Method for catalyzing, grafting and modifying polyolefin by using benzophenone derivative

Abstract

The invention discloses a method for catalytic grafting modification of polyolefin by using a benzophenone derivative, and relates to the technical field of grafting modification of high polymer materials, and the method is characterized by comprising the following steps: adding a raw material, an unsaturated monomer containing an electron withdrawing group and a catalyst into an organic solvent, uniformly stirring, carrying out continuous illumination reaction for 5-150 minutes under the action of a specific light source, filtering, washing, and drying to obtain the benzophenone derivative. Grafting modification of the surface of the polyolefin plastic is realized, and the catalyst is a benzophenone derivative. The preparation method is suitable for various polyolefin materials and forms, and has the advantages of simple and rapid preparation process, safe operation and small environmental pollution.

Description

Technical Field

[0001] The present invention relates to the technical field of graft modification of polymer materials, and more specifically, it relates to a method for catalytic graft modification of polyolefins with benzophenone derivatives. Background Art

[0002] In recent years, people have made considerable efforts to solve the problem of polyolefin inertness, including modifying polyolefins using physical methods. For example, filling modification, blending modification, etc. can achieve microscopic regulation of certain properties, have strong operability, and can greatly reduce costs, and are still the main means at present. However, these methods cannot truly solve the problem of polyolefin surface inertness and only slightly adjust certain properties of polyolefins to a certain extent. Chemical modification modifies polyethylene through chemical methods, changes the types of atoms or atomic groups on the macromolecule and their bonding methods, and achieves a qualitative leap. In view of this, the present invention proposes a method for catalytic graft modification of polyolefins with benzophenone derivatives. Summary of the Invention

[0003] The purpose of the present invention is to provide a method for catalytic graft modification of polyolefins with benzophenone derivatives, which is suitable for various polyolefin materials and forms, and at the same time has the advantages of simple and fast preparation process, safe operation, and small environmental pollution.

[0004] The above technical purpose of the present invention is achieved through the following technical solutions:

[0005] A method for catalytic graft modification of polyolefins with benzophenone derivatives, comprising the following steps:

[0006] Add raw materials, an unsaturated monomer containing an electron-withdrawing group, and a catalyst to an organic solvent, stir evenly, and under the action of a specific light source, continuously irradiate and react for 5 min - 150 min to achieve graft modification on the surface of the polyolefin plastic, and the catalyst is a benzophenone derivative.

[0007] The present invention is further set as: the molar ratio of the polyolefin to the unsaturated monomer containing an electron-withdrawing group is (5 - 20):10.

[0008] The present invention is further set as: the raw material is a polyolefin or a polymer containing an alkyl chain, and the polyolefin includes one or more of polyethylene, polypropylene, and polystyrene.

[0009] The present invention is further set as: the unsaturated monomer containing an electron-withdrawing group is an olefin monomer with a polar group, the polar group is amino, carboxyl, hydroxyl, sulfonic acid group, epoxy group, halogen, amide, cyano, and silyl group, and the olefin is one or more of monoolefins and polyolefins.

[0010] The present invention is further configured as follows: the organic solvent includes one or more of tetrahydrofuran (THF), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), dichloromethane (DCM), chloroform (CHCl3), toluene (C6H5CH3), xylene, dichlorobenzene, trichlorobenzene, petroleum ether, acetone (AC), methyl tert-butyl ether (MTBE), N-methylpyrrolidone (NMP), ethyl acetate (EA), methanol (MeOH), ethanol (EtOH), acetonitrile (ACN), ethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC), diethyl carbonate (DEC), dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC).

[0011] The present invention is further configured as follows: the molar ratio of the polyolefin to the organic solvent is (1-3):10.

[0012] The present invention is further configured as follows: the benzophenone derivatives include one or more of monosubstituted benzophenone derivatives, disubstituted benzophenone derivatives and polysubstituted benzophenone derivatives.

[0013] The present invention is further configured as follows: the molar ratio of the benzophenone derivative to the polyolefin is (1-15):100.

[0014] The present invention is further configured as follows: the specific light source is an ultraviolet light source (1-380nm).

[0015] The present invention is further configured as follows: the illumination reaction time is 30 min-90 min.

[0016] In summary, the present invention has the following beneficial effects:

[0017] Under the excitation of a specific light source, the benzophenone derivative absorbs the wavelength to reach an excited state, thereby seizing the CH bond of the polyolefin plastic, and then the C free radical that loses the H atom couples with the unsaturated monomer containing an electron-withdrawing group to achieve grafting modification of the surface of the polyolefin plastic. In this application, the role of benzophenone is to be a catalyst for the breakage of the CH bond; the role of the specific light source is to activate benzophenone; the role of the unsaturated monomer containing an electron-withdrawing group is to modify the grafting modification of the polyolefin surface; the role of the wetting agent is to reduce the interface impedance and increase the contact area. The preparation method is simple in process and mild in reaction conditions, and can achieve surface modification of different polyolefins and different states, such as powder, fiber, line, film, block, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 A schematic diagram of a benzophenone derivative involved in the application example scheme;

[0019] Figure 2Schematic diagram of (3,5-difluoro)(4-fluoro) benzophenone involved in the solution of the application example

[0020] Figure 3 Infrared characterization diagram of the modified polyethylene film in Example 1 of this application and Comparative Example 1

[0021] Figure 4 Water contact angle test result diagram of the modified polyethylene film in Example 1 of this application and Comparative Example 1

[0022] Figure 5 Infrared characterization diagram of the modified polyethylene film in Example 2 of this application and Comparative Example 2

[0023] Figure 6 Water contact angle test result diagram of the modified polyethylene film in Example 2 of this application and Comparative Example 2

[0024] Figure 7 Infrared characterization diagram of the modified polyethylene film in Example 3 of this application and Comparative Example 3

[0025] Figure 8 Water contact angle test result diagram of the modified polyethylene film in Example 3 of this application and Comparative Example 3

[0026] Figure 9 Infrared characterization diagram of the modified polyethylene film in Example 4 of this application and Comparative Example 4

[0027] Figure 10 Water contact angle test result diagram of the modified polyethylene film in Example 4 of this application and Comparative Example 4

[0028] Figure 11 Infrared characterization diagram of the modified polyethylene film in Example 5 of this application and Comparative Example 5

[0029] Figure 12 Water contact angle test result diagram of the modified polyethylene film in Example 5 of this application and Comparative Example 5

[0030] Figure 13 Schematic diagram of the general strategy for catalytic grafting modification of polyolefins with a class of benzophenone derivatives in this application Detailed implementation mode

[0031] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0032] Example 1

[0033] Put 0.1 mol of polyethylene film into a mixed solution consisting of 0.5 mol of acetonitrile, 0.1 mol of α-methylacrylic acid, and 0.01 mol of (3,5-difluoro)(4-fluoro)benzophenone. Keep the whole reaction under continuous light irradiation at 365 nm for 1 h. Take the polyethylene film after the reaction and Soxhlet extract it in a benzophenone solution for 48 h to remove the unreacted monomers adsorbed on the surface.

[0034] Example 2

[0035] Put 0.1 mol of polyethylene film into a mixed solution consisting of 0.5 mol of acetonitrile, 0.1 mol of butyl 2,2,3,4,4,4-hexafluoracrylate, and 0.01 mol of (3,5-difluoro)(4-fluoro)benzophenone. Keep the whole reaction under continuous light irradiation at 365 nm for 1 h. Take the polyethylene film after the reaction and Soxhlet extract it in a benzophenone solution for 48 h to remove the unreacted monomers adsorbed on the surface.

[0036] Example 3

[0037] Put 0.1 mol of polyethylene film into a mixed solution consisting of 0.5 mol of acetonitrile, 0.1 mol of glycidyl methacrylate, and 0.01 mol of (3,5-difluoro)(4-fluoro)benzophenone. Keep the whole reaction under continuous light irradiation at 365 nm for 1 h. Take the polyethylene film after the reaction and Soxhlet extract it in a benzophenone solution for 48 h to remove the unreacted monomers adsorbed on the surface.

[0038] Example 4

[0039] Put 0.1 mol of polyethylene film into a mixed solution consisting of 0.5 mol of acetonitrile, 0.1 mol of butyl methacrylate, and 0.01 mol of (3,5-difluoro)(4-fluoro)benzophenone. Keep the whole reaction under continuous light irradiation at 365 nm for 1 h. Take the polyethylene film after the reaction and Soxhlet extract it in a benzophenone solution for 48 h to remove the unreacted monomers adsorbed on the surface.

[0040] Example 5

[0041] Put 0.1 mol of polyethylene film into a mixed solution consisting of 0.5 mol of acetonitrile, 0.1 mol of methyl methacrylate, and 0.01 mol of (3,5-difluoro)(4-fluoro)benzophenone. Keep the whole reaction under continuous light irradiation at 365 nm for 1 h. Take the polyethylene film after the reaction and Soxhlet extract it in a benzophenone solution for 48 h to remove the unreacted monomers adsorbed on the surface.

[0042] Comparative Example 1

[0043] Put 0.1 mol of polyethylene film into a mixed solution of 0.5 mol of acetonitrile and 0.1 mol of α-methylacrylic acid. The whole reaction is kept under continuous illumination with a 365 nm light source for 1 h. Take the reacted polyethylene film and Soxhlet extract it in methyl ketone solution for 48 h to remove the unreacted monomers adsorbed on the surface.

[0044] Comparative Example 2

[0045] Put 0.1 mol of polyethylene film into a mixed solution of 0.5 mol of acetonitrile and 0.1 mol of butyl 2,2,3,4,4,4-hexafluoracrylate. The whole reaction is kept under continuous illumination with a 365 nm light source for 1 h. Take the reacted polyethylene film and Soxhlet extract it in methyl ketone solution for 48 h to remove the unreacted monomers adsorbed on the surface.

[0046] Comparative Example 3

[0047] Put 0.1 mol of polyethylene film into a mixed solution of 0.5 mol of acetonitrile and 0.1 mol of glycidyl methacrylate. The whole reaction is kept under continuous illumination with a 365 nm light source for 1 h. Take the reacted polyethylene film and Soxhlet extract it in methyl ketone solution for 48 h to remove the unreacted monomers adsorbed on the surface.

[0048] Comparative Example 4

[0049] Put 0.1 mol of polyethylene film into a mixed solution of 0.5 mol of acetonitrile and 0.1 mol of butyl methacrylate. The whole reaction is kept under continuous illumination with a 365 nm light source for 1 h. Take the reacted polyethylene film and Soxhlet extract it in methyl ketone solution for 48 h to remove the unreacted monomers adsorbed on the surface.

[0050] Comparative Example 5

[0051] Put 0.1 mol of polyethylene film into a mixed solution of 0.5 mol of acetonitrile and 0.1 mol of methyl methacrylate. The whole reaction is kept under continuous illumination with a 365 nm light source for 1 h. Take the reacted polyethylene film and Soxhlet extract it in methyl ketone solution for 48 h to remove the unreacted monomers adsorbed on the surface.

[0052] Test Example

[0053] Fourier transform infrared characterization: Use Fourier transform infrared spectroscopy to characterize the reaction examples and comparative examples;

[0054] Water contact angle measurement: Use deionized water as the solvent to characterize the water contact angles of the reaction examples and comparative examples;

[0055] In this application, in Example 1, α-methylacrylic acid is used as the unsaturated monomer containing an electron-withdrawing group, with reference to Figure 9, polyethylene film was added to an acetonitrile solution of α-methacrylic acid and (3,5-difluoro)(4-fluoro)benzophenone, and reacted under 365nm light for 1h. With (3,5-difluoro)(4-fluoro)benzophenone as a catalyst, under the excitation of 365nm light source, (3,5-difluoro)(4-fluoro)benzophenone absorbed the light source to reach an excited state, thereby capturing the CH bond of polyolefin plastic, and then the C free radical that lost the H atom coupled with α-methacrylic acid to achieve grafting modification on the surface of polyolefin plastic.

[0056] In this application, Example 2 uses 2,2,3,4,4,4-butyl hexafluoroacrylate as the unsaturated monomer containing an electron-withdrawing group, referring to Figure 9 , polyethylene film was added to acetonitrile solution of 2,2,3,4,4,4-butyl hexafluoroacrylate and (3,5-difluoro)(4-fluoro)benzophenone, and reacted under 365nm light for 1h. With (3,5-difluoro)(4-fluoro)benzophenone as the catalyst, under the excitation of 365nm light source, (3,5-difluoro)(4-fluoro)benzophenone absorbed the light source to reach the excited state, thereby seizing the CH bond of polyolefin plastic, and then the C free radical that lost the H atom coupled with 2,2,3,4,4,4-butyl hexafluoroacrylate to achieve graft modification on the surface of polyolefin plastic.

[0057] In this application, Example 3 uses glycidyl methacrylate as an unsaturated monomer containing an electron-withdrawing group, referring to Figure 9 , polyethylene film was added to an acetonitrile solution of glycidyl methacrylate and (3,5-difluoro)(4-fluoro)benzophenone, and reacted under 365nm light for 1h. With (3,5-difluoro)(4-fluoro)benzophenone as a catalyst, under the excitation of a 365nm light source, (3,5-difluoro)(4-fluoro)benzophenone absorbed the light source to reach an excited state, thereby capturing the CH bond of the polyolefin plastic, and then the C free radical that lost the H atom coupled with the unsaturated monomer containing an electron-withdrawing group to achieve grafting modification on the surface of the polyolefin plastic.

[0058] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for catalytic graft modification of polyolefins with benzophenone derivatives, characterized in that : It includes the following steps: Add raw materials, unsaturated monomers containing electron-withdrawing groups, and a catalyst into an organic solvent, stir evenly, and under the action of a specific light source, continuously carry out a light reaction for 5 min - 150 min to achieve graft modification on the surface of polyolefin plastics. The catalyst is a benzophenone derivative.

2. A method for catalytic graft modification of polyolefin with benzophenone derivative according to claim 1, characterized in that: The molar ratio of the polyolefin to the unsaturated monomer containing an electron-withdrawing group is (5 - 20) :

10.

3. A method for catalytic graft modification of polyolefin with benzophenone derivative according to claim 1, characterized in that: The raw material is a polyolefin or a polymer containing an alkyl chain. The polyolefin includes one or more of polyethylene, polypropylene, and polystyrene.

4. A method for catalytic graft modification of polyolefin with benzophenone derivative according to claim 1, characterized in that: The unsaturated monomer containing an electron-withdrawing group is an olefin monomer with a polar group. The polar group is amino, carboxyl, hydroxyl, sulfonic acid group, epoxy group, halogen, amide, cyano, and silyl group. The olefin is one or more of monoolefins and polyolefins.

5. A method for catalytic graft modification of polyolefin with benzophenone derivative according to claim 1, characterized in that: The organic solvent includes one or more of tetrahydrofuran (THF), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), dichloromethane (DCM), chloroform (CHCl3), toluene (C6H5CH3), xylene, dichlorobenzene, trichlorobenzene, petroleum ether, acetone (AC), methyl tert-butyl ether (MTBE), N-methylpyrrolidone (NMP), ethyl acetate (EA), methanol (MeOH), ethanol (EtOH), acetonitrile (ACN), ethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC).

6. The method for catalytic graft modification of polyolefin with benzophenone derivative according to claim 1, characterized in that: The molar ratio of the polyolefin to the organic solvent is (1 - 3) :

10.

7. A method for catalytic graft modification of polyolefin by benzophenone derivative according to claim 1, characterized in that: The benzophenone derivative includes one or more of monosubstituted benzophenone derivatives, disubstituted benzophenone derivatives, and polysubstituted benzophenone derivatives.

8. A method for catalytic graft modification of polyolefin with benzophenone derivative according to claim 1, characterized in that: The molar ratio of the benzophenone derivative to the polyolefin is (1 - 15) :

100.

9. A method for catalytic graft modification of polyolefin with benzophenone derivative according to claim 1, characterized in that: The specific light source is an ultraviolet light source (1 - 380 nm).

10. A method for catalytic graft modification of polyolefin with benzophenone derivative according to claim 1, characterized in that: The light reaction time is 30 min - 90 min.

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