CN114957518A - Method for preparing polar functional group-containing olefin by iron-catalyzed polyolefin chain carbon-hydrogen bond alkylation - Google Patents

Method for preparing polar functional group-containing olefin by iron-catalyzed polyolefin chain carbon-hydrogen bond alkylation Download PDF

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CN114957518A
CN114957518A CN202210762552.0A CN202210762552A CN114957518A CN 114957518 A CN114957518 A CN 114957518A CN 202210762552 A CN202210762552 A CN 202210762552A CN 114957518 A CN114957518 A CN 114957518A
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iron
ferrous
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ferric
polyolefin
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曾荣
张宗楠
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Xian Jiaotong University
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Abstract

A method for preparing polyolefin containing polar functional groups by iron-catalyzed carbon-hydrogen bond alkylation of polyolefin chains comprises the following steps: under the action of iron compound, providing proper temperature and/or light energy, functionalizing the carbon-hydrogen bond of polyolefin compound in solvent in the presence of electron-deficient olefin compound and additive, and realizing controllable and catalytic functional group conversion to obtain corresponding polar functional group-containing polyolefin product; the method directly utilizes the commercialized polyolefin compound to carry out carbon-hydrogen bond functionalization, has the advantages of simple reaction, simple operation, short reaction time, mild reaction condition, high atom economy, high reaction yield, easy separation and purification of products, good substrate universality and the like, and has great application potential in the fields of metal catalysis, polymer modification, new material synthesis, waste plastic recovery and the like by utilizing cheap metal to carry out reaction.

Description

Method for preparing polar functional group-containing olefin by iron-catalyzed polyolefin chain carbon-hydrogen bond alkylation
Technical Field
The invention relates to a synthetic method of a product containing polar functional groups, in particular to a method for preparing polyolefin containing polar functional groups by carbon-hydrogen bond alkylation of polyolefin chains under iron catalysis, which is a synthetic method for preparing the product containing polar functional groups by carbon-hydrogen bond activation and olefin addition conversion in polyolefin compound chains under iron catalysis.
Background
Polyolefin compounds are important high molecular polymers, and among them, the most widely used polyolefins are polyethylene, polypropylene, polyvinyl chloride, polystyrene and the like, which are main sources of three synthetic materials, namely plastics, so that the polyolefins are indispensable in human daily life. However, the use of a large amount of plastic also brings about a serious pollution problem, namely 'white pollution', and the recycling of waste plastic is a problem which people want to solve at present.
The functionalization modification of the carbon-hydrogen bond on the polyolefin compound is an important means for changing the property, performance and added value of the polyolefin compound, and further realizes the reutilization and performance reconstruction of the waste plastic. Because the carbon-hydrogen bond on the polymer chain segment has good stability, the carbon-hydrogen bond alkylation of the catalytic polyolefin compound is only reported. The current report of Journal of Applied Polymer Science,1969,13,1625, which uses excess peroxide to generate active free radicals, but the use of excess peroxide leads to partial degradation of the Polymer, therefore, it is necessary to develop a new method for modifying the carbon-hydrogen bond of polyolefin compound for functionalization.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing polyolefin compounds containing polar functional groups by iron-catalyzed carbon-hydrogen bond alkylation of polyolefin chains, which is to perform functional group reaction on polyolefin compounds with different polymerization degrees, namely, under the acceleration of an iron catalyst and an additive and under the irradiation of visible light, polyolefin compounds with different polar functional groups are generated through hydrocarbon fracture and olefin addition reaction; has the advantages of simple reaction, mild oxidation condition, short reaction time, simple operation and the like.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for preparing polyolefin containing polar functional groups by iron-catalyzed carbon-hydrogen bond alkylation of polyolefin chains comprises the following steps:
under the action of an iron compound, temperature and/or light energy are provided, and the breaking and addition of carbon-hydrogen bonds on chains of a polyolefin compound are realized in a corresponding organic solvent in the presence of electron-deficient olefin and an additive, so that a controllable functionalized product is obtained, wherein the reaction equation is as follows:
Figure BDA0003724592600000021
the polyolefin compound has any molecular weight and comprises low-density polyethylene, high-density polyethylene, linear low-density polyethylene and polyethylene copolymer, polypropylene and polypropylene copolymer, polystyrene and polystyrene copolymer, polyvinyl chloride and polyvinyl chloride copolymer, polyisobutylene and polyisobutylene copolymer, polyvinyl fluoride and polyvinyl fluoride copolymer, polyvinyl alcohol, polyacrylate and polyacrylonitrile;
the electron-deficient olefin comprises alkenyl malononitrile and derivatives thereof, maleic anhydride, maleimide and derivatives thereof, unsaturated aldehyde and derivatives thereof, unsaturated ketone and derivatives thereof, acrylonitrile, and acrylic acid and derivatives thereof.
The general formula of the alkenyl malononitrile and the derivative thereof is
Figure BDA0003724592600000022
The maleimide and the derivative thereof have the general formula
Figure BDA0003724592600000023
Unsaturated aldehydes and derivatives thereof have the general formula
Figure BDA0003724592600000031
Unsaturated ketones and derivatives thereof of the general formula
Figure BDA0003724592600000032
The general formula of acrylonitrile is
Figure BDA0003724592600000033
Acrylic acid and derivatives thereof
Figure BDA0003724592600000034
Wherein R is 1 、R 2 、R 3 、R 4 、R 5 、 R 6 、R 7 、R 8 、R 9 Including hydrogen, alkyl, substituted or unsubstituted phenyl, naphthyl, pyridine, thiophene, furan, pyrrole, indole, carbazole; the substitution includes fluorine, chlorine, bromine, iodine, hydroxyl, carboxyl, mercapto, amino, primary amino, secondary amino, imino, nitro, cyano, alkyl, ester, silicon, acyl, butyloxycarbonyl, isopropyloxycarbonyl, ethyloxycarbonyl and phenyl.
A method for preparing polyolefin with polar functional group by iron-catalyzed carbon-hydrogen bond alkylation of polyolefin chain comprises the following reaction steps:
(1) sequentially adding an iron compound, an additive, a polyolefin compound, electron-deficient olefin and an organic solvent into a dry reaction tube, stirring and dissolving the mixture in an inert gas atmosphere after the addition is finished, uniformly mixing the mixture, and irradiating the reaction tube under light with specific power and wavelength and continuously stirring the mixture or heating the reaction tube;
(2) and (2) after the reaction in the step (1) is completed, removing the reaction tube from the light source, adding ethanol to expel out solid, filtering, and washing to completely remove the residual unsaturated olefin.
The iron compound is an iron-containing compound, including ferric iron or ferrous iron compounds; the ferric iron comprises ferric trichloride, ferric tribromide, ferric trifluoromethanesulfonate, ferric tetrafluoroborate, ferric hexafluorophosphate, ferric sulfate, ferric nitrate, ferric acetate, ferric trifluoroacetate, ferric citrate, ferric oxalate, ferric acrylate, tris (2,2,6, 6-tetramethyl-3, 5-heptanedionato) iron, ferric hydroxide, ferric acetylacetonate, ferric fluoride iron-containing compounds and hydrates thereof; the ferrous iron comprises ferrous chloride, ferrous bromide, ferrous iodide, ferrous trifluoromethanesulfonate, ferrous tetrafluoroborate, ferrous hexafluorophosphate, ferrous sulfate, ferrous nitrate, ferrous acetate, ferrous trifluoroacetate, ferrous citrate, ferrous oxalate, ferrous acrylate, ferrous bis (2,2,6, 6-tetramethyl-3, 5-heptanedionate), ferrous hydroxide, ferrous acetylacetonate, ferrous fluoride iron-containing compounds and hydrates thereof.
Preferably, the corresponding iron compound is ferric chloride, ferric tribromide, ferrous chloride, ferrous bromide, or ferrous acetate.
The corresponding organic solvent is one or more of water, hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, nitrohydrocarbon solvents, ether solvents, nitrile solvents, ester solvents, alcohol solvents, amine solvents, amide solvents, sulfone solvents and sulfoxide solvents.
The hydrocarbon solvent is one or more of benzene, toluene and saturated alkane compounds, the halogenated hydrocarbon solvent is one or more of trifluoromethylbenzene, chlorobenzene, dichloromethane, 1, 2-dichloroethane, chloroform and carbon tetrachloride, and the nitrohydrocarbon solvent is one or more of nitrobenzene and nitromethane; the ether solvent is one or more of tetrahydrofuran, 1, 4-dioxane, methyl tert-butyl ether and diethyl ether; the nitrile solvent is one or more of acetonitrile, benzonitrile and tert-butyl acetonitrile; the ester solvent is one or more of ethyl acetate, n-butyl acetate and isobutyl acetate; the alcohol solvent is one or more of methanol, ethanol, tert-butyl alcohol, n-butyl alcohol and cyclohexanol, and the amine solvent is one or more of triethylamine, diethylamine and diisopropylethylamine; the amide solvent is one or more of dimethylformamide and dimethylacetamide; the sulfoxide solvent is dimethyl sulfoxide, and can be used in any proportion in various cases.
Preferably, the corresponding organic solvent is chlorobenzene, trifluorotoluene, 1, 2-dichloroethane, dichloromethane.
The additive is alkali metal salt of halide, alkali metal salt of organic acid compound, alkali metal salt of phenolic compound, ammonium salt of halide, ammonium salt of organic acid compound, ammonium salt of phenolic compound, wherein the halide is fluoride, chloride, bromide, iodide; the alkali metal salt is lithium salt, sodium salt, potassium salt or cesium salt; the organic acid compound is substituted or unsubstituted aryl carboxylic acid, substituted or unsubstituted alkyl carboxylic acid, substituted or unsubstituted aryl sulfonic acid, substituted or unsubstituted alkyl sulfonic acid, substituted or unsubstituted aryl phosphoric acid and substituted or unsubstituted alkyl phosphoric acid; the phenols are substituted or unsubstituted phenol compounds; the ammonium salt is tetramethylammonium salt, tetraethylammonium salt or tetrabutylammonium salt.
Preferably, the additive is sodium chloride, potassium chloride, tetrabutylammonium chloride.
The molar ratio of the iron compound to the polymer monomer is (0.001-0.01): 1, the molar ratio of the electron-deficient olefin to the polymer monomer is (0.025-0.5): 1; the molar ratio of the iron compound to the additive is (0.1-10): 1; the organic solvent is added in an excessive amount.
The temperature conditions provided are: the reacted system was placed at 25 ℃ to 150 ℃.
The lighting condition of the light energy comprises: the reacted system is exposed to visible light and/or monochromatic or mixed light of a wavelength of less than 500 nm.
And (3) exposing the reacted system to light with the wavelength of 350-500nm for irradiation.
The innovation point of the invention is to develop a controllable and efficient one-step functionalization method of the polyolefin compound with cheap and easily available raw materials. The invention provides a controllable and catalytic functionalization method for polyolefins, which can efficiently and quickly obtain corresponding polyolefin derivatives under the catalysis of an iron compound and the action of an additive under the condition of providing heat energy and/or light energy and/or microwaves; the reaction method has the advantages of mild conditions, neutral redox, short reaction time, safety, greenness, simple operation, no need of a large amount of high-valence metal salt, wide applicability of substrates and capability of preparing the polyolefin derivatives on a large scale. The method has great significance in industrial production. Has the following beneficial effects:
(1) the reaction only needs cheap and easily available iron catalyst.
(2) The reaction can be realized by using visible light as a light source and a blue LED lamp with the power of 1-200W.
(3) The polyolefin compound which is widely available, cheap and easily available is used as a substrate, and the reaction time is short.
(4) The polyolefin compounds with different alkyl substituents can be quickly and simply synthesized.
(5) The product is easy to separate and purify, and can be further derived to prepare useful high polymers.
The invention provides a convenient and rapid strategy for the preparation of various polyolefin compounds, can avoid using a large amount of heavy metal salt and strong oxidant by directly utilizing cheap and abundant polyolefin compounds as raw materials, has great attraction on industrial production, and has great application potential in the fields of plastic recovery, polymer modification and the like by utilizing cheap metals for reaction.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described in the following embodiments to fully understand the objects, aspects and effects of the present invention. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The following examples are helpful in understanding the present invention, but are not intended to limit the scope of the present invention.
Example 1
Ferric chloride (0.2 mol%), tetrabutylammonium chloride (0.2 mol%), low density polyethylene (LDPE,2.0 mmol monomer equivalents), methyl acrylate (20 mol%), chlorobenzene (3 ml) were added to the dry reaction tube in sequence, after the end of the additionStirring and dissolving the mixture in an inert gas atmosphere, uniformly mixing, placing the reaction tube in an oil bath at 120 ℃ and irradiating the reaction tube under light (hv) with the wavelength of 390nm, continuously stirring, removing the reaction tube from a light source after the reaction is finished, adding ethanol to separate out a solid, filtering, washing and drying in vacuum to obtain a target product. 1 H NMR (400MHz,CDCl 3 ) Delta 33.66(s,3H), 2.50-2.23 (m,1.89H), 1.85-0.56 (m,45.64H). The functionalization rate can be controlled from 5 to 15 mol% depending on the reaction time.
Figure BDA0003724592600000061
Figure BDA0003724592600000071
Figure BDA0003724592600000081
The iron compound is selected from ferric chloride, ferric tribromide, ferric acetate, ferrous chloride, ferrous bromide and ferrous acetate which are listed in the above embodiment; iron trifluoromethanesulfonate, iron tetrafluoroborate, iron hexafluorophosphate, iron sulfate, iron nitrate, iron trifluoroacetate, iron citrate, iron oxalate, iron acrylate, iron tris (2,2,6, 6-tetramethyl-3, 5-heptanedionate), iron hydroxide, iron acetylacetonate, iron fluoride-containing compound and hydrates thereof were also used in place of iron trichloride in examples 1 and 15, and the remaining reaction conditions were the same, and it was found that the products obtained by the reaction and the functionalization rate were similar;
ferrous iodide, ferrous trifluoromethanesulfonate, ferrous tetrafluoroborate, ferrous hexafluorophosphate, ferrous sulfate, ferrous nitrate, ferrous trifluoroacetate, ferrous citrate, ferrous oxalate, ferrous acrylate, ferrous bis (2,2,6, 6-tetramethyl-3, 5-heptanedionate), ferrous hydroxide, ferrous acetylacetonate, a ferrous fluoride-containing compound and hydrates thereof were also used in place of the ferrous chloride in example 5, and the remaining reaction conditions were the same, and it was found that the resulting products of the reaction and the functionalization rates were similar.
Except for the organic solvent listed in the above examples, the organic solvent listed in the summary of the invention was used to replace PhCF3 in example 2, and the reaction conditions were the same, and the product obtained by the reaction and the functionalization rate were found to be similar.
The additives other than those listed in the above examples, the tetrabutylammonium chloride in example 9 was replaced with the additives listed in the summary of the invention, and the reaction conditions were the same, and the products obtained by the reaction and the functionalization rate were found to be similar.
In conclusion, the method can use cheap and easily-obtained polyolefin as a substrate to carry out functionalization of different substituents on carbon-hydrogen bonds of the polyolefin, and has the advantages of mild conditions, simple operation, short reaction time, greenness, high efficiency and wide application space.
The invention adopts the reaction condition of providing heat energy and/or light energy and/or microwaves, can realize the functionalization of the polyolefin compound by one or more modes of simple heating, illumination or microwaves even under the condition of direct irradiation of a blue LED lamp, does not need harsh reaction conditions such as high temperature, strong oxidant and the like or the addition of noble metal catalyst, has mild reaction conditions, is green and environment-friendly, is suitable for industrial production, and provides a new strategy for the diversity of chemical synthesis.

Claims (9)

1. A method for preparing polyolefin containing polar functional groups by iron-catalyzed carbon-hydrogen bond alkylation of polyolefin chains is characterized by comprising the following steps:
under the action of an iron compound, temperature and/or light energy are provided, and the breaking and addition of carbon-hydrogen bonds on chains of a polyolefin compound are realized in a corresponding organic solvent in the presence of electron-deficient olefin and an additive, so that a controllable functionalized product is obtained, wherein the reaction equation is as follows:
Figure FDA0003724592590000011
the polyolefin compound has any molecular weight and comprises low-density polyethylene, high-density polyethylene, linear low-density polyethylene and polyethylene copolymer, polypropylene and polypropylene copolymer, polystyrene and polystyrene copolymer, polyvinyl chloride and polyvinyl chloride copolymer, polyisobutylene and polyisobutylene copolymer, polyvinyl fluoride and polyvinyl fluoride copolymer, polyvinyl alcohol, polyacrylate and polyacrylonitrile;
the electron-deficient olefin comprises alkenyl malononitrile and derivatives thereof, maleic anhydride, maleimide and derivatives thereof, unsaturated aldehyde and derivatives thereof, unsaturated ketone and derivatives thereof, acrylonitrile, and acrylic acid and derivatives thereof;
the general formula of the alkenyl malononitrile and the derivative thereof is
Figure FDA0003724592590000012
The maleimide and the derivative thereof have the general formula
Figure FDA0003724592590000013
Unsaturated aldehydes and derivatives thereof have the general formula
Figure FDA0003724592590000014
Unsaturated ketones and derivatives thereof of the general formula
Figure FDA0003724592590000015
The general formula of acrylonitrile is
Figure FDA0003724592590000021
Acrylic acid and derivatives thereof
Figure FDA0003724592590000022
Wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 Including hydrogen, alkyl, substituted or unsubstituted phenyl, naphthyl, pyridine, thiophene, furan, pyrrole, indole, carbazole; said substitutionIncluding fluorine, chlorine, bromine, iodine, hydroxyl, carboxyl, mercapto, amino, primary amino, secondary amino, imino, nitro, cyano, alkyl, ester, silicon, acyl, butyloxycarbonyl, isopropyloxycarbonyl, ethyloxycarbonyl and phenyl.
2. A method for preparing polyolefin containing polar functional groups by iron-catalyzed carbon-hydrogen bond alkylation of polyolefin chains is characterized by comprising the following reaction steps:
(1) sequentially adding an iron compound, an additive, a polyolefin compound, electron-deficient olefin and an organic solvent into a dry reaction tube, stirring and dissolving the mixture in an inert gas atmosphere after the addition is finished, uniformly mixing the mixture, and irradiating the reaction tube under light with specific power and wavelength and continuously stirring the mixture or heating the reaction tube;
(2) and (2) after the reaction in the step (1) is completed, removing the reaction tube from the light source, adding ethanol to expel out solid, filtering, and washing to completely remove the residual unsaturated olefin.
3. The method for preparing the polyolefin chain with polar functional group by the carbon-hydrogen bond alkylation under the catalysis of iron according to claim 1 or 2, wherein the iron compound is an iron-containing compound, and comprises ferric iron or ferrous iron compound; the ferric iron comprises ferric trichloride, ferric tribromide, ferric trifluoromethanesulfonate, ferric tetrafluoroborate, ferric hexafluorophosphate, ferric sulfate, ferric nitrate, ferric acetate, ferric trifluoroacetate, ferric citrate, ferric oxalate, ferric acrylate, ferric tris (2,2,6, 6-tetramethyl-3, 5-heptanedionate), ferric hydroxide, ferric acetylacetonate, ferric fluoride iron-containing compounds and hydrates thereof; the ferrous iron comprises ferrous chloride, ferrous bromide, ferrous iodide, ferrous trifluoromethanesulfonate, ferrous tetrafluoroborate, ferrous hexafluorophosphate, ferrous sulfate, ferrous nitrate, ferrous acetate, ferrous trifluoroacetate, ferrous citrate, ferrous oxalate, ferrous acrylate, ferrous bis (2,2,6, 6-tetramethyl-3, 5-heptanedionate), ferrous hydroxide, ferrous acetylacetonate, ferrous fluoride iron-containing compounds and hydrates thereof.
4. The method for preparing the polar functional group-containing polyolefin by iron-catalyzed carbon-hydrogen bond alkylation of the polyolefin chain according to claim 1 or 2, wherein the corresponding organic solvent is one or more of water, a hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, a nitrohydrocarbon solvent, an ether solvent, a nitrile solvent, an ester solvent, an alcohol solvent, an amine solvent, an amide solvent, a sulfone solvent and a sulfoxide solvent.
5. The method of claim 4, wherein the hydrocarbon solvent is one or more selected from benzene, toluene and saturated alkane compounds, the halogenated hydrocarbon solvent is one or more selected from trifluoromethylbenzene, chlorobenzene, dichloromethane, 1, 2-dichloroethane, chloroform and carbon tetrachloride, and the nitrohydrocarbon solvent is one or more selected from nitrobenzene and nitromethane; the ether solvent is one or more of tetrahydrofuran, 1, 4-dioxane, methyl tert-butyl ether and diethyl ether; the nitrile solvent is one or more of acetonitrile, benzonitrile and tert-butyl acetonitrile; the ester solvent is one or more of ethyl acetate, n-butyl acetate and isobutyl acetate; the alcohol solvent is one or more of methanol, ethanol, tert-butyl alcohol, n-butyl alcohol and cyclohexanol, and the amine solvent is one or more of triethylamine, diethylamine and diisopropylethylamine; the amide solvent is one or more of dimethylformamide and dimethylacetamide; the sulfoxide solvent is dimethyl sulfoxide, and can be used in any proportion in various cases.
6. The method for preparing the polyolefin chain with polar functional group by the carbon-hydrogen bond alkylation under the catalysis of iron according to claim 1 or 2, characterized in that the organic solvent is acetonitrile, tert-butyl acetonitrile, ethyl acetate, dichloromethane;
the iron compound is ferric trichloride, ferric tribromide, ferrous chloride, ferrous bromide and ferrous acetate;
the additive is sodium chloride, potassium chloride and tetrabutyl ammonium chloride;
and (3) exposing the reacted system to light with the wavelength of 350-500nm for irradiation.
7. The method for preparing poly-olefins containing polar functional groups by iron catalyzed hydrocarbon chain carbon hydrogen bond alkylation according to claim 1 or 2, wherein the additive is alkali metal salt of halide, alkali metal salt of organic acid compound, alkali metal salt of phenolic compound, ammonium salt of halide, ammonium salt of organic acid compound, ammonium salt of phenolic compound, wherein the halide is fluoride, chloride, bromide, iodide; the alkali metal salt is lithium salt, sodium salt, potassium salt or cesium salt; the organic acid compound is substituted or unsubstituted aryl carboxylic acid, substituted or unsubstituted alkyl carboxylic acid, substituted or unsubstituted aryl sulfonic acid, substituted or unsubstituted alkyl sulfonic acid, substituted or unsubstituted aryl phosphoric acid and substituted or unsubstituted alkyl phosphoric acid; the phenols are substituted or unsubstituted phenol compounds; the ammonium salt is tetramethylammonium salt, tetraethylammonium salt or tetrabutylammonium salt.
8. The method for preparing polyolefin chain poly-olefin containing polar functional group by iron-catalyzed carbon-hydrogen bond alkylation according to claim 1 or 2, wherein the molar ratio of the iron compound to the polymer monomer is (0.001-0.01): 1, the molar ratio of the electron-deficient olefin to the polymer monomer is (0.025-0.5): 1; the molar ratio of the iron compound to the additive is (0.1-10): 1; the organic solvent is added in an excessive amount.
9. The method for preparing the polyolefin chain with polar functional group by the carbon-hydrogen bond alkylation under the catalysis of iron according to claim 1 or 2, wherein the temperature condition is provided as follows: placing the reacted system at 25-150 ℃;
the lighting condition of the light energy comprises: the reacted system is exposed to visible light and/or monochromatic or mixed light of a wavelength of less than 500 nm.
CN202210762552.0A 2022-06-30 2022-06-30 Method for preparing polar functional group-containing olefin by iron-catalyzed polyolefin chain carbon-hydrogen bond alkylation Pending CN114957518A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0872469A1 (en) * 1997-04-15 1998-10-21 Union Carbide Chemicals & Plastics Technology Corporation Process for producing aldehyde acids or salts thereof
CA2554006A1 (en) * 2004-02-26 2005-09-09 Universiteit Gent Metal complexes for use in olefin metathesis and atom group transfer reactions
CN103819594A (en) * 2014-01-28 2014-05-28 汕头大学 Polyolefin plastic light-biodegradable modified additive as well as preparation and application thereof
CN113321579A (en) * 2021-05-27 2021-08-31 中山大学 Oxidative degradation method of aryl-containing polymer and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0872469A1 (en) * 1997-04-15 1998-10-21 Union Carbide Chemicals & Plastics Technology Corporation Process for producing aldehyde acids or salts thereof
CA2554006A1 (en) * 2004-02-26 2005-09-09 Universiteit Gent Metal complexes for use in olefin metathesis and atom group transfer reactions
CN103819594A (en) * 2014-01-28 2014-05-28 汕头大学 Polyolefin plastic light-biodegradable modified additive as well as preparation and application thereof
CN113321579A (en) * 2021-05-27 2021-08-31 中山大学 Oxidative degradation method of aryl-containing polymer and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GUOXIANG ZHANG,ZONGNAN ZHANG，RONG ZENG: ""Photoinduced FeCl3-Catalyzed Alkyl Aromatics Oxidation toward Degradation of Polystyrene at Room Temperature"", pages 3225 *
YUNHE JIN 等: ""Convenient C(sp3)–H bond functionalisation of light alkanes and other compounds by iron photocatalysis"", 《GREEN CHEMISTRY》, pages 6984 *

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