CN110804142A

CN110804142A - Novel ATRP reagent based on black phosphorus and preparation method and application thereof

Info

Publication number: CN110804142A
Application number: CN201911159712.7A
Authority: CN
Inventors: 张斌; 顾敏超; 车强; 樊菲; 陈彧
Original assignee: East China University of Science and Technology
Current assignee: East China University of Science and Technology
Priority date: 2019-11-22
Filing date: 2019-11-22
Publication date: 2020-02-18

Abstract

The invention belongs to a method for grafting BP nano-sheets by an Atom Transfer Radical Polymerization (ATRP) reagent containing acyl chloride groups in molecules through a covalent modification method to obtain a novel ATRP reagent based on black phosphorus. The method is suitable for various ATRP reagents containing acyl chloride in molecules and can be effectively suitable for a series of ATRP polymerized monomers, a platform is provided for the modification of the black phosphorus nanosheet, and the black phosphorus nanosheet material modified by the material of the method has outstanding solubility and charge transmission property compared with pure black phosphorus nanosheets, so that the black phosphorus nanosheet material has wide application prospect in the aspect of photoelectric devices. The invention is suitable for ATRP reagents containing acyl chloride in molecules, such as 2-bromine isobutyryl bromide (BIBB), 2-chloropropionyl chloride and the like.

Description

Novel ATRP reagent based on black phosphorus and preparation method and application thereof

Technical Field

The invention belongs to the technical field of preparation of black phosphorus materials and covalent grafting of the black phosphorus materials and an ATRP polymerization initiator through covalent modification so as to conveniently perform polymerization modification on the surfaces of black phosphorus nanosheets, and particularly relates to modification of the black phosphorus nanosheets by using diazonium salts and covalent grafting of an ATRP reagent and the black phosphorus nanosheets.

Background

The development of two-dimensional materials over the past decade has made a breakthrough in that materials with thicknesses of only one or a few atomic layers are excellent materials for exploring fundamental quantum physics and exploring the size impact of semiconductor materials because of extremely small thicknesses and weak interlayer interactions. The two-dimensional materials that have received the most widespread attention are graphene, which exhibits a weak on-off ratio in electronic devices because of its lack of an intrinsic band gap, and transition metal disulfides, a class of "MX₂"type materials, where the metals M are typically molybdenum, tungsten, and platinum, tin, etc. which have received attention recently, and X is typically sulfur, selenium, and tellurium. Most of the transition metal disulfides are semiconductors with a large band gap (>1.5eV), such as molybdenum disulfide and tungsten disulfide, their poor charge transport capability and poor fermi level matching at the semiconductor-metal interface severely limit their practical applications.

Since the first synthesis of black phosphorus over 100 years ago, researchers first stripped a few layers of black phosphorus 2014. As the scale is reduced, black phosphorus exhibits a range of semiconductor characteristics such as thickness-dependent band gap, spectrum encompassing visible to near infrared, and hole-dominated bipolar transport properties, which make black phosphorus a potential base material for next-generation electronic and optoelectronic products.

The orthorhombic lattice structure with low symmetry of black phosphorus results in-plane anisotropy, thereby achieving crystal orbital control of basic optical and electronic properties. Researchers have invested a lot of resources in the theoretical and experimental fields to study the basic physical and chemical characteristics of black phosphorus and phospholene, and meanwhile, people have designed special methods such as interface regulation, defect regulation, band gap regulation and the like to prepare heterostructures for designing efficient black phosphorus-based photoelectric devices and functional devices.

The ATRP reagent grafted black phosphorus nanosheet material containing acyl chloride designed by the invention is a general material for in-situ polymerization growth of high molecules on the surface of black phosphorus, and provides a platform for covalent grafting of black phosphorus.

Disclosure of Invention

The invention aims to provide a novel ATRP reagent based on black phosphorus and a preparation method and application thereof

The invention also aims to covalently graft ATRP reagent containing acyl chloride in the molecule and black phosphorus; provides a platform for graft polymerization of black phosphorus nanosheets and a method for chemically protecting black phosphorus through covalent modification by using an ATRP reagent.

The technical scheme of the invention is as follows:

a novel black phosphorus-based ATRP reagent has the following structural formula BP-BIBB:

the invention also provides a preparation method of the novel ATRP reagent based on black phosphorus, which comprises the following steps:

1) under the inert gas atmosphere, adding black phosphorus nanosheets, 4-hydroxybenzene diazo tetrafluoroborate (compound 1) and tetrabutyl ammonium hexafluorophosphate (compound 2) into an acetonitrile solvent for reaction, and separating and purifying to obtain BP-C₆H₄OH; the preferred molar ratio of compound 1: compound 2 ═ 1: 1-1: 2 is added into 20 to 60ml of acetonitrile solvent, compound 1, compound 2 and BP-C₆H₄The structural formula of OH is as follows:

2) under the inert gas atmosphere, adding BP-C₆H₄OH, triethylamine (compound 3) and BIBB (compound 4) are reduced in Tetrahydrofuran (THF) solution, and BP-BIBB is obtained through separation and purification; the preferred molar ratio of compound 3: compound 4 ═ 1: 2-2: 1 in Tetrahydrofuran (THF) solution 20-60 ml;

the structural formula of BP-BIBB is as follows:

the invention also provides application of the novel ATRP reagent based on black phosphorus in-situ ATRP polymerization reaction, in particular application of the novel ATRP reagent in-situ growth of polymers with black phosphorus nanosheets as substrates, and the novel ATRP reagent is suitable for common ATRP polymerization monomers such as methyl methacrylate and the like.

The invention also provides a specific application of the novel ATRP reagent based on black phosphorus in polymerization, in an inert gas atmosphere, BP-BIBB, solketal acrylate (compound 5), cuprous iodide (compound 6), N, N, N ', N ', N ' -pentamethyl diethylene triamine (compound 7) are heated and react for about 1-12 hours in a dry tetrahydrofuran solvent, products are precipitated by dropping methanol after the reaction is finished, and BP-PSA is obtained by suction filtration and washing; the results for compound 5, compound 6, compound 7, BP-PSA are as follows:

CuI

compound 6;

one of the novel ATRP reagents based on black phosphorus is used for obtaining BP-PSA, and covalent grafting of high-molecular PSA can enable black phosphorus nanosheets to obtain better solubility in an organic solvent, so that organic electronic devices based on black phosphorus can be prepared by using a low-cost solution method including spraying and printing.

The novel black phosphorus nanosheet material modified by the ATRP reagent BIBB prepared by the invention can be suitable for various monomers which are initiated by the BIBB and are suitable for ATRP polymerization, such as methyl methacrylate. FIG. 1 is an infrared spectrum of a material at BP-C₆H₄Infrared spectra of OH at 834 and 1417cm^-1The infrared characteristic peak at (b) is attributed to the generation of C-P bond, and 1382cm^-1The infrared characteristic peak is attributed to stretching vibration of-OH; 1639cm in the infrared spectrum of BP-BIBB^-1The appearance of an infrared characteristic peak assigned to C ═ O means that BIBB and BP-C₆H₄Successful grafting of OH also indicates the successful synthesis of the novel ATRP reagent BP-BIBB.

The invention provides a method for grafting BP nanosheet by an Atom Transfer Radical Polymerization (ATRP) reagent containing acyl chloride in a molecule through a covalent modification method to obtain a novel ATRP reagent based on black phosphorus. The method is suitable for various ATRP reagents containing acyl chloride in molecules and can be effectively used for a series of ATRP polymerized monomers, a platform is provided for the modification of the black phosphorus nanosheet, and the black phosphorus nanosheet material modified by the material of the method has outstanding solubility in an organic solvent compared with a pure black phosphorus nanosheet, so that the black phosphorus nanosheet material has a wide application prospect in the aspect of photoelectric devices.

Drawings

FIG. 1 is an infrared spectrum of a novel black phosphorus nanosheet material modified by an ATRP reagent BIBB prepared by the present invention.

Detailed Description

Example 1: a specific synthetic method of a novel ATRP reagent based on black phosphorus comprises the following steps:

1)BP-C₆H₄and (3) synthesis of OH: under the protection of nitrogen, dissolving 4-hydroxybenzene diazo tetrafluoroborate (62mg, 0.3mmol) and tetrabutyl ammonium hexafluorophosphate (1162mg,0.3mmol) in 30ml of acetonitrile, dripping the solution into 30mg of black phosphorus nanosheets dispersed in 10ml of acetonitrile, stirring for 3 hours, centrifuging to remove the solvent, and washing the obtained solid with acetonitrile for multiple times to obtain BP-C₆H₄OH。IR：834(C-P)，1417(C-P)，1382(-OH).

2) Synthesis of BP-BIBB: BP-OH (50mg), triethylamine (1.29ml,9mmol), was dispersed in 30ml of tetrahydrofuran solvent under nitrogen protection, and then BIBB (2.1g,9mmol) was dissolved in 15ml of tetrahydrofuran at 0 ℃ and dropped, kept at 0 ℃ for one hour, and then kept at room temperature for 24 hours; BP-BIBB was obtained by washing with tetrahydrofuran several times after centrifugation.

3) Synthesis of BP-PSA: BP-BIBB (30mg), CuI (19mg) and solketalacrylate (1860mg) were dispersed in 8ml of a tetrahydrofuran solution under nitrogen protection, N, N, N ', N', N "-pentamethyldiethylenetriamine (17.3mg) was added thereto, and the mixture was reacted at 60 ℃ for 6 hours, and after the reaction was completed, the product was dropped into methanol to precipitate, and was dissolved in tetrahydrofuran again and precipitated again into methanol to obtain BP-PSA.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the concept of the present invention, and these modifications and decorations should also be regarded as being within the protection scope of the present invention.

Claims

1. A novel ATRP reagent based on black phosphorus is characterized in that: the structural formula is shown as DDAT-BP in the following formula:

2. a method for preparing a novel black phosphorus-based ATRP reagent according to claim 1, which is characterized in that: comprises the following steps:

1) under the inert gas atmosphere, adding black phosphorus nanosheets, 4-hydroxybenzene diazo tetrafluoroborate (compound 1) and tetrabutyl ammonium hexafluorophosphate (compound 2) into an acetonitrile solvent for reaction, and separating and purifying to obtain BP-C₆H₄OH; compound 1, compound 2, BP-C₆H₄The structural formula of OH is as follows:

2) under the inert gas atmosphere, adding BP-C₆H₄OH, triethylamine (compound 3) and BIBB (compound 4) are reduced in Tetrahydrofuran (THF) solution, and BP-BIBB is obtained through separation and purification;

the structural formula of BP-BIBB is as follows:

3. the application of the novel black phosphorus-based ATRP reagent in-situ ATRP polymerization reaction, in particular to the application of in-situ growth polymer taking black phosphorus nanosheets as substrates, in the conventional ATRP polymerization monomers such as methyl methacrylate and the like.

4. The use of the novel ATRP reagent based on black phosphorus of claim 1 in polymerization, wherein BP-BIBB, solketal acrylate (compound 5), cuprous iodide (compound 6), N', N "-pentamethyldiethylenetriamine (compound 7) is heated in dry tetrahydrofuran solvent for about 1-12 hours, after the reaction, the product is precipitated by dropping into methanol, and is washed by suction filtration to obtain BP-PSA; the results for compound 5, compound 6, compound 7, BP-PSA are as follows:

5. the application of the novel ATRP reagent grafted black phosphorus nanosheet composite material disclosed by claim 1 in-situ ATRP polymerization reaction, particularly in-situ growth polymers taking black phosphorus nanosheets as substrates, is suitable for common ATRP polymerization monomers such as methyl methacrylate and the like.