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CN-122011422-A - Polymethyl methacrylate polymer covalently modified graphene oxide composite material with end group containing manganese porphyrin group and preparation method thereof

CN122011422ACN 122011422 ACN122011422 ACN 122011422ACN-122011422-A

Abstract

A graphene oxide composite material covalently modified by polymethyl methacrylate polymer with a terminal group containing a manganese porphyrin group and a preparation method thereof belong to the technical field of nonlinear optical materials, and are characterized in that the composite material is formed by covalently modifying graphene oxide by polymethyl methacrylate with a terminal group containing a manganese porphyrin group, the preparation method of the material comprises the steps of preparing polymethyl methacrylate with a manganese porphyrin group at the end group through an atom transfer radical polymerization method, and carrying out covalent connection with graphene oxide to prepare a polymethyl methacrylate covalent modified graphene oxide composite material with the manganese porphyrin group at the end group, wherein the material is a nonlinear optical material. The method can prepare the composite material with good nonlinear optical performance.

Inventors

  • ZHANG SHOUFENG
  • LIANG CHEN

Assignees

  • 吉林建筑大学

Dates

Publication Date
20260512
Application Date
20260328

Claims (7)

  1. 1. The graphene oxide composite material is characterized in that the composite material is formed by covalent bonds of polymethyl methacrylate groups with manganese porphyrin as end groups and graphene oxide, the chemical formula of the composite material is MnPor-PMMA n -GO, and the structural formula of the graphene oxide composite material is as follows: 。
  2. 2. The graphene oxide composite material covalently modified by polymethyl methacrylate polymer with a terminal group containing manganese porphyrin group according to claim 1, which is characterized in that the preparation method of the composite material comprises the following steps: Firstly, monohydroxy porphyrin and Mn (CH 3 COO) 2.4H2O are added into a three-neck flask, and DMF is added to dissolve reactants. It was placed in a thermostat water bath and stirred overnight under reflux. Subsequently, the reaction was allowed to settle by pouring it into distilled water and allowed to stand overnight. Centrifuge 5 min with a bench top centrifuge 10000 r/min. Collecting precipitate, drying, and drying for 24 h to obtain blue-violet solid powder with chemical formula of MnPor-OH; Step two, mnPor-OH, anhydrous dichloromethane and triethylamine are added into a two-neck flask, stirred at room temperature, alpha-bromo isobutyryl bromide dissolved by the anhydrous dichloromethane is added into the mixed solution through a constant pressure dropping funnel, and the reaction is continued under an ice water bath. After the reaction was completed, the mixed solution was washed with 0.1 mol L -1 of diluted hydrochloric acid solution, saturated sodium bicarbonate solution and saturated NaCl solution, respectively, dried by adding anhydrous Na 2 SO 4 , filtered, and the drying agent was filtered, and the dichloromethane solvent was removed by distillation under reduced pressure. Purifying the obtained crude product by column chromatography, wherein the eluent is dichloromethane and petroleum ether, and collecting a first color band product to obtain blue-violet solid powder with a chemical formula of MnPor-Br; preparing a polymethyl methacrylate polymer with a manganese porphyrin group-containing end group by an ATRP method, specifically, placing cuprous bromide, N, N, N ', N ' ', N ' ' -pentamethyl divinyl triamine and N, N-dimethylformamide on one side of an H-type reaction tube under the protection of nitrogen, stirring at room temperature, placing N, N-dimethylformamide, mn-Por-Br and methyl methacrylate on the other side of the H-type reaction tube, fully stirring, then mixing the mixture on two sides of the H-type reaction tube, exposing the mixture to air to terminate the reaction after the reaction is finished, removing copper complex remained in a reaction system by using THF (THF), settling and purifying in cold methanol by using neutral alumina, filtering to collect insoluble matters, and drying under vacuum to obtain light purple solid powder of a polymethyl methacrylate value polymer with a porphyrin group-containing end group, wherein the chemical formula is MnPor-PMMA n ; And fourthly, preparing MnPor-PMMA n -GO by adopting Williamson ether synthesis reaction, wherein the preparation method comprises the following steps of firstly adding acetonitrile into a two-neck flask, adding anhydrous potassium carbonate into the two-neck flask, stirring at room temperature, adding graphene oxide into the solution, continuously stirring, finally, adding Por-PMMA n into a reaction system, stirring at 80 ℃ for 24h, and centrifugally separating a crude product, and washing the crude product by dichloromethane, ethanol and deionized water respectively to obtain the brown solid powder of the graphene oxide composite material of which the end group contains porphyrin group and the polymethyl methacrylate polymer is covalently modified, wherein the chemical formula of the brown solid powder is Por-PMMA n -GO.
  3. 3. The graphene oxide composite material covalently modified by a polymethyl methacrylate polymer having a terminal group containing a manganese porphyrin group according to claim 1, wherein n is a polymerization degree of PMMA in a range of 105≤n≤200.
  4. 4. The method for preparing a graphene oxide composite material covalently modified by a polymethyl methacrylate polymer having a manganese porphyrin group at a terminal group according to claim 2, wherein in the first step, the molar ratio of monohydroxy porphyrin to Mn (CH 3 COO) 2.4H2O is 1:2.5.
  5. 5. The method for preparing a graphene oxide composite material covalently modified by a polymethyl methacrylate polymer with a terminal group containing a manganese porphyrin group according to claim 2, wherein in the second step, the mobile phase purified by column chromatography is a mixture of dichloromethane and petroleum ether, and the volume ratio of the mobile phase to the petroleum ether is 1:10.
  6. 6. The method for preparing a graphene oxide composite material covalently modified by a polymethyl methacrylate polymer with a manganese porphyrin group-containing end group according to claim 2, wherein in the third step, the molar ratio of cuprous bromide, N, N, N ', N ' ', N ' ' -pentamethyldivinyl triamine and Mn-Por-Br is 1:1:1.
  7. 7. The method for preparing a graphene oxide composite material covalently modified by a polymethyl methacrylate polymer with a terminal group containing a manganese porphyrin group according to claim 2, wherein in the fourth step, anhydrous potassium carbonate is excessively added until an acetonitrile solution is clarified from colorless.

Description

Polymethyl methacrylate polymer covalently modified graphene oxide composite material with end group containing manganese porphyrin group and preparation method thereof Technical Field A polymethyl methacrylate polymer covalent modified graphene oxide composite material with a terminal group containing a manganese porphyrin group and a preparation method thereof belong to the technical field of nonlinear optical materials. Background Porphyrin is an organic compound with a macrocyclic conjugated structure, which is generally defined as a substance with substituents linked on the porphine ring, and since the periphery of the porphyrin is substituted by various substituents, the central metal particles can be changed and even the size of the ring can be expanded, so that the porphyrin has good molecular modifiable property, and has an 18 pi electron conjugated structure, and has been widely introduced into the research of nonlinear optics field by extensive researchers. The nonlinear optical principle of porphyrin can be explained by a five-level model, that is, porphyrin in a ground state (S 0) is irradiated by light with a specific wavelength, electrons in the porphyrin generate electron transitions to reach a first excited state (S 1), at this time, electrons have three directions, one of which is to reach a second excited state (S 2) by further absorbing energy, the other of which is to further absorb energy by electrons in S 1, reach a triplet state (τ 1) by intersystem crossing and then reach a triplet excited state (τ 2) by irradiation of intense light (referred to as laser), which is the basic principle of reverse saturation absorption, and the third of which is to drop electrons in S 1 back to S 0 by releasing energy. Therefore, how to make more porphyrin reach S 1 is one of the key problems of how to enhance the nonlinear optical properties of porphyrin molecules, namely, reducing the band gap between S 0-S1. In a great deal of research in the past, porphyrin was modified with a central metal through a peripheral substituent such that the characteristic absorption peak of the porphyrin was red shifted. Although some progress has been made, due to the increased planarity and rigidity of the metallization, a significant aggregation tendency (e.g., J aggregation) occurs between porphyrin molecules, which results in a decrease in the solubility of the porphyrin, severely inhibiting its potential for use in practical applications. And a great deal of research at the present stage is focused on researching the nonlinear optical characteristics of porphyrin in a liquid system, which has weaker guiding significance for practical application, and if porphyrin is directly doped in a solid system, the performance is nonuniform due to poor solubility of porphyrin, so that the application potential of the porphyrin nonlinear optical material in practical application is seriously hindered. Graphene oxide has sp2 hybridized honeycomb lamellar morphology and has a good pi electron conjugated structure, so that the graphene oxide is widely introduced into the nonlinear optical field. And the surface of the porphyrin has a large amount of oxygen-containing functional groups, so that covalent grafting can be carried out on the porphyrin, and the aggregation tendency among porphyrin molecules is inhibited. On the basis, porphyrin and graphene oxide can also form an electron donor-acceptor system, electron transfer is realized through the conjugated structure of the graphene oxide, the relaxation time of electrons in porphyrin is increased, the absorption section of S 1 is improved, and the composite material can show better and excellent nonlinear optical characteristics. Therefore, it is expected to solve the above problems to metalize porphyrin, covalently bond with graphene oxide, and dope the composite material into a solid matrix in a chemical bonding manner. At present, the combination of metalloporphyrin, macromolecule and graphene oxide has not been reported yet. Disclosure of Invention The invention relates to a polymethyl methacrylate polymer covalent modified graphene oxide composite material with a manganese porphyrin group-containing end group and a preparation method thereof, and the prepared composite material shows good nonlinear optical performance, has good dispersibility in a solid organic reagent, can be used for preparing optical plastics, has good application prospect in the nonlinear optical field, and has a structural formula shown as follows: The molecular weight of the polymethyl methacrylate polymer with the end group containing the manganese porphyrin group is in the range of 5000-10000. The invention relates to a graphene oxide composite material covalently modified by polymethyl methacrylate polymer with a manganese porphyrin group at the end group and a preparation method thereof, which belong to the technical field of nonlinear optical materials, and are characterized in that the composi