CN114891135B - Method for preparing poly-alkene containing polar oxygen function by carbon-hydrogen bond oxidation of polyolefin chain under iron catalysis - Google Patents
Method for preparing poly-alkene containing polar oxygen function by carbon-hydrogen bond oxidation of polyolefin chain under iron catalysis Download PDFInfo
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Abstract
A method for preparing polyolefin chain poly-alkene containing polar oxygen function by iron catalytic carbon hydrogen bond oxidation comprises the following steps: under the action of an iron compound, providing appropriate temperature and/or light energy, and oxidizing carbon-hydrogen bonds of a polyvinyl compound in a solvent in the presence of an oxidant and an additive to realize catalytic functional group conversion to obtain a corresponding oxidation product; the method directly utilizes the commercial polyethylene compound to perform carbon-hydrogen bond oxidation in a catalytic manner, has the advantages of simple reaction, simple operation, short reaction time, mild reaction conditions, high atom economy, higher reaction yield, easy separation and purification of products, good substrate universality and the like, and is suitable for synthesizing the polyethylene compound containing oxygen functional groups and derivatives thereof; meanwhile, cheap metal is utilized to carry out reaction, and the method has great application potential in the fields of metal catalysis, polymer modification, new material synthesis, waste plastic recovery and the like.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a method for preparing polar oxygen functional group-containing olefin by oxidizing carbon-hydrogen bonds of a polyolefin chain under the catalysis of iron, which is a novel synthetic method for preparing an oxidation-containing product by breaking the carbon-hydrogen bonds in the polyethylene compound chain and oxidizing an oxidant under the catalysis of iron.
Background
Polyethylene compounds are important high molecular polymers, which are the main sources of three synthetic materials, plastics, so that polyethylene is 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 oxidation modification of the carbon-hydrogen bond on the polyvinyl compound is an important means for changing the property, performance and added value of the polyvinyl compound, and further realizes the reutilization of the waste plastic. Because the carbon-hydrogen bond on the polymer chain segment has good stability, controllable and catalytic carbon-hydrogen bond oxidation of polyethylene compounds is rarely reported. The oxidation of carbon-hydrogen bond of the existing polyvinyl compound is mainly realized by depending on noble metals such as Ru, ni, mn and the like under the action of a strong oxidant. For example, hartwig, burkline division, university of california, reported that ruthenium, nickel complexes catalyze the oxidation of polyethylene by organic oxidants (Chem 2021,7,137-145 j.am. Chem. Soc.2021,143,4531 acs cent. Sci.2017,3, 895.) with noble metal catalysts, which are costly. Professor Boaen and Hillmyer at the university of Minnesota in the United states reported that metallic Mn catalyzes the same type of reaction (Macromolecules 2003,36, 7027), and that the catalysts are difficult to synthesize and expensive. Cheap metal-catalyzed oxidation of polyvinyls still faces great challenges, but also has a very broad application potential.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing polyolefin with polar oxygen functional groups by iron-catalyzed hydrocarbon chain carbon-hydrogen bond oxidation, which is to perform functional group reaction on polyethylene compounds with different polymerization degrees, namely to generate a series of polyethylene compounds with oxygen functional groups by the reaction of hydrocarbon fracture and oxidant oxidation under the promotion of iron catalyst and oxidant and under the irradiation of visible light; the method has the advantages of simple reaction, mild oxidation conditions, high atom economy, short reaction time, simple operation and the like; the method provides a convenient and fast strategy for the preparation of various polyethylene compounds, can avoid using a large amount of heavy metal salt and strong oxidant by directly utilizing cheap and abundant polyethylene compounds as raw materials, is very attractive in industrial production, and has great application potential in the fields of plastic recovery, polymer modification and the like by utilizing cheap metals for reaction.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for preparing polyolefin with polar oxygen functional group by iron-catalyzed carbon-hydrogen bond oxidation of polyolefin chain comprises the following steps:
under the action of an iron compound, heating temperature and/or light energy are provided, and in the presence of an oxidant and an additive and in a corresponding organic solvent, the scission and addition of chain carbon-hydrogen bonds in a polyvinyl compound are realized, so that a controllable oxidation product is obtained, wherein the reaction equation is as follows:
the polyethylene is of any molecular weight, and the polyethylene comprises low-density polyethylene, high-density polyethylene, linear low-density polyethylene and a copolymer of polyethylene.
The oxidant comprises hydrogen peroxide, peroxyalcohol, peroxyacid, nitric oxide, air, oxygen and laughing gas.
The peroxyalcohols have the general formula
The peroxy acid has the formula
The nitrogen oxides have the formula
Wherein R is 1 、R 2 、R 3 、R 4 、R 5 Including hydrogen, alkyl, phenyl.
A method for oxidizing carbon-hydrogen bonds of polyethylene chains under the catalysis of iron comprises the following reaction steps:
(1) Sequentially adding an iron compound, an additive, a polyvinyl compound, an oxidant and an organic solvent into a dried reaction tube, stirring and dissolving after the addition is finished, uniformly mixing, and irradiating the reaction tube under light with specific power and wavelength and continuously stirring or heating the reaction tube to a specific temperature;
(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, ferric tris (2, 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, 6-tetramethyl-3, 5-heptanedionate), ferrous hydroxide, ferrous acetylacetonate, ferrous fluoride and iron compounds and hydrates thereof.
Preferably, the corresponding iron catalyst is ferric chloride, ferric tribromide, ferrous chloride, ferrous bromide, or ferrous acetate.
The 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, and the molar ratio of the oxidant 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 heating temperature conditions provided are as follows: the reacted system was placed at 25 ℃ to 150 ℃.
The light 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.
Preferably, the reacted system is exposed to light having a wavelength of 350-500 nm.
The innovation point of the invention is to develop a controllable and efficient one-step oxidation method of the polyvinyl compound with cheap and easily obtained raw materials. The invention provides a controllable and catalytic oxidation method for polyethylene, which can efficiently and quickly obtain corresponding oxygen-containing functional group polyethylene 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, short reaction time, safety, greenness, simple operation, no need of a large amount of high-valence metal salt, wide substrate applicability and capability of preparing the polyethylene 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 polyvinyl compound which is widely available, cheap and easily available is used as a substrate, and the reaction time is short.
(4) And the oxidant is convenient to use and easy to obtain.
(5) The method can quickly and simply synthesize the polyvinyl compounds with different oxygen-containing functional groups.
(6) The product is easy to separate and purify, and can be further derived to prepare useful high polymers.
Detailed Description
The idea and the technical effect of the present invention will be clearly and completely described in the following with reference to the embodiments, so as to fully understand the purpose, the scheme and the effect of the present invention. It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict. The following examples are provided to aid in the understanding of the present invention, but are not intended to limit the scope of the invention.
Example 1
Adding ferric trichloride (1.0 mol%), tetrabutylammonium chloride (1.0 mol%), low density polyethylene (LDPE, 2.0 mmol monomer equivalent) and chlorobenzene (2 ml) into a dry reaction tube in sequence, stirring and dissolving under the air after the addition is finished, uniformly mixing, placing the reaction tube under light (hv) with the wavelength of 390nm for room temperature irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, adding ethanol to separate out solids, filtering, washing and drying in vacuum to obtain a target product. 1 H NMR(400MHz,C 2 D 2 Cl 4 110 ℃ C. Delta.3.78-3.50 (m, 8.6H), 2.97-2.25 (m, 8.51H), 2.15-0.58 (m, 400H). The functionalization rate (2-10 mol%) is controlled depending on the reaction time.
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; also, iron trifluoromethanesulfonate, iron tetrafluoroborate, iron hexafluorophosphate, iron sulfate, iron nitrate, iron trifluoroacetate, iron citrate, iron oxalate, iron acrylate, iron tris (2, 6-tetramethyl-3, 5-heptanedionate), iron hydroxide, iron acetylacetonate, iron fluoride-containing compound and hydrates thereof were used instead of iron trichloride in example 1, 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, 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.
The organic solvent except for those listed in the above examples, phCF3 in example 2 was replaced with the other organic solvents listed in the summary of the invention, 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 polyethylene as a substrate to carry out oxidation of different substituents on carbon-hydrogen bonds of the polyethylene, 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 oxidation of the polyethylene 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, does not need to add 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 (10)
1. A method for preparing polyolefin with polar oxygen function by carbon-hydrogen bond oxidation of polyolefin chains under iron catalysis is characterized by comprising the following steps:
under the action of iron compound, heating temperature and/or light energy are provided, and the breaking and addition of carbon-hydrogen bonds on chains in polyvinyl compounds are realized in corresponding organic solvent in the presence of oxidant and additive, so as to obtain controllable oxidation product,
the polyethylene has any molecular weight, and comprises low-density polyethylene, high-density polyethylene, linear low-density polyethylene and a copolymer of polyethylene;
the oxidant comprises hydrogen peroxide, peroxyalcohol, peroxyacid, nitrogen oxide, air and oxygen;
the peroxyalcohols have the formula
The peroxy acid has the formula
The nitrogen oxide is of the formula
Compound of (2), NO 2 NO or laughing gas, wherein R 1 、R 2 、R 3 、R 4 、R 5 Including hydrogen, alkyl, phenyl;
the iron compound is an iron-containing compound, including ferric iron or ferrous iron compounds;
the additive is an alkali metal salt of a halide, an alkali metal salt of an organic acid compound, an alkali metal salt of a phenolic compound, an ammonium salt of a halide, an ammonium salt of an organic acid compound, an ammonium salt of a phenolic compound.
2. The method for preparing the polyolefin chain with the polar oxygen functional group by the carbon-hydrogen bond oxidation through iron catalysis according to claim 1 is characterized in that the reaction steps are as follows:
(1) Sequentially adding an iron compound, an additive, a polyvinyl compound, an oxidant and an organic solvent into a dried reaction tube, stirring and dissolving after the addition is finished, uniformly mixing, and irradiating the reaction tube under light with specific power and wavelength and continuously stirring or heating the reaction tube to a specific temperature;
(2) And (2) after the reaction in the step (1) is completed, removing the reaction tube from the light source, adding ethanol to expel solid, filtering, and washing to completely remove the residual unsaturated olefin.
3. The method for preparing the poly-alkene containing the polar oxygen function through carbon-hydrogen bond oxidation of the polyolefin chain catalyzed by iron according to claim 1 or 2, wherein the trivalent 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, 6-tetramethyl-3, 5-heptanedionate), ferric hydroxide, ferric acetylacetonate, ferric fluoride 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, 6-tetramethyl-3, 5-heptanedionate), ferrous hydroxide, ferrous acetylacetonate, ferrous fluoride iron-containing compounds and hydrates thereof.
4. The method for preparing the polar oxygen functional group-containing olefin by the carbon-hydrogen bond oxidation of the polyolefin chain under the catalysis of the iron according to claim 1 or 2, wherein the organic solvent is one or more of 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 the sulfoxide solvent can be used in any proportion in various cases.
6. The method for preparing poly-alkene containing polar oxygen function by carbon-hydrogen bond oxidation of polyolefin chain catalyzed by iron as claimed in claim 4, wherein the organic solvent is chlorobenzene, trifluorotoluene, 1, 2-dichloroethane, dichloromethane.
7. The method for preparing polyolefin chains with polar oxygen functional groups by carbon-hydrogen bond oxidation catalyzed by iron according to claim 1 or 2, wherein the halide is fluoride, chloride, bromide or 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 the polyolefin chain with the polar oxygen functional group by the carbon-hydrogen bond oxidation under the catalysis of the iron according to claim 1 or 2, wherein the additive is sodium chloride, potassium chloride or tetrabutylammonium chloride.
9. The method for preparing polyolefin chain poly-alkene containing polar oxygen function by iron-catalyzed carbon-hydrogen bond oxidation according to claim 1 or 2,
the molar ratio of the iron compound to the polymer monomer is (0.001-0.01): 1, and the molar ratio of the oxidizing agent to the polymer monomer is (0.025-0.5): 1; the molar ratio of iron compound to additive is (0.1-10): 1;
the heating temperature conditions provided are as follows: placing the reacted system at 25-150 ℃;
the specific lighting conditions include: the reacted system is exposed to visible light and/or monochromatic or mixed light with a wavelength of less than 500 nm.
10. The method for preparing polyolefin chain poly-alkene containing polar oxygen function by iron-catalyzed carbon-hydrogen bond oxidation according to claim 1 or 2,
the iron catalyst is ferric chloride, ferric tribromide, ferrous chloride, ferrous bromide and ferrous acetate;
and (3) exposing the reacted system to light with the wavelength of 350-500nm for irradiation.
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| CN1215412A (en) * | 1996-04-05 | 1999-04-28 | 埃克森化学专利公司 | Process for oxidative functionalization of polymers containing alkylstyrene |
| US20040249086A1 (en) * | 2003-06-05 | 2004-12-09 | Boaen Nicole K. | Oxyfunctionalization of polyolefins |
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| CN1215412A (en) * | 1996-04-05 | 1999-04-28 | 埃克森化学专利公司 | Process for oxidative functionalization of polymers containing alkylstyrene |
| US20040249086A1 (en) * | 2003-06-05 | 2004-12-09 | Boaen Nicole K. | Oxyfunctionalization of polyolefins |
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| Oxidative α‑C−C Bond Cleavage of 2° and 3° Alcohols to Aromatic Acids with O2 at Room Temperature via Iron Photocatalysis;Zongnan Zhang;《Org. Lett.》;20210326;第23卷;2915-2920 * |
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