene.
The beneficial effects that this application can produce include:
(1) According to the preparation method of the vinyl polymer, the Grignard reagent lithium chloride complex reagent is successfully introduced into the macromolecule chain polymerization.
(2) According to the preparation method of the vinyl polymer, the Barbier reaction is successfully introduced into the macromolecular chain polymerization, and the polymerization of the styrene monomer is realized through a one-pot method.
(3) The preparation method of the vinyl polymer provided by the application overcomes the problem that the common Grignard reagent cannot realize styrene polymerization; the polymerization of the chlorostyrene and the bromostyrene is realized, and the monomer range of the polymerization initiated by the lithium reagent and the magnesium reagent is expanded; and the fluorescent halogenated polystyrene is obtained, and a simple and efficient method for synthesizing the fluorescent polymer is developed.
(4) The preparation method of the vinyl polymer provided by the application has the advantages that the obtained polymer has high molecular weight, narrow molecular weight distribution and high conversion rate up to 99%, and is promising for the synthesis of block copolymers.
Drawings
FIG. 1 shows the nuclear magnetic spectrum of polystyrene prepared in example 1 of the present application.
FIG. 2 is a gel permeation chromatogram of polystyrene prepared in example 1 of the present application.
FIG. 3 shows the nuclear magnetic spectrum of poly-4-chlorostyrene prepared in example 2 of the present application.
FIG. 4 is a gel permeation chromatogram of poly-4-chlorostyrene prepared in example 2 herein.
FIG. 5 is a graph showing the effects of poly-4-chlorostyrene prepared in example 2 of the present application under a 365nm ultraviolet lamp.
FIG. 6 is a fluorescence spectrum of poly-4-chlorostyrene prepared in example 2 of the present application.
FIG. 7 shows the nuclear magnetic spectrum of polystyrene prepared in example 3 of the present application.
FIG. 8 is a gel permeation chromatogram of polystyrene prepared in example 3 of the present application.
FIG. 9 shows the nuclear magnetic spectrum of poly (p-divinylbenzene) prepared in example 4 of the present application.
FIG. 10 is a gel permeation chromatogram of poly (p-divinylbenzene) prepared in example 4 of the present application.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the starting materials in the examples of the present application were all purchased commercially, wherein tetrahydrofuran in the reaction was finely obtained, methanol for quenching was obtained by degassing, tetrahydrofuran for post-treatment, and dichloromethane and methanol were analytically pure.
The tetrahydrofuran refining process includes the following steps: cutting 5g of sodium metal into slices, shearing into filaments, adding the filaments into a flask filled with 200mL of THF, adding 1g of benzophenone serving as a color developing agent, connecting a condenser pipe to the flask, introducing the atmosphere above the condenser pipe, heating and refluxing at normal pressure, collecting the evaporated THF when the color of the solution in the flask becomes purple, collecting the THF in a solvent storage bulb bottle, and sealing and storing for later use.
The methanol degassing method comprises the following steps: taking 10mL of chromatographically pure methanol in a 25mL sealed tube, cooling by liquid nitrogen, solidifying, vacuumizing for five minutes, screwing a bottle cap, heating and melting by a blower to allow gas in the liquid to escape, and repeating for three times. And finally, introducing nitrogen into the sealed tube, and sealing and storing for later use.
The analysis method in the examples of the present application is as follows:
polymer characterization and fluorescence spectrometer Shimadzu-RF-5301 pc were performed using a nuclear magnetic resonance spectrometer AVANCE III HD, gel permeation chromatograph Agilent 1260 Infinity II GPC.
According to one embodiment of the application, a preparation method of a vinyl polymer is provided, wherein a vinyl compound is used as a reaction monomer, tetrahydrofuran is used as a reaction solvent, and a high polymer with narrow molecular weight distribution is efficiently synthesized by a one-pot method. The preparation method comprises the following preparation processes:
(1) Synthesis of mixtures containing vinyl polymers
Scheme one (grignard reagent lithium chloride complex reagent as initiator): a50 mL Schlenk reaction tube equipped with a magnetic stirrer was evacuated while water was removed by baking with a heat gun, and after cooling, nitrogen gas was purged, and oxygen removal by water removal was repeated three times. The reaction tube was then filled with nitrogen and placed at the corresponding temperature. And (3) sequentially injecting tetrahydrofuran and a Grignard reagent lithium chloride complex reagent into the reaction tube from the rubber stopper, uniformly stirring, and then adding a reaction monomer. The reaction was terminated after a certain time at this temperature.
Scheme two (halohydrocarbon and magnesium as initiator): magnesium was added to a 50mL Schlenk reaction tube equipped with a magnetic stirrer and evacuated while water was removed by baking with a heat gun, and after cooling, nitrogen gas was purged and oxygen removal by water removal was repeated three times. The reaction tube was then filled with nitrogen and placed at the corresponding temperature. And (3) sequentially injecting tetrahydrofuran, reaction monomers and halogenated hydrocarbon into the reaction tube from the rubber stopper, and reacting for a certain time at the temperature to finish the reaction.
And (3) post-treatment: slowly adding methanol under the protection of nitrogen to quench, stirring for 30min, opening a rubber plug, transferring the solution into a separating funnel, adding dichloromethane and water, extracting for 3 times by using dichloromethane solution, collecting lower-layer organic layer extract, adding anhydrous magnesium sulfate, drying for 1h, performing suction filtration to obtain colorless clear filtrate, and removing the solvent in a rotary evaporator to obtain a mixture containing the vinyl polymer;
(2) Purification of mixtures containing vinyl polymers
Dissolving the mixture containing the vinyl polymer obtained in the step (1) by using a small amount of tetrahydrofuran, precipitating and purifying in a precipitator, performing suction filtration to obtain a filter cake, namely the vinyl polymer, and finally performing various characterizations after vacuum drying.
The vinyl monomer in step (1) is one of styrene, naphthylene, o-m-p-chlorostyrene, o-m-p-bromostyrene, o-m-p-fluorostyrene, and 4-vinyl trityl alcohol, but is not limited thereto.
The reaction time in the step (1) is within 5 min-48 h according to the reaction activity of the monomer.
The reaction temperature in the step (1) is within 0-45 ℃ according to the reactivity of the monomer.
The precipitator in the step (2) is methanol.
The following are reaction formulas and vinyl monomers of one embodiment of the present invention, and the scope of protection is not limited to the following grignard reagent lithium chloride complexes, such as the following halogenated hydrocarbons and the following monomers:
grignard reagent lithium chloride complex as initiator:
halogenated hydrocarbons and magnesium as initiators:
EXAMPLE 1 polymerization of styrene monomer with Isopropylmagnesium chloride lithium chloride Complex reagent
(1) Synthesis of crude product of polystyrene
A50 mL Schlenk reaction tube equipped with a magnetic stirrer was evacuated while water was removed by baking with a heat gun, and after cooling, nitrogen gas was purged, and oxygen removal by water removal was repeated three times. The reaction tube was then filled with nitrogen and placed in a 45 ℃ oil bath. 4mL of tetrahydrofuran and 0.3mL of isopropylmagnesium chloride lithium chloride THF solution (concentration: 1.3M) were sequentially introduced into the reaction tube through the rubber stopper, and 2g of styrene was added thereto after stirring uniformly. After 5h, the reaction was stopped to give a viscous reaction stock. Slowly adding 1mL of methanol under the protection of nitrogen for quenching, stirring for 30min, opening a rubber plug, transferring the solution into a separating funnel, adding dichloromethane and water, extracting for 3 times by using dichloromethane solution, collecting the lower organic layer extract, adding anhydrous magnesium sulfate, drying for 1h, carrying out suction filtration to obtain colorless clear filtrate, and removing the solvent in a rotary evaporator to obtain the crude product of the corresponding polymer.
(2) Purification of crude polystyrene product
Dissolving the crude product of the polystyrene obtained above by 50mL of THF, precipitating and purifying in 750mL of precipitator methanol, and filtering to obtain a filter cake, namely pure polystyrene.
(3) Characterization of the polystyrene
The obtained pure polystyrene was dried in vacuum and then characterized. The results are shown in FIGS. 1-2.
As shown in fig. 1, the delta =1.10-2.32 alkyl region shows peaks characteristic to high molecules of methylene and methine groups. From this, it was confirmed that the polystyrene of example 1 was successfully prepared.
As shown in fig. 2, a gel permeation chromatogram of polystyrene was shown, with a weight average molecular weight of 44200 and a molecular weight distribution of 1.153.
Example 2 polymerization of 4-chlorostyrene monomer initiated by isopropyl magnesium chloride lithium chloride complex reagent gives luminescent polymers.
(1) Synthesis of crude Poly-4-chlorostyrene
A50 mL Schlenk reaction tube equipped with a magnetic stirrer was evacuated while water was removed by baking with a heat gun, and after cooling, nitrogen gas was purged, and oxygen removal by water removal was repeated three times. The reaction tube was then filled with nitrogen and placed in a 45 ℃ oil bath. 10mL of tetrahydrofuran and 0.23mL of a Grignard reagent, lithium chloride complex THF solution (concentration: 1.3M) were sequentially injected into the reaction tube from the rubber stopper, and after stirring the mixture uniformly, 2g of 4-chlorostyrene was added. After 2h, the reaction was stopped to give a viscous reaction stock. Slowly adding 1mL of methanol under the protection of nitrogen for quenching, stirring for 30min, opening a rubber plug, transferring the solution into a separating funnel, adding DCM and water, extracting for 3 times by using the DCM solution, collecting the lower-layer organic-layer extract, adding anhydrous magnesium sulfate, drying for 1h, carrying out suction filtration to obtain colorless clear filtrate, and removing the solvent in a rotary evaporator to obtain the crude product of the corresponding macromolecule.
(2) Purification of crude poly-4-chlorostyrene
And dissolving the crude product of the poly-4-chlorostyrene obtained above by using 50mL of THF, precipitating and purifying in 750mL of precipitator methanol, and performing suction filtration to obtain a filter cake, namely the pure polystyrene.
(3) Characterization of poly-4-chlorostyrene
The obtained pure polystyrene was dried in vacuum and then characterized. The results are shown in FIGS. 3-6.
As shown in fig. 3, the delta =1.02-2.10 alkyl region shows peaks characteristic to macromolecules of methylene and methine groups. It was thus confirmed that poly-4-chlorostyrene in example 2 was successfully prepared.
As shown in fig. 4, a gel permeation chromatogram of polychlorostyrene was shown, with a weight average molecular weight of 695300 and a molecular weight distribution of 1.58.
As shown in fig. 5, a picture of polychlorostyrene powder under a 365nm uv lamp is shown.
As shown in fig. 6, the excitation spectrum and emission spectrum of the polychlorostyrene powder.
Therefore, the method of using the Grignard reagent lithium chloride complex reagent as the initiator to initiate the polymerization of the vinyl monomer has feasibility.
Example 3 polymerization of styrene monomer was initiated with chloroisopropane and magnesium.
(1) Synthesis of crude product of polystyrene
A50 mL Schlenk reaction tube equipped with a magnetic stirrer was charged with 92.3mg of magnesium, evacuated while baking with a heat gun to remove water, purged with nitrogen after cooling, and oxygen removal by water removal was repeated three times. The reaction tube was then filled with nitrogen and placed in a 45 ℃ oil bath. Into the reaction tube were sequentially injected 4mL of tetrahydrofuran, 2g of styrene and 352uL of chloroisopropyl alcohol from a rubber stopper. After 24h, the reaction was stopped to give a viscous reaction stock. Slowly adding 1mL of methanol under the protection of nitrogen for quenching, stirring for 30min, opening a rubber plug, transferring the solution into a separating funnel, adding dichloromethane and water, extracting for 3 times by using dichloromethane solution, collecting lower-layer organic-layer extract, adding anhydrous magnesium sulfate, drying for 1h, carrying out suction filtration to obtain colorless clear filtrate, and removing the solvent in a rotary evaporator to obtain a crude product of the corresponding macromolecule.
(2) Purification of crude polystyrene product
And dissolving the crude product of the polystyrene with 50mL of THF, precipitating and purifying in 750mL of precipitator methanol, and filtering to obtain a filter cake, namely the pure polystyrene.
(3) Characterization of the polystyrene
The obtained pure polystyrene was dried in vacuum and then characterized. The results are shown in FIGS. 7-8.
As shown in fig. 7, the delta =1.15-2.38 alkyl region shows peaks characteristic to high molecules of methylene and methine groups. It was thus confirmed that the polystyrene of example 3 was successfully prepared.
As shown in fig. 8, a gel permeation chromatogram of polystyrene was shown, with a weight average molecular weight of 15400 and a molecular weight distribution of 1.09.
Therefore, a method of initiating polymerization of vinyl monomers using chloroisopropane and magnesium as initiators is feasible.
Example 4 Chloroisopropane and magnesium co-initiated polymerization of p-divinylbenzene monomer.
(1) Synthesis of crude product of poly (p-divinylbenzene)
A25 mL Schlenk reaction tube equipped with a magnetic stirrer was charged with 37.4mg of magnesium, evacuated while baking with a heat gun to remove water, purged with nitrogen after cooling, and oxygen removal by water removal was repeated three times. The reaction tube was then filled with nitrogen and placed in a 45 ℃ oil bath. 2mL of tetrahydrofuran, 1g of p-divinylbenzene and 141uL of chloroisopropyl were injected into the reaction tube from the rubber stopper in this order. And stopping the reaction after 24 hours of reaction to obtain a reaction stock solution. Slowly adding 1mL of methanol under the protection of nitrogen for quenching, stirring for 30min, opening a rubber plug, transferring the solution into a separating funnel, adding dichloromethane and water, extracting for 3 times by using dichloromethane solution, collecting the lower organic layer extract, adding anhydrous magnesium sulfate, drying for 1h, carrying out suction filtration to obtain colorless clear filtrate, and removing the solvent in a rotary evaporator to obtain the crude product of the corresponding polymer.
(2) Purification of crude poly (p-divinylbenzene)
And dissolving the crude product of the polystyrene with 25mL of THF, precipitating and purifying in 300mL of precipitator methanol, and performing suction filtration to obtain a filter cake, namely the pure poly-p-divinylbenzene.
(3) Characterization of Poly-p-divinylbenzene
The obtained pure poly-p-divinylbenzene was dried in vacuum and then characterized. The results are shown in FIGS. 9-10.
As shown in fig. 9, the delta =1.00-2.27 alkyl region shows peaks characteristic to high molecules of methylene and methine groups. It was thus confirmed that the polydivinylbenzene of example 4 was successfully prepared.
As shown in fig. 10, a gel permeation chromatogram of polydivinylbenzene was shown, with a weight average molecular weight of 84600 and a molecular weight distribution of 1.73.
Therefore, the method for jointly initiating the polymerization of the p-divinylbenzene monomer by the chloroisopropane and the magnesium has feasibility.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Example 5 benzophenone was involved as an additive in the co-initiation of styrene monomer polymerization with chloroisopropane and magnesium.
(1) Synthesis of crude product of polystyrene
A50 mL Schlenk reaction tube equipped with a magnetic stirrer was charged with 92.3mg of magnesium, evacuated while baking with a heat gun to remove water, purged with nitrogen after cooling, and oxygen removal by water removal was repeated three times. The reaction tube was then filled with nitrogen and placed in a 45 ℃ oil bath. 4mL of tetrahydrofuran containing 0.7g of benzophenone, 2g of styrene and 352uL of chloroisopropyl were injected into the reaction tube from the rubber stopper in this order. After 24h, the reaction was stopped to give a viscous reaction stock. Slowly adding 1mL of methanol under the protection of nitrogen for quenching, stirring for 30min, opening a rubber plug, transferring the solution into a separating funnel, adding dichloromethane and water, extracting for 3 times by using dichloromethane solution, collecting lower-layer organic-layer extract, adding anhydrous magnesium sulfate, drying for 1h, carrying out suction filtration to obtain colorless clear filtrate, and removing the solvent in a rotary evaporator to obtain a crude product of the corresponding macromolecule.
(2) Purification of crude polystyrene product
Dissolving the crude product of the polystyrene obtained above by 50mL of THF, precipitating and purifying in 750mL of precipitator methanol, and filtering to obtain a filter cake, namely pure polystyrene.
Therefore, the method that the benzophenone participates in the chloro-isopropyl and the magnesium as the initiator to initiate the vinyl monomer polymerization has feasibility.
Although the present invention has been described with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method for producing an ethylene-based polymer, comprising: reacting a material containing a vinyl monomer and an initiator in the presence of an inert gas to obtain a vinyl polymer;
wherein the initiator refers to a co-initiator of a halogenated hydrocarbon and magnesium or a mono-initiator of a grignard reagent lithium chloride complex.
2. The production method according to claim 1, wherein the vinyl polymer has a molecular weight of 1000 to 5000000; the molecular weight distribution range is 1-30.
3. The method of claim 1, wherein the vinyl monomer is selected from one or more compounds having a formula shown in formula II:
wherein Y is selected from one of Br, cl and F;
R 1 is selected from C 6 ～C 30 Aryl of (C) 1 ～C 30 One of alkyl, carbonyl, nitrile, nitro, methoxy and vinyl;
R 2 is selected from C 6 ～C 30 Aryl of, C 1 ～C 30 And (3) alkyl and carbonyl.
4. The method of claim 1, wherein the grignard reagent lithium chloride complex is at least one selected from the group consisting of compounds having a structural formula represented by formula III:
wherein X is selected from one of Cl and Br;
R 3 is selected from C 1 ～C 30 Alkyl of (C) 6 ～C 30 One of the aryl groups of (a);
the value range of m is 1-20.
5. The method of claim 1, wherein the halogenated hydrocarbon is at least one selected from the group consisting of compounds having a formula shown in formula IV:
wherein Z is selected from one of F, cl, br and I;
R 4 is selected from C 1 ～C 30 Alkyl of (C) 6 ～C 30 One of aryl groups of (a);
the value range of r is 1-20.
6. The method of claim 1, wherein the material further comprises an additive;
the additive is selected from at least one of compounds with a structural formula shown in formula V:
wherein, X' is selected from one of F, cl, br and I;
R 5 is selected from C 1 ～C 30 Alkyl of (C) 6 ～C 30 One of the aryl groups of (a);
R 6 is selected from C 1 ～C 30 Alkyl of (C) 6 ～C 30 One of aryl groups of (a);
R 7 is selected from C 1 ～C 30 Alkyl of (C) 6 ～C 30 One of aryl groups of (1).
7. The preparation method according to claim 6, wherein the molar ratio of the initiator to the additive is 10.
8. The method according to claim 1, wherein the molar ratio of the initiator to the vinyl monomer is 1.
9. The method according to claim 1, wherein the conditions of reaction I are: the reaction temperature is-78-100 ℃, and the reaction time is 5 min-48 h.
10. The method of claim 1, wherein the mass comprising the vinyl monomer and the initiator further comprises a solvent; the solvent is at least one of tetrahydrofuran, diethyl ether, benzene, toluene and n-hexane;
preferably, the addition amount of the solvent is 0.1-2.0 mL/mmol of the monomer;
preferably, the preparation method further comprises a post-treatment step; the post-processing step comprises:
(1) Mixing the reacted mixed system with a quenching agent, quenching and extracting to obtain a mixture containing the vinyl polymer;
(2) Mixing a mixture containing a vinyl polymer with a precipitator, and reacting II to obtain the vinyl polymer;
preferably, the step (2) comprises mixing the mixture containing the vinyl polymer with the organic solvent, and then mixing with the precipitant;
preferably, the volume ratio of the precipitant to the organic solvent is 15 to 20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110797190.4A CN115612002B (en) | 2021-07-14 | 2021-07-14 | Preparation method of vinyl polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110797190.4A CN115612002B (en) | 2021-07-14 | 2021-07-14 | Preparation method of vinyl polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115612002A true CN115612002A (en) | 2023-01-17 |
| CN115612002B CN115612002B (en) | 2024-02-23 |
Family
ID=84854513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110797190.4A Active CN115612002B (en) | 2021-07-14 | 2021-07-14 | Preparation method of vinyl polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115612002B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008028166A1 (en) * | 2006-09-01 | 2008-03-06 | Carnegie Mellon University | Universal grignard metathesis polymerization |
| US20090203861A1 (en) * | 2007-12-17 | 2009-08-13 | Gwangju Institute Of Science And Technology | Anionic polymerization method for styrene derivative containing pyridine as functional group |
| CN106632998A (en) * | 2016-12-30 | 2017-05-10 | 中国石油大学(华东) | Barbier-reaction-based method for preparing high molecules |
| CN106700036A (en) * | 2016-12-30 | 2017-05-24 | 中国石油大学(华东) | Macromolecule with aggregation-induced luminescence effect, and preparation method of macromolecule |
| EP3385298A1 (en) * | 2017-04-03 | 2018-10-10 | Qatar Foundation For Education Science And Community Development | Method of making a pyrrolo bisthiazole homopolymer |
| CN111269397A (en) * | 2018-12-05 | 2020-06-12 | 中国科学院福建物质结构研究所 | Polymerization method and polymer prepared by same |
-
2021
- 2021-07-14 CN CN202110797190.4A patent/CN115612002B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008028166A1 (en) * | 2006-09-01 | 2008-03-06 | Carnegie Mellon University | Universal grignard metathesis polymerization |
| US20090203861A1 (en) * | 2007-12-17 | 2009-08-13 | Gwangju Institute Of Science And Technology | Anionic polymerization method for styrene derivative containing pyridine as functional group |
| CN106632998A (en) * | 2016-12-30 | 2017-05-10 | 中国石油大学(华东) | Barbier-reaction-based method for preparing high molecules |
| CN106700036A (en) * | 2016-12-30 | 2017-05-24 | 中国石油大学(华东) | Macromolecule with aggregation-induced luminescence effect, and preparation method of macromolecule |
| EP3385298A1 (en) * | 2017-04-03 | 2018-10-10 | Qatar Foundation For Education Science And Community Development | Method of making a pyrrolo bisthiazole homopolymer |
| CN111269397A (en) * | 2018-12-05 | 2020-06-12 | 中国科学院福建物质结构研究所 | Polymerization method and polymer prepared by same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115612002B (en) | 2024-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Baskaran | Strategic developments in living anionic polymerization of alkyl (meth) acrylates | |
| JP2010255008A (en) | Star block copolymer | |
| EP0109915B1 (en) | Process for the functionalization of polystyrene resins | |
| KR101768293B1 (en) | Novel initiator in anionic polymerization and method for preparing a conjugated diene polymer using the same | |
| Richards | Catalyst Systems in Anionic Copolymerisations | |
| JP4623690B2 (en) | Star block copolymer | |
| CN115612002B (en) | Preparation method of vinyl polymer | |
| AU2001274216B2 (en) | Polymerisation initiator and use | |
| JP4727801B2 (en) | Alkenylphenol-based star block copolymer and method for producing the same | |
| Lindsell et al. | Polymerization by alkaline earth metal compounds—I. Studies on the polymerization of methylmethacrylate by triphenylmethyl metal derivatives and related compounds of calcium, strontium and barium | |
| CN103554365B (en) | One class is based on rare-earth catalysis system butadiene-isoprene copolymer and preparation method thereof | |
| JP4549507B2 (en) | Polymerization method of methacrylic acid ester or acrylic acid ester | |
| US3928302A (en) | Alkaline earth metal organometallic compounds, their preparation by metallation and catalysts comprising same | |
| CN114920897A (en) | Two deuterated polymers and preparation method thereof | |
| US20030166804A1 (en) | Trivalent organic lanthanoid complex, catalyst for production of (meth) acrylic polymer, and (meth) acrylic polymer | |
| CN112625160A (en) | End group functionalized polymer and method for carrying out Glaser coupling polymerization reaction by utilizing copper acetylide | |
| WO1995014046A1 (en) | Highly active pi-allylnickel-based polymerization initiators | |
| JP3057508B2 (en) | Method for producing p-alkenylphenol-based polymer | |
| JP5226160B2 (en) | Method for anionic polymerization of a monomer by contacting the monomer with a monofunctional anionic polymerization initiator | |
| CN1429849A (en) | Organic lithium compound containing tin and its preparation method | |
| Ihara et al. | Polymerization of methyl methacrylate initiated with organomanganate reagents | |
| JP3744246B2 (en) | Process for producing poly (pt-butoxystyrene) | |
| JP4341136B2 (en) | Method for producing polymer having functional group at terminal of main chain | |
| CN112175123B (en) | Poly-conjugated diene liquid rubber and preparation method and application thereof | |
| Ninago et al. | Lithium naphthalenides in non-polar or in low-polarity media: some insights regarding their use as initiators in anionic polymerizations |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |