阅读说明：本技术 一种兼具紫外阻隔与抗菌功能的聚乙烯醇复合材料及其制备方法 (Polyvinyl alcohol composite material with ultraviolet blocking and antibacterial functions and preparation method thereof ) 是由 唐群 武经纬 冯少雄 张焱 吴同发 李秋霖 于 2021-09-13 设计创作，主要内容包括：本发明属于高分子复合材料技术领域,涉及一种兼具紫外阻隔与抗菌功能的聚乙烯醇复合材料及其制备方法,它是由如下原料制备而成的：聚乙烯醇、钴配合物晶体[Co-(4)(H-(8)P-(3)NC-(3)O-(9))-(2)]·H-(2)O,式中(H-(8)P-(3)NC-(3)O-(9))为氨基三亚甲基磷酸失去4个质子的阴离子。本发明还提供了上述聚乙烯醇复合材料的制备方法。本发明所制备得到的聚乙烯醇复合材料具有优异的紫外线阻隔性能、抑菌性能、氨气响应性能、力学性能、水汽透过性、热稳定性,同时还能保持高的光学透明性,且制备工艺简单、适于放大生产,在包装、抗菌材料、氨气检测等领域具有潜在应用价值。(The invention belongs to the technical field of polymer composite materials, and relates to a polyvinyl alcohol composite material with ultraviolet blocking and antibacterial functions and a preparation method thereof, wherein the polyvinyl alcohol composite material is prepared from the following raw materials: polyvinyl alcohol, cobalt complex crystal [ Co 4 (H 8 P 3 NC 3 O 9 ) 2 ]·H 2 O, in the formula (H) 8 P 3 NC 3 O 9 ) The anion of 4 protons is lost for aminotrimethylene phosphate. The invention also provides a preparation method of the polyvinyl alcohol composite material. The polyvinyl alcohol composite material prepared by the invention has excellent ultraviolet barrier property, antibacterial property, ammonia response property, mechanical property, water vapor permeability and thermal stability, and can keep high optical transparency, andthe preparation process is simple, is suitable for large-scale production, and has potential application value in the fields of packaging, antibacterial materials, ammonia gas detection and the like.)

1. The polyvinyl alcohol composite material with the ultraviolet blocking and antibacterial functions is characterized by comprising the following components in parts by weight: 100 parts of polyvinyl alcohol and 3-12 parts of cobalt complex crystal;

the chemical formula of the cobalt complex crystal is [ Co₄(H₈P₃NC₃O₉)₂]·H₂O, in the formula (H)₈P₃NC₃O₉) The anion of 4 protons is lost for aminotrimethylene phosphate.

2. The polyvinyl alcohol composite material with the functions of ultraviolet blocking and antibacterial as claimed in claim 1, wherein the preparation method of the cobalt complex crystal comprises the following steps:

dissolving cobalt nitrate in a mixed solvent of deionized water and DMF, stirring for 10min, uniformly mixing, slowly adding aminotrimethylene phosphoric acid, stirring and mixing for 1h, then placing the mixture in a reaction kettle, reacting for 48h at 140 ℃, cooling to room temperature, filtering, washing and drying to obtain a cobalt complex crystal;

the mass ratio of the cobalt nitrate to the aminotrimethylene phosphoric acid to the deionized water to the DMF is 15: 11: 200: 950.

3. the preparation method of the polyvinyl alcohol composite material with the ultraviolet blocking and antibacterial functions as claimed in any one of claims 1 to 2, characterized by comprising the following steps:

(1) dispersing 3-12 parts of cobalt complex crystals in 3000 parts of distilled water, performing ultrasonic treatment at room temperature for 1 hour, and stirring for 2 hours to obtain a cobalt complex uniform dispersion liquid for later use;

(2) adding 100 parts of polyvinyl alcohol into the cobalt complex uniform dispersion liquid obtained in the step (1), firstly stirring at room temperature for 1h, then heating to 85 ℃, stirring for 2h, and ultrasonically removing bubbles to obtain a uniform film forming liquid for later use;

(3) and (3) pouring the film forming liquid obtained in the step (2) into a flat-bottomed glass dish, and drying in a vacuum oven at 55 ℃ for 24 hours to obtain the polyvinyl alcohol composite material with the ultraviolet blocking and antibacterial functions.

Technical Field

The invention belongs to the technical field of polymer composite materials, and particularly relates to a polyvinyl alcohol composite material with ultraviolet blocking and antibacterial functions and a preparation method thereof.

Background

Coordination chemistry has abundant research contents, the research on the structure and the properties of the coordination chemistry is very important at present, and almost all fields relate to the coordination chemistry, wherein metal organic chemistry is an important research direction in the coordination chemistry. In recent years, many metal organic complexes with ultraviolet blocking and antibacterial functions have been developed, and the ultraviolet blocking and antibacterial effects are remarkable. The metal organic complex material can be better compatible with the polymer due to the function modifiability and the controllability of the structure of the metal organic complex material, and can conveniently realize the preparation of the organic/inorganic composite material.

Along with the continuous improvement of the quality of life of people and the increasing attention of people on the living environment, the traditional white plastic garbage causes great pollution to the human living environment, and therefore, the research of novel environment-friendly materials is urgent. The polyvinyl alcohol is a biodegradable material, is a non-toxic, non-corrosive and environment-friendly organic high molecular polymer, and has wide application prospect. However, the pure polyvinyl alcohol material lacks functions of ultraviolet blocking, antibiosis, ammonia response and the like, so that the practical application of the pure polyvinyl alcohol material is limited. The invention takes polyvinyl alcohol as a substrate and functional cobalt complex as a filler to prepare the composite material, thereby enhancing the ultraviolet barrier, antibacterial, ammonia response, mechanics, thermal stability and other properties of the polyvinyl alcohol and widening the application field thereof.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a polyvinyl alcohol composite material with ultraviolet blocking and antibacterial functions and a preparation method thereof. The composite material has excellent ultraviolet blocking performance, antibacterial performance, ammonia response performance, mechanical property, water vapor permeability, thermal stability and higher hygroscopicity, can keep high optical transparency, has simple preparation process, is environment-friendly and low in cost, and is suitable for amplification production.

The technical scheme of the invention is as follows:

the polyvinyl alcohol composite material with the ultraviolet blocking and antibacterial functions is characterized by comprising the following components in parts by weight: 100 parts of polyvinyl alcohol and 3-12 parts of cobalt complex crystal;

the chemical formula of the cobalt complex crystal is H₂O, in the formula (H)₈P₃NC₃O₉) The anion of 4 protons is lost for aminotrimethylene phosphate.

The preparation method of the cobalt complex crystal comprises the following steps:

dissolving cobalt nitrate in a mixed solvent of deionized water and DMF, stirring for 10min, uniformly mixing, slowly adding aminotrimethylene phosphoric acid, stirring and mixing for 1h, then placing the mixture in a reaction kettle, reacting for 48h at 140 ℃, cooling to room temperature, filtering, washing and drying to obtain a cobalt complex crystal;

the mass ratio of the cobalt nitrate to the aminotrimethylene phosphoric acid to the deionized water to the DMF is 15: 11: 200: 950.

a preparation method of a polyvinyl alcohol composite material with ultraviolet blocking and antibacterial functions comprises the following steps:

(1) dispersing 3-12 parts of cobalt complex crystals in 3000 parts of distilled water, performing ultrasonic treatment at room temperature for 1 hour, and stirring for 2 hours to obtain a cobalt complex uniform dispersion liquid for later use;

(2) adding 100 parts of polyvinyl alcohol into the cobalt complex uniform dispersion liquid obtained in the step (1), firstly stirring at room temperature for 1h, then heating to 85 ℃, stirring for 2h, and ultrasonically removing bubbles to obtain a uniform film forming liquid for later use;

(3) and (3) pouring the film forming liquid obtained in the step (2) into a flat-bottomed glass dish, and drying in a vacuum oven at 55 ℃ for 24 hours to obtain the polyvinyl alcohol composite material with the ultraviolet blocking and antibacterial functions.

Compared with the prior art, the invention has the following beneficial effects:

the polyvinyl alcohol composite material prepared by the invention has excellent ultraviolet blocking performance, bacteriostatic performance, ammonia response performance, mechanical property, water vapor permeability, thermal stability and higher hygroscopicity, and can keep high optical transparency, and the preparation process is simple, is suitable for amplification production, and has potential application value in the fields of packaging, antibacterial materials, ammonia detection and the like.

Detailed Description

In order to better explain the present invention, the present invention is further explained in detail below with reference to specific examples, but the embodiments of the present invention are not limited thereto.

In the following specific examples and comparative formula and preparation method, the polyvinyl alcohol is a product provided by Shanghai Aladdin Biotechnology GmbH, with alcoholysis degree of 98-99 mol% and viscosity of 54.0-66 mPa.s; cobalt nitrate is an analytical pure-grade reagent provided by chemical corporation of Shirong; DMF (N, N-dimethylformamide) is an analytical pure grade reagent provided by chemical corporation, julong; aminotrimethylene phosphate was used as a product provided by Shanghai Michelin Biochemical technology Ltd.

In the following specific examples and comparative example formulations, preparation methods, the cobalt complex crystals have the chemical formula H₂O, in the formula (H)₈P₃NC₃O₉) The preparation method of the amino trimethylene phosphate which loses 4-proton anions comprises the following steps:

dissolving cobalt nitrate in a mixed solvent of deionized water and DMF, stirring for 10min, uniformly mixing, slowly adding aminotrimethylene phosphoric acid, stirring and mixing for 1h, then placing the mixture in a reaction kettle, reacting for 48h at 140 ℃, cooling to room temperature, filtering, washing and drying to obtain a cobalt complex crystal;

the mass ratio of the cobalt nitrate to the aminotrimethylene phosphoric acid to the deionized water to the DMF is 15: 11: 200: 950.

example 1

The polyvinyl alcohol composite material with the ultraviolet blocking and antibacterial functions is characterized by comprising the following components in parts by weight: 100 parts of polyvinyl alcohol and 3 parts of cobalt complex crystals.

The preparation method comprises the following steps:

(1) dispersing 3 parts of cobalt complex crystals in 3000 parts of distilled water, performing ultrasonic treatment at room temperature for 1 hour, and stirring for 2 hours to obtain a cobalt complex uniform dispersion liquid for later use;

(2) adding 100 parts of polyvinyl alcohol into the cobalt complex uniform dispersion liquid obtained in the step (1), firstly stirring at room temperature for 1h, then heating to 85 ℃, stirring for 2h, and ultrasonically removing bubbles to obtain a uniform film forming liquid for later use;

(3) and (3) pouring the film forming liquid obtained in the step (2) into a flat-bottomed glass dish, and drying in a vacuum oven at 55 ℃ for 24 hours to obtain the polyvinyl alcohol composite material with the ultraviolet blocking and antibacterial functions.

Example 2

The polyvinyl alcohol composite material with the ultraviolet blocking and antibacterial functions is characterized by comprising the following components in parts by weight: 100 parts of polyvinyl alcohol and 6 parts of cobalt complex crystals.

The preparation method comprises the following steps:

(1) dispersing 6 parts of cobalt complex crystals in 3000 parts of distilled water, performing ultrasonic treatment at room temperature for 1 hour, and stirring for 2 hours to obtain a cobalt complex uniform dispersion liquid for later use;

(2) adding 100 parts of polyvinyl alcohol into the cobalt complex uniform dispersion liquid obtained in the step (1), firstly stirring at room temperature for 1h, then heating to 85 ℃, stirring for 2h, and ultrasonically removing bubbles to obtain a uniform film forming liquid for later use;

(3) and (3) pouring the film forming liquid obtained in the step (2) into a flat-bottomed glass dish, and drying in a vacuum oven at 55 ℃ for 24 hours to obtain the polyvinyl alcohol composite material with the ultraviolet blocking and antibacterial functions.

Example 3

The polyvinyl alcohol composite material with the ultraviolet blocking and antibacterial functions is characterized by comprising the following components in parts by weight: 100 parts of polyvinyl alcohol and 9 parts of cobalt complex crystals.

The preparation method comprises the following steps:

(1) dispersing 9 parts of cobalt complex crystals in 3000 parts of distilled water, performing ultrasonic treatment at room temperature for 1 hour, and stirring for 2 hours to obtain a cobalt complex uniform dispersion liquid for later use;

(2) adding 100 parts of polyvinyl alcohol into the cobalt complex uniform dispersion liquid obtained in the step (1), firstly stirring at room temperature for 1h, then heating to 85 ℃, stirring for 2h, and ultrasonically removing bubbles to obtain a uniform film forming liquid for later use;

(3) and (3) pouring the film forming liquid obtained in the step (2) into a flat-bottomed glass dish, and drying in a vacuum oven at 55 ℃ for 24 hours to obtain the polyvinyl alcohol composite material with the ultraviolet blocking and antibacterial functions.

Example 4

The polyvinyl alcohol composite material with the ultraviolet blocking and antibacterial functions is characterized by comprising the following components in parts by weight: 100 parts of polyvinyl alcohol and 12 parts of cobalt complex crystals.

The preparation method comprises the following steps:

(1) dispersing 12 parts of cobalt complex crystals in 3000 parts of distilled water, performing ultrasonic treatment at room temperature for 1 hour, and stirring for 2 hours to obtain a cobalt complex uniform dispersion liquid for later use;

(2) adding 100 parts of polyvinyl alcohol into the cobalt complex uniform dispersion liquid obtained in the step (1), firstly stirring at room temperature for 1h, then heating to 85 ℃, stirring for 2h, and ultrasonically removing bubbles to obtain a uniform film forming liquid for later use;

(3) and (3) pouring the film forming liquid obtained in the step (2) into a flat-bottomed glass dish, and drying in a vacuum oven at 55 ℃ for 24 hours to obtain the polyvinyl alcohol composite material with the ultraviolet blocking and antibacterial functions.

Comparative example

The preparation of pure polyvinyl alcohol material includes the following steps:

(1) adding 100 parts of polyvinyl alcohol into 3000 parts of true distilled water, stirring at room temperature for 1 hour, heating to 85 ℃, stirring for 2 hours, and ultrasonically removing bubbles to obtain uniform film forming liquid for later use;

(2) pouring the film-forming liquid obtained in the step (1) into a flat-bottomed glass dish, and drying in a vacuum oven at 55 ℃ for 24 hours to obtain the pure polyvinyl alcohol material.

And (3) performance testing:

the pure polyvinyl alcohol material prepared by the comparative example and the polyvinyl alcohol composite material prepared by the example are subjected to performance test, wherein the ultraviolet-visible performance is tested by using an ultraviolet-visible spectrometer (Lamdba365, platinum Elmer instruments Co., Ltd.), and the average transmittance of ultraviolet rays (UVA, UVB and UVC) is calculated by referring to GB/T18830-2009; tensile properties were tested according to GB/T1040-2006; the water vapor transmission coefficient is tested according to ASTM E96, and the thermal stability is measured by a thermal weight loss analyzer (SDT-Q600, TA company, USA); performing antibacterial property test of the material according to QBT 2591-2003;

the hygroscopicity test method is as follows:

a film sample having dimensions of 20mm by 0.1mm was placed in a vacuum oven at 40 ℃ and, after drying for 72 hours, the mass of the film sample (noted as M)₀) (ii) a Then, the dried film sample was placed in a closed container at a relative humidity of 57% and a temperature of 25 ℃ for 48 hours, and the mass (denoted as M) of the film sample was measured₁) (ii) a Moisture absorption (%) of the film sample was 100 ═ M (M)₁-M₀)/M₀。

The ammonia response test method is as follows:

cutting the film material into a shape with a consistent size, then exposing the cut film material in an ammonia environment, and recording the color change information of the film material by using a high-quality computer color difference meter.

The above performance test data are shown in table 1.

Table 1 sample performance test data

The experimental result proves that the pure polyethylene material prepared by the comparative example is colorless and transparent, the color of the pure polyethylene material does not change obviously after being exposed in an ammonia gas environment, or the pure polyethylene material also presents colorless and transparent optical properties, the polyethylene nano composite material prepared by the example is light purple, and the color of the polyethylene nano composite material rapidly changes into reddish brown (within 5 min) after being exposed in the ammonia gas environment; as shown in Table 1, the polyvinyl alcohol nanocomposite prepared by the invention has excellent ultraviolet blocking performance, antibacterial performance, ammonia response performance, mechanical property, water vapor permeability, thermal stability and high hygroscopicity, can maintain high optical transparency, has simple preparation process, easily controlled chemical components, good repeatability and high yield, has potential application value in the fields of packaging materials, decoration materials and the like, is suitable for large-scale production, and expands the application field of the polyvinyl alcohol composite.

The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.