CN110003377B

CN110003377B - Polymer, preparation method and application thereof

Info

Publication number: CN110003377B
Application number: CN201910214239.1A
Authority: CN
Inventors: 陈少军; 陈恒; 黄俊贤
Original assignee: Shenzhen University
Current assignee: Shenzhen University
Priority date: 2019-03-20
Filing date: 2019-03-20
Publication date: 2021-01-12
Anticipated expiration: 2039-03-20
Also published as: CN110003377A

Abstract

The invention discloses a polymer with an ultraviolet absorption function and a preparation method thereof, and particularly relates to copolymerization of monomers with three different ultraviolet absorption wave bands, so that the ultraviolet absorption range is greatly expanded. The effect of shielding the full-wave band ultraviolet rays is achieved. The polymer film obtained by the invention has strong visible light transmission, fluorescence, easy processing, excellent stability and excellent ultraviolet shielding performance. Can be widely applied to the fields of aviation, construction, agriculture, optical devices and the like.

Description

Polymer, preparation method and application thereof

Technical Field

The invention belongs to the field of polymers, and particularly relates to a polymer with an ultraviolet absorption function, and a preparation method and application thereof.

Background

Ultraviolet light is an invisible light having a wavelength in the range of 10 to 400nm and a very high energy. Ultraviolet light can be subdivided into three parts: UVA (320-400nm), UVB (280-320nm) and UVC (100-280 nm). UVC is blocked by the ozone layer, but the intensity of UVC irradiated to the earth surface by the sun is increasing due to the recent expansion of ozone holes. The energy of the ultraviolet light is enough to destroy many chemical bonds in the material, and a photochemical reaction is initiated, so that the molecular chains in the material are broken and the compounds are decomposed, and the mechanical property and the service life of the material are influenced. In addition, the active free radicals on the broken molecular chain can generate photooxidation reaction with oxygen in the air, so that the material is yellowed to influence the appearance of the material. A great deal of research shows that excessive ultraviolet radiation not only has certain negative effects on various materials, but also can cause damage to organisms in different degrees, such as skin tanning and sunburn, and increase the prevalence rate of diseases such as skin cancer, cataract and the like.

Polymethyl methacrylate is an important class of engineering plastics. The light-transmitting film has the advantages of high light transmittance, easiness in processing, good weather resistance and the like, and is widely applied to the fields of aviation, buildings, agriculture, optical devices and the like. However, since polymethyl methacrylate itself has poor ultraviolet shielding properties, further use thereof in practical production and life is limited. The development of polymethylmethacrylate-based uv-shielding materials has been a research hotspot and has received much attention from researchers.

Currently, the method for improving the UV-shielding performance of polymethyl methacrylate is usually to dope a UV absorber. The ultraviolet absorbers are divided into two classes, one class being inorganic ultraviolet absorbers, mainly mica, talc, carbon black and metal oxides such as TiO₂CeO, ZnO and the like, which have wide absorption in an ultraviolet band and good stability. However, the compatibility of the inorganic ultraviolet absorbent and polymethyl methacrylate is poor, and the transparency of the system is easily reduced after film formation. The phenomena of migration, blooming and the like can be generated when the material is used for a long time, and the service life of the material is influenced. The other is an organic ultraviolet absorbent which mainly comprises organic compounds such as salicylates, cinnamates, benzophenones, benzotriazoles, triazines, substituted acrylonitriles and the like. The organic ultraviolet absorber can achieve an ultraviolet absorbing effect by a light absorbing effect. They usually have special chromophores and co-chromophores, which strongly absorb ultraviolet light in a certain wavelength band and convert the absorbed ultraviolet light into thermal energy, fluorescence or phosphorescence, thereby achieving the purpose of absorbing ultraviolet light.

With the widespread use of organic uv absorbers, many researchers have modified uv absorbers by using aliphatic chains to improve their compatibility with polymethyl methacrylate. However, the conventional physical blending method reduces the mechanical properties of polymethyl methacrylate, and these small-molecular ultraviolet absorbers easily escape from the substrate during high-temperature processing, reducing the ultraviolet shielding properties of the finished product, and causing waste of raw materials.

How to prepare a high molecular ultraviolet shielding material with good compatibility, excellent stability, long service life and high ultraviolet shielding efficiency becomes one of the technical problems which scientific researchers address.

Disclosure of Invention

The invention aims to provide a polymer and a preparation method thereof, and aims to solve the technical problems of poor compatibility, poor stability, short service life and low ultraviolet shielding efficiency of the conventional ultraviolet absorbing polymer material.

The invention also aims to provide a polymer film and a preparation method thereof, which are used for solving the problems of poor mechanical property, high processing difficulty, incomplete ultraviolet shielding range and low efficiency of the conventional polymer film.

In order to achieve the above object, according to one aspect of the present invention, there is provided a polymer prepared from methyl methacrylate, thiazole pyridonic acid ethylene glycol methacrylate, 4-methylacrylamide methyl benzoate in a mass ratio of 1: (0.01-10): (0.01-10) polymerization.

In another aspect of the invention, a polymer film is provided that is processed from the polymer.

In another aspect, the present invention provides a method for preparing the polymer, comprising the steps of:

according to the mass ratio of 1: (0.01-10): (0.01-10) dissolving methyl methacrylate, thiazole pyridonic acid ethylene glycol methacrylate, 4-methyl acrylamide methyl benzoate and a trace amount of initiator in a solvent for polymerization reaction.

The copolymer is isolated and purified.

Preferably, the temperature of the polymerization reaction is 50 to 100 ℃.

Preferably, the reaction time of the polymerization reaction is 2 to 36 hours.

Preferably, the initiator comprises any one or more of cyclohexanone peroxide, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, dicyclohexyl peroxydicarbonate, potassium persulfate, ammonium persulfate, and azobisisobutyronitrile.

Preferably, the solvent comprises any one or more of acetone, ethanol, dichloromethane, ethyl acetate, tetrahydrofuran and toluene.

Preferably, the shielding gas comprises one or more of carbon dioxide, nitrogen and argon.

Preferably, the separation and purification treatment includes any one or more of concentration, dissolution-precipitation, water washing, centrifugation, and suction filtration.

The invention also provides a preparation method of the polymer film, which comprises the following steps:

dissolving the polymer in a solvent;

pouring the obtained solution into a container, and drying at 25-60 ℃ for 8-24h to obtain the film.

Preferably, the solution has a concentration of 1 to 30 wt%.

The application of the polymer in preparing ultraviolet shielding materials or devices.

Compared with the existing products, the polymer of the invention has the advantages of more uniform texture performance, higher ultraviolet shielding efficiency, more comprehensive range and better mechanical performance.

The polymer film is prepared by adopting the polymer material, so that the ultraviolet shielding performance is better, for example, ultraviolet rays are almost completely shielded within the range of 200-400nm, namely, the efficiency is higher, the shielding range is wider, the texture is uniform, the mechanical performance is better, and the good performance ensures that the film can achieve the same shielding effect under the condition of thinner thickness, so that the raw materials are saved, the cost is saved, and the application range is wider.

The preparation method of the polymer adopts specific monomer polymerization, saves raw materials on the premise of ensuring the performance, simplifies the preparation steps, and is easier to process due to the uniform texture of a single polymer, and the prepared polymerized ultraviolet has higher shielding efficiency, wider range, uniform texture, easy processing and better mechanical performance.

The polymer film preparation method can ensure the performance while saving raw materials due to the adoption of the polymer, and the prepared polymer film has the advantages of higher ultraviolet shielding efficiency, wider range, easy processing, uniform texture, better mechanical property, easy processing and wider application range.

Drawings

The invention will be further described with reference to the accompanying drawings and examples, in which:

FIG. 1 is a nuclear magnetic resonance spectrum of a terpolymer according to an embodiment of the present invention;

FIG. 2 is a graph showing the UV absorption of ethyleneglycol thiazolepyridone methacrylate according to an embodiment of the present invention;

FIG. 3 is a graph showing UV absorption measurements of methyl 4-methylacrylamidobenzoate in accordance with an example of the present invention;

FIG. 4 is a graph showing UV transmittance measurements of polymer films and polymethyl methacrylate films according to examples of the present invention.

Detailed Description

In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly understood, the present invention is further described in detail below with reference to the following embodiments and the attached tables. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In one aspect, embodiments of the invention provide a polymer. The polymer is prepared from methyl methacrylate, thiazole pyridonic acid ethylene glycol methacrylate and 4-methyl acrylamide methyl benzoate according to the mass ratio of 1: (0.01-10): (0.01-10) polymerization. The single polymer formed by copolymerization enables the polymer to be uniform in texture, physical and chemical properties of various polymers are not required to be considered, the polymer is easy to process, the shielding efficiency is higher, the same properties can be achieved by fewer raw materials, and the raw materials are indirectly saved.

In another aspect of the present invention, there is provided a method for preparing the polymer, wherein the formula is as follows:

the polymer is prepared by three monomers through copolymerization reaction in one step, the performance of the prepared polymer is improved while the process is simplified, and the polymer is more convenient to further process, and the specific preparation method of the polymer comprises the following steps:

s01: according to the mass ratio of 1: (0.01-10): (0.01-10) dissolving methyl methacrylate, thiazole pyridonic acid ethylene glycol methacrylate, 4-methyl acrylamide methyl benzoate and a trace amount of initiator in a solvent for polymerization reaction.

S02: the copolymer is isolated and purified.

Specifically, the temperature of the polymerization reaction in the step S01 is 50 to 100 ℃. The temperature is selected to control the rate of polymerization to a suitable level, without overheating too quickly and causing uncontrolled progress, and without too slow a rate of reaction due to too low a temperature.

Specifically, the reaction time of the polymerization reaction in the step S01 is 2-36 h. And setting reaction time after monitoring according to different reaction temperatures, so that the reaction is completely finished.

Specifically, the initiator in step S01 includes any one or more of cyclohexanone peroxide, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, dicyclohexyl peroxydicarbonate, potassium persulfate, ammonium persulfate, and azobisisobutyronitrile. These are all common initiators, polymerization modes can be changed by adopting different polymerization degrees of the initiators, and proper initiators can be selected according to specific requirements.

The solvent in step S01 may include any one or more of acetone, ethanol, dichloromethane, ethyl acetate, tetrahydrofuran, and toluene. And selecting a proper solvent according to the solubility of the polymer, so that the polymer can take the solubility and the convenience of purifying and preparing a film.

The specific protective gas in step S01 includes one or more of carbon dioxide, nitrogen, and argon. According to different requirements, different protective gases can be selected, nitrogen with low price is selected under most conditions, and argon with higher price but better performance can be selected under the condition of preparing polymers with higher performance requirements.

The separation and purification treatment in step S02 specifically includes any one or more of concentration, dissolution-precipitation, water washing, centrifugation, and suction filtration. More specifically, in one embodiment, the terpolymer is precipitated by first concentrating the polymer and then dissolving the polymer in a solvent.

Based on the polymer and the preparation method thereof, the embodiment of the invention provides a polymer film. Due to the adoption of the polymer, the polymer film disclosed by the embodiment of the invention has excellent ultraviolet shielding performance, can be processed into a thinner film and keeps the ultraviolet shielding performance, has higher practicability, and has a simpler film processing process due to uniform texture.

The thickness of the polymer film of the embodiment of the present invention is generally 10 to 1000. mu.m. The raw material is wasted due to too large thickness, the transmittance of other visible light is reduced, and the ultraviolet shielding effect cannot be achieved due to too thin thickness.

a01: dissolving the polymer in a solvent;

a02: pouring the obtained solution into a container, and drying at 25-60 ℃ for 8-24h to obtain the film.

Specifically, the concentration of the solution in the step A01 is 1-30 wt%. The solution with the concentration range can enable the solution to have certain viscosity after pouring, can not form a film due to too thin concentration, and can not form a film due to too large concentration before being uniformly spread, so that the film thickness is not uniform.

The solvent in the step a01 may include any one or more of acetone, ethanol, dichloromethane, ethyl acetate, tetrahydrofuran, and toluene. The selection of the solvent is comprehensively considered according to the dissolution condition in the preparation and the actual market price condition.

The drying temperature in the step a02 is specifically set to allow the organic solvent to evaporate as quickly as possible, and not to make the polymer film uncured due to too high temperature.

The polymer has good ultraviolet shielding performance and various physical properties, and can be widely applied to preparation of ultraviolet shielding materials or devices.

The polymer and the production method thereof, and the polymer film and the production method thereof of the present invention will now be described in further detail with reference to specific examples.

1. Polymer and method for producing the same

Example 1.1

5 g of methyl methacrylate, 0.1 g of thiazole pyridone acid ethylene glycol methacrylate, 0.1 g of 4-methylacrylamide methyl benzoate, 5 mg of azobisisobutyronitrile and 30 ml of toluene are mixed uniformly under the condition of stirring, nitrogen is introduced for 20 minutes, then a system is sealed, and the reaction is carried out for 12 hours at the temperature of 90 ℃. And carrying out rotary evaporation, dissolution and precipitation treatment on the product to obtain the pure terpolymer.

Example 1.2

5 g of methyl methacrylate, 0.5 g of thiazole pyridonic acid ethylene glycol methacrylate, 0.5 g of 4-methyl acrylamide methyl benzoate, 10 mg of benzoyl peroxide and 30 ml of tetrahydrofuran are mixed uniformly under the condition of stirring, argon is introduced for 15 minutes, and the mixture is condensed and refluxed for reaction for 12 hours at the temperature of 85 ℃. And carrying out rotary evaporation, water washing, suction filtration and drying treatment on the product to obtain the pure terpolymer.

Example 1.3

5 g of methyl methacrylate, 0.5 g of thiazole pyridone acid ethylene glycol methacrylate, 0.5 g of 4-methylacrylamide methyl benzoate, 10 mg of benzoyl peroxide and 30 ml of toluene are uniformly mixed under the condition of stirring, argon is introduced for 30 minutes, then the system is sealed, and the reaction is carried out for 24 hours at 85 ℃. And carrying out rotary evaporation and vacuum drying treatment on the product to obtain the pure terpolymer.

2. Polymer film and method for producing the same

Example 2.1

5 g of terpolymer is dissolved in toluene under the condition of stirring at 60 ℃, the solution is poured into a glass tank, the solution is dried for 18 hours at 25 ℃, and finally the film is torn off to obtain the full-waveband ultraviolet shielding film. The polymer film was subjected to an ultraviolet absorption test. The test results are shown in fig. 4: the ultraviolet absorption range of the film covers 200-400nm, and the absorption efficiency is extremely high.

Example 2.2

5 g of terpolymer is dissolved in toluene under the condition of stirring at 60 ℃, the solution is poured into a glass tank, the solution is dried for 12 hours at 40 ℃, and finally the film is torn off to obtain the full-waveband ultraviolet shielding film.

Example 2.3

5 g of terpolymer is dissolved in dichloromethane under the condition of stirring at 60 ℃, the solution is poured into a glass tank, the solution is dried for 8 hours at 60 ℃, and finally the film is torn off to obtain the full-waveband ultraviolet shielding film.

3. UV absorber polymer monomers

Comparative example 1

Uniformly mixing 10 mmol of pyridonic acid, 20 mmol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1 mmol of 4-dimethylaminopyridine and 50 ml of dichloromethane under stirring, adding 15 mmol of hydroxyethyl methacrylate after 2 hours, reacting at normal temperature for 12 hours, and extracting to obtain the thiazole pyridonic acid ethylene glycol methacrylate monomer. The monomer was subjected to an ultraviolet absorption test, and the test results are shown in fig. 2.

Comparative example 2

Uniformly mixing 10 mmol of methyl 4-aminobenzoate, 15 mmol of methacrylic anhydride, 1 mmol of 4-dimethylaminopyridine and 50 ml of dichloromethane under the condition of stirring, reacting at normal temperature for 12 hours, and extracting to obtain a methyl 4-methacrylamide benzoate monomer. The monomer was subjected to an ultraviolet absorption test, and the test results are shown in fig. 3.

The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims

1. A polymer characterized by: the polymer is prepared from methyl methacrylate, thiazole pyridonic acid ethylene glycol methacrylate and 4-methyl acrylamide methyl benzoate according to the mass ratio of 1: (0.01-10): (0.01-10) polymerization.

2. A polymer film formed from the polymer of claim 1.

3. A method of preparing the polymer of claim 1, comprising the steps of:

according to the mass ratio of 1: (0.01-10): (0.01-10) dissolving methyl methacrylate, thiazole pyridonic acid ethylene glycol methacrylate, 4-methyl acrylamide methyl benzoate and a trace amount of initiator in a solvent for polymerization reaction;

the copolymer is isolated and purified.

4. A process for preparing a polymer according to claim 3, wherein: the temperature of the polymerization reaction is 50-100 ℃.

5. A process for preparing a polymer according to claim 3, wherein: the reaction time of the polymerization reaction is 2-36 h.

6. A process for preparing a polymer according to claim 3, wherein: the initiator comprises one or more of cyclohexanone peroxide, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, dicyclohexyl peroxydicarbonate, potassium persulfate, ammonium persulfate and azobisisobutyronitrile; and/or

The solvent comprises any one or more of acetone, ethanol, dichloromethane, ethyl acetate, tetrahydrofuran and toluene.

7. A process for preparing a polymer according to claim 3, wherein: the separation and purification treatment comprises any one or more of concentration, dissolution-precipitation, water washing, centrifugation and suction filtration.

8. The method of preparing a polymer film according to claim 2, comprising the steps of:

dissolving the polymer of claim 1 in a solvent;

and coating the obtained solution to form a film, and drying to prepare the polymer film.

9. The method for producing a polymer film according to claim 8, wherein: the concentration of the solution is 1-30 wt%.

10. Use of the polymer film according to claim 2 for the preparation of uv-screening materials or devices.