阅读说明：本技术 具有光限幅特性的复合材料及其制备方法 (Composite material with optical limiting characteristic and preparation method thereof ) 是由 刘洋 彭响方 施展华 李仙 王恩泽 梁成露 耿立宏 方辉 于 2020-06-04 设计创作，主要内容包括：本发明属于功能复合材料技术领域,具体涉及一种具有光限幅特性的复合材料及其制备方法。本发明提供一种具有光限幅特性的复合材料,所述复合材料的组分包括基材和TiS<Sub>2</Sub>纳米片,复合材料中TiS<Sub>2</Sub>纳米片的质量百分含量≤2％,所述基材选自：PMMA、PU、聚酰亚胺或无机玻璃。本发明将TiS<Sub>2</Sub>以纳米片形式与基材复合,得到TiS<Sub>2</Sub>均匀分散的复合材料,由于采用了TiS2纳米片,所得复合材料为固体材料,并且具有优异的光限幅性能。(The invention belongs to the technical field of functional composite materials, and particularly relates to a composite material with an optical limiting characteristic and a preparation method thereof. The invention provides a composite material with optical limiting property, and the components of the composite material comprise a base material and TiS 2 Nanosheets, TiS in composite 2 The mass percentage of the nano-sheets is less than or equal to 2 percent, and the base material is selectedFrom: PMMA, PU, polyimide or inorganic glass. The invention uses TiS 2 Compounding with a substrate in a nanosheet form to obtain TiS 2 The composite material with uniform dispersion is a solid material due to the adoption of the TiS2 nanosheets, and has excellent light amplitude limiting performance.)

1. A composite material having optical limiting properties, the components of the composite material comprising a substrate and TiS₂Nanosheets, TiS in composite₂The mass percentage of the nano-sheets is less than or equal to 2 percent, and the base material is selected from the following components: polymethyl methacrylate, polyurethane, polyimide or inorganic glass.

2. The composite material with optical limiting characteristics as claimed in claim 1, wherein the composite material is prepared by bulk polymerization or solution polymerization.

3. The composite material with optical limiting characteristics as claimed in claim 2, wherein the solution polymerization process is: dissolving the substrate with the benign solvent, and adding TiS₂Blending the nanosheet dispersion liquid to obtain a blended liquid; then placing the blending solution at a temperature below the boiling point of the solvent for 12-80 hours to obtain the base material/TiS₂A nanosheet composite.

4. The composite material with optical limiting characteristics as claimed in claim 2, wherein the bulk polymerization process is: firstly, raw material resin, initiator and TiS of a base material₂Pre-polymerizing the nano-sheet dispersion liquid at the temperature of Tg-60-Tg-40 ℃ until the mixed solution is in a glycerol shape, and immediately cooling the mixed solution to room temperature; polymerizing the mixed solution at the temperature of Tg-80 to Tg-50 ℃ for 12 to 48 hours; then heating to Tm-50-Tm-20 ℃ for high-temperature polymerization for 1-10 hours to obtain the base material/TiS₂A composite material; wherein, the Tg and the Tm respectively refer to the glass transition temperature and the melting point of the substrate.

5. The composite material with optical limiting properties of claim 3 or 4, wherein the TiS is₂The mass concentration of the nano-sheet dispersion liquid is 0.1-0.2 mg/ml.

6. The method for preparing a composite material having light-limiting characteristics as claimed in any one of claims 1 to 5, wherein the method is a bulk polymerization method or a solution polymerization method.

7. The method of claim 6, wherein the solution polymerization process is: dissolving the substrate with the benign solvent, and adding TiS₂Blending the nanosheet dispersion liquid to obtain a blended liquid; then placing the blending solution at a temperature below the boiling point of the solvent for 12-80 hours to obtain the base material/TiS₂A nanosheet composite;

further, the solvent is selected from acetone, toluene or chloroform.

8. The method of claim 6, wherein the bulk polymerization process comprises: firstly, raw material resin, initiator and TiS of a base material₂Pre-polymerizing the nano-sheet dispersion liquid at the temperature of Tg-60-Tg-40 ℃ until the mixed solution is in a glycerol shape, and immediately cooling the mixed solution to room temperature; polymerizing the mixed solution at the temperature of Tg-80 to Tg-50 ℃ for 12 to 48 hours; then heating to Tm-50-Tm-20 ℃ for high-temperature polymerization for 1-10 hours to obtain the base material/TiS₂A composite material; wherein, the Tg and the Tm respectively refer to the glass transition temperature and the melting point of the substrate.

9. The method of claim 8, wherein the initiator is selected from the group consisting of: benzoyl peroxide, cumene hydroperoxide or azobisisobutyronitrile.

10. The method of claim 8 or 9, wherein when the substrate is polymethyl methacrylate, the bulk polymerization method is: firstly, methyl methacrylate, an initiator and TiS₂Pre-polymerizing the nanosheet dispersion liquid at 60-80 ℃ until the mixed solution is in a glycerol shape, and immediately putting the mixed solution into an ice water bath to cool to room temperature; polymerizing the mixed solution at the low temperature of 40-70 ℃ for 12-48 hours; then heating to 80-110 ℃ for high-temperature polymerization for 1-10 hours to obtain TiS₂Polymethyl methacrylate composite material; wherein, methyl methacrylate, initiator and TiS₂The mass ratio of the nano sheets is as follows: 97.484-99.468 parts of methyl methacrylate, 0.516-0.527 part of initiator and TiS₂0.005-2 parts of nano sheet.

Technical Field

The invention belongs to the technical field of functional composite materials, and particularly relates to a composite material with an optical limiting characteristic and a preparation method thereof.

Background

The high-intensity laser electronic equipment has the advantages of good beam quality, small volume, simple structure, convenient use and the like, and is widely applied to important fields of sensing, communication, industrial production, military, medical treatment and the like; however, high-intensity laser is easy to damage optically sensitive organs and devices such as human eyes and optical sensors, and therefore, there is an urgent need to prepare and research optical limiting materials with excellent performance such as low optical limiting threshold, high laser damage threshold, fast response speed, wide laser wavelength protection range, high laser protection efficiency, and the like.

Optical limiting refers to a material having a high transmittance under low intensity laser irradiation and a low transmittance under high intensity laser irradiation when the material is irradiated with laser light; the optical limiting process is realized by utilizing nonlinear optical effects such as nonlinear absorption, nonlinear refraction or nonlinear scattering of optical materials. Good optical limiting materials have high linear transmittance and low optical energy threshold, low limiting transmittance, and fast laser response.

Disclosure of Invention

The invention provides a novel composite material with optical limiting property, which takes polymethyl methacrylate (PMMA), Polyurethane (PU), polyimide, inorganic glass and the like as base materials, TiS₂Nano meterThe sheet is used as optical limiting material, and the substrate and TiS are₂The composite material with integrated structure and function is prepared by adopting simple methods such as bulk polymerization or solution polymerization and the like, and can be used as an optical limiting solid composite material with excellent performance to ensure that TiS₂The device formation in the laser protection field becomes possible.

The technical scheme of the invention is as follows:

the first technical problem to be solved by the invention is to provide a composite material with optical limiting property, and the components of the composite material comprise a substrate and TiS₂Nanosheets, TiS in composite₂The mass percentage of the nano-sheets is less than or equal to 2 percent, and the base material is selected from the following components: polymethyl methacrylate (PMMA), Polyurethane (PU), polyimide, or inorganic glass.

Further, the composite material with the optical limiting characteristic is prepared by adopting a bulk polymerization method or a solution polymerization method.

Further, the solution polymerization method is as follows: dissolving the substrate with the benign solvent, and adding TiS₂Blending the nanosheet dispersion liquid to obtain a blended liquid; then placing the blending solution at a temperature below the boiling point of the solvent for 12-80 hours to obtain the base material/TiS₂A nanosheet composite.

Further, the bulk polymerization method is: firstly, raw material resin, initiator and TiS of a base material₂Pre-polymerizing the nano-sheet dispersion liquid at the temperature of Tg-60-Tg-40 ℃ until the mixed solution is in a glycerol shape, and immediately cooling the mixed solution to room temperature; polymerizing the mixed solution at the temperature of Tg-80 to Tg-50 ℃ for 12 to 48 hours; then heating to Tm-50-Tm-20 ℃ for high-temperature polymerization for 1-10 hours to obtain the base material/TiS₂A composite material; wherein, the Tg and the Tm respectively refer to the glass transition temperature and the melting point of the substrate.

Further, the initiator is selected from: benzoyl peroxide, cumene hydroperoxide or azobisisobutyronitrile.

Further, the TiS₂The mass concentration of the nano-sheet dispersion liquid is 0.1-0.2 mg/ml.

In the present invention, TiS₂The nano-sheet dispersion is prepared by the following method: mixing TiS₂Dispersion of original powderIn the presence of isopropanol: refluxing acetonitrile (volume ratio, isopropanol: acetonitrile is 1: 39) for 12-36 hours at the azeotropic point of the solvent, carrying out ultrasonic treatment on the dispersion liquid for 1-6 hours, finally centrifuging for 30-60 minutes at 2000 revolutions, and taking supernatant to obtain TiS₂A nanosheet dispersion.

The second technical problem to be solved by the present invention is to provide a method for preparing the above composite material with optical limiting characteristics, wherein the preparation method is bulk polymerization or solution polymerization.

Further, the solution polymerization method is as follows: dissolving the substrate with the benign solvent, and adding TiS₂Blending the nanosheet dispersion liquid to obtain a blended liquid; then placing the blending solution at a temperature below the boiling point of the solvent for 12-80 hours to obtain the base material/TiS₂A nanosheet composite.

Further, in the above solution polymerization method, the solvent is selected from acetone, toluene or chloroform.

Further, the bulk polymerization method is: firstly, raw material resin, initiator and TiS of a base material₂Pre-polymerizing the nano-sheet dispersion liquid at the temperature of Tg-60-Tg-40 ℃ until the mixed solution is in a glycerol shape, and immediately cooling the mixed solution to room temperature; polymerizing the mixed solution at the temperature of Tg-80 to Tg-50 ℃ for 12 to 48 hours; then heating to Tm-50-Tm-20 ℃ for high-temperature polymerization for 1-10 hours to obtain the base material/TiS₂A composite material; wherein, the Tg and the Tm respectively refer to the glass transition temperature and the melting point of the substrate.

Further, when the substrate is polymethyl methacrylate, the bulk polymerization method is: firstly, methyl methacrylate, an initiator and TiS₂Pre-polymerizing the nanosheet dispersion liquid at 60-80 ℃ until the mixed solution is in a glycerol shape, and immediately putting the mixed solution into an ice water bath to cool to room temperature; polymerizing the mixed solution at the low temperature of 40-70 ℃ for 12-48 hours; then heating to 80-110 ℃ for high-temperature polymerization for 1-10 hours to obtain TiS₂Polymethyl methacrylate composite material; wherein, methyl methacrylate, initiator and TiS₂The mass ratio of the nano sheets is as follows: 97.484-99.468 parts of methyl methacrylate, 0.516-0.527 part of initiator and TiS₂0.005-2 weight% of nanosheetAnd (4) portions are obtained.

Further, in the above method, the initiator is selected from the group consisting of: benzoyl peroxide, cumene hydroperoxide or azobisisobutyronitrile.

In the bulk polymerization of the present invention, the prepolymerization reaction is carried out first for the following purposes: because the density of methyl methacrylate and the like is less than that of the polymer, the volume shrinkage is obvious in the polymerization process, and the volume excessive shrinkage can be avoided by prepolymerization; in addition, a large amount of heat can be generated in the monomer polymerization process, if the heat cannot be dissipated in time, the automatic acceleration can be easily generated to initiate the implosion, the prepolymerization is beneficial to the heat dissipation in the polymerization process, and the implosion is prevented; the purpose of carrying out high-temperature polymerization is as follows: because the polymerization cannot be completely carried out and part of the monomers are not reacted during the prepolymerization at low temperature, the reaction needs to be carried out for a while at higher temperature, so that the reaction tends to be complete.

The invention has the beneficial effects that:

(1) the invention uses TiS₂Compounding with a substrate in the form of a nanosheet suspension to obtain TiS₂Uniformly dispersed solid composite material and having excellent optical limiting properties, thereby making TiS₂The device formation in the laser protection field becomes possible.

(2) The composite material is prepared by a bulk polymerization method or a solution blending method, and has the advantages of convenient operation, safety, environmental protection and simple required equipment.

(3) The composite material prepared by the invention has better NLO performance.

Drawings

FIG. 1a is a TiS obtained in example 1 of the present invention₂A PMMA composite glass ultraviolet lamp irradiation picture; FIG. 1b is a photograph of a PMMA UV lamp produced in comparative example 1 of the present invention; under the ultraviolet lamp, TiS₂The nanoplatelets will produce fluorescence; thus by comparison with TiS₂The picture of the PMMA composite material and the pure PMMA under an ultraviolet lamp can be judged to be TiS₂Dispersion in PMMA composite; in FIG. 1, TiS is compared with colorless and transparent pure PMMA₂The surface of the/PMMA composite material presents uniform light blue, which shows that TiS₂Uniformly dispersed in PMMA.

FIG. 2(a) is a TiS obtained in example 1 of the present invention₂Graph of input and output energy relationship of/PMMA composite glass and PMMA prepared in comparative example 1; FIG. 2(b) shows TiS obtained in example 1₂The input energy and the normalized transmittance of the PMMA composite material are plotted; in fig. 2, as the incident laser energy density increases, the initial threshold (F) is reached_SLaser energy density value corresponding to the starting point at which the normalized transmittance starts to decrease), TiS₂The normalized transmittance of the PMMA composite material is continuously reduced, which shows that the PMMA composite material has optical limiting performance; in addition, the lower initial threshold value can enable the composite material to have a wider laser protection range, and the TiS prepared by the composite material₂The initial threshold value of the PMMA composite material is as low as 0.07J/cm²So that TiS₂The PMMA composite material can effectively prevent the laser peak power from being 10mW/cm²And the above lasers, such as Nd: YAG pulsed solid-state laser, Nd: Ce: YAG laser, etc.

FIG. 3a is a photograph of a PMMA sample from comparative example 1 of the present invention; FIG. 3b is a TiS obtained in example 1 of the present invention₂A photo of a/PMMA composite glass sample; as can be seen in FIG. 3, TiS₂Although the visible light transmittance of the composite material is reduced to a certain extent, the visible light transmittance is still at a higher level, namely 82%.

Detailed Description

The following examples are given to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.

In the invention, the methyl methacrylate and the initiator are purchased and the purity is analytically pure, TiS₂The concentration of the nano-sheet solution is 0.2 mg/ml; TiS₂The nano-sheet dispersion is prepared by the following method: mixing TiS₂Dispersion of the original powder in isopropanol: refluxing in acetonitrile (1: 39) at the azeotropic point of the solvent for 24 hours, performing ultrasonic treatment on the dispersion liquid for 4 hours, finally centrifuging at 2000 rpm for 30 minutes, and taking supernatant to obtain TiS₂A nanosheet dispersion.