Copper metal organic framework modified starch-based composite film and preparation method thereof
阅读说明：本技术 一种铜金属有机框架改性淀粉基复合膜及其制备方法 (Copper metal organic framework modified starch-based composite film and preparation method thereof ) 是由 邹志明 余劲灵 胡文凯 黄雪雯 李和平 于 2021-09-13 设计创作，主要内容包括：本发明属于淀粉基复合材料技术领域,涉及一种铜金属有机框架改性淀粉基复合膜及其制备方法,按重量份计,由以下组分组成：淀粉100份,甘油30份,铜金属有机框架1～7份。本发明利用铜金属有机框架作为改性剂,能够有效地改善淀粉基材料的性能。本发明所制备得到的铜金属有机框架改性淀粉基复合膜具有优异的紫外线屏蔽性能、高能短波蓝光阻隔性能、力学性能、水汽阻隔性能以及低的吸湿性,且制备工艺简单环保,成本低廉,适于放大生产,在包装、紫外线防护等领域具有很好的应用前景。(The invention belongs to the technical field of starch-based composite materials, and relates to a copper metal organic framework modified starch-based composite film and a preparation method thereof, wherein the copper metal organic framework modified starch-based composite film comprises the following components in parts by weight: 100 parts of starch, 30 parts of glycerol and 1-7 parts of copper metal organic framework. The invention uses the copper metal organic frame as a modifier, and can effectively improve the performance of the starch-based material. The copper metal organic framework modified starch-based composite film prepared by the invention has excellent ultraviolet shielding performance, high-energy short-wave blue light barrier performance, mechanical property, water vapor barrier performance and low hygroscopicity, and the preparation process is simple and environment-friendly, has low cost, is suitable for amplification production, and has good application prospects in the fields of packaging, ultraviolet protection and the like.)
1. The copper metal organic frame modified starch-based composite film is characterized by comprising the following components in parts by weight: 100 parts of starch, 30 parts of plasticizer and 1-7 parts of copper metal organic frame;
the starch is corn starch;
the plasticizer is glycerol;
the chemical formula of the copper metal organic framework is { [ Cu (AIP) ]2(PIY)(H2O)2]·4H2O}nWherein AIP is 5-amino isophthalic acid, PIY is 2, 3-diamino-5-bromopyridine;
the copper metal organic framework is nano particles, and the average particle size is 7-19 nm.
2. The copper metal organic framework modified starch-based composite film according to claim 1, wherein the preparation method of the copper metal organic framework comprises the following steps: respectively dissolving 5-amino isophthalic Acid (AIP) and 2, 3-diamino-5-bromopyridine (APY) in ethanol to prepare a solution of 0.133 mmol/L5-amino isophthalic Acid (AIP) and a solution of 0.066 mmol/L2, 3-diamino-5-bromopyridine (APY); pouring 15mL of 5-amino isophthalic Acid (AIP) solution and 15mL of 2, 3-diamino-5-bromopyridine (APY) solution into a round-bottom flask, stirring for 1h, uniformly mixing, placing in a constant-temperature water bath kettle at 80 ℃, stirring and refluxing for 1h to obtain a mixed solution; and then, dropwise adding 15mL of 0.133mmol/L copper chloride ethanol solution into the mixed solution at room temperature, stirring for 15min at room temperature, placing the obtained mixed solution in a 80 ℃ constant-temperature water bath kettle, stirring and refluxing for 1h, then placing the mixed solution at room temperature for 30min, and then carrying out centrifugal separation, washing with water and drying to obtain the copper metal organic framework.
3. The method for preparing the copper metal organic framework modified starch-based composite film according to any one of claims 1 to 2, characterized by comprising the steps of:
(1) adding 100 parts of starch and 30 parts of plasticizer into 1600 parts of deionized water, stirring for 30 minutes at room temperature, and stirring and dissolving at 85 ℃ to obtain a starch solution for later use;
(2) dispersing 1-7 parts of a copper metal organic frame in 1200 parts of deionized water, and stirring for 1 hour to obtain a uniform dispersion liquid for later use;
(3) adding the dispersion liquid obtained in the step (2) into the starch solution obtained in the step (1), and stirring for 1h at 85 ℃ to obtain uniform film forming liquid;
(4) and (4) pouring the film forming liquid in the step (3) onto an organic glass dish, and drying in a vacuum oven at 50 ℃ for 24 hours to obtain the copper metal organic framework modified starch-based composite film.
Technical Field
The invention relates to the technical field of starch-based composite materials, in particular to a copper metal organic framework modified starch-based composite film and a preparation method thereof.
Background
The starch has rich sources, low price, complete degradable property, high biocompatibility and good film forming property, and is one of the most potential natural biodegradable materials. After the starch and the plasticizer are blended, the thermoplastic starch with excellent film-forming property can be prepared. Therefore, the thermoplastic starch-based biodegradable material has potential application value in various fields of food packaging, agricultural production, papermaking, electronic devices and the like. However, thermoplastic starch-based materials exhibit some limitations, such as poor mechanical properties and water vapor barrier properties, uv-shielding properties, high-energy short-wave blue light barrier properties. This severely restricts the application of thermoplastic starch-based composites in the fields of packaging, ultraviolet protection, etc. Therefore, further studies are still needed for the modification of thermoplastic starch-based materials.
Disclosure of Invention
The invention aims to provide a copper metal organic framework modified starch-based composite film and a preparation method thereof aiming at the defects of the prior art, wherein thermoplastic starch is taken as a base material, a copper metal organic framework is taken as a filler, copper metal organic framework nano particles are added into a starch matrix, the ultraviolet shielding performance, the high-energy short-wave blue light blocking performance, the mechanical property and the water vapor blocking performance of a starch-based film material can be effectively improved, the modified film material has lower hygroscopicity, the preparation process is simple and environment-friendly, the cost is low, and the modified film material is suitable for amplification production.
The technical scheme of the invention is as follows:
a copper metal organic framework modified starch-based composite film comprises the following components in parts by weight: 100 parts of starch, 30 parts of plasticizer and 1-7 parts of copper metal organic frame.
The starch is corn starch; the plasticizer is glycerol.
The chemical formula of the copper metal organic framework is {. 4H2O}nWherein AIP is 5-amino isophthalic acid, and PIY is 2, 3-diamino-5-bromopyridine.
The copper metal organic framework is self-made nano particles, and the average particle size is 7-19 nm.
The preparation method of the copper metal organic framework comprises the following steps:
respectively dissolving 5-amino isophthalic Acid (AIP) and 2, 3-diamino-5-bromopyridine (APY) in ethanol to prepare a solution of 0.133 mmol/L5-amino isophthalic Acid (AIP) and a solution of 0.066 mmol/L2, 3-diamino-5-bromopyridine (APY); pouring 15mL of 5-amino isophthalic Acid (AIP) solution and 15mL of 2, 3-diamino-5-bromopyridine (APY) solution into a round-bottom flask, stirring for 1h, uniformly mixing, placing in a constant-temperature water bath kettle at 80 ℃, stirring and refluxing for 1h to obtain a mixed solution; and then, dropwise adding 15mL of 0.133mmol/L copper chloride ethanol solution into the mixed solution at room temperature, stirring for 15min at room temperature, placing the obtained mixed solution in a 80 ℃ constant-temperature water bath kettle, stirring and refluxing for 1h, then placing the mixed solution at room temperature for 30min, and then carrying out centrifugal separation, washing with water and drying to obtain the copper metal organic framework.
A preparation method of a copper metal organic framework modified starch-based composite film comprises the following steps:
(1) adding 100 parts of starch and 30 parts of plasticizer into 1600 parts of deionized water, stirring for 30 minutes at room temperature, and stirring and dissolving at 85 ℃ to obtain a starch solution;
(2) dispersing 1-7 parts of a copper metal organic frame in 1200 parts of deionized water, and stirring for 1 hour to obtain a uniform dispersion liquid;
(3) adding the dispersion liquid obtained in the step (2) into the starch solution obtained in the step (1), and stirring for 1h at 85 ℃ to obtain uniform film forming liquid;
(4) and (4) pouring the film forming liquid in the step (3) onto an organic glass dish, and drying in a vacuum oven at 50 ℃ for 24 hours to obtain the copper metal organic framework modified starch-based composite film.
The invention has the following beneficial effects:
the invention utilizes the self-made copper metal organic frame as a modifier, and can effectively improve the performance of the starch-based composite membrane material. The copper metal organic framework modified starch-based composite film prepared by the invention has excellent ultraviolet shielding performance, mechanical property, surface hydrophobic property and water vapor barrier property, the modified film material has lower hygroscopicity, the preparation process is simple and environment-friendly, the cost is low, the copper metal organic framework modified starch-based composite film is suitable for amplification production, and the copper metal organic framework modified starch-based composite film has good application prospects in the fields of packaging, ultraviolet protection and the like.
Drawings
FIG. 1 is a photograph of a pure starch film obtained in comparative example 1.
FIG. 2 is a photograph of a starch-based composite film obtained in example 4.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
In the specific examples and comparative formulations, 5-aminoisophthalic Acid (AIP) was provided by shanghai jen chemical technology, ltd, 2, 3-diamino-5-bromopyridine (APY) was provided by shanghai haohnhong biomedical science and technology, copper chloride dihydrate was provided by xigan chemical ltd, analytical grade reagent, and ethanol was provided by tianjin yu fine chemical ltd; corn starch (CAS number: 9005-25-8) was purchased from Aladdin Biotechnology, Inc., and glycerol (glycerol) was an analytical grade reagent supplied by Sjogren science, Inc.
In the formulas of the specific examples and the comparative examples, the copper metal organic framework is self-made nanoparticles (the average particle size is 7-19 nm), and the preparation method comprises the following steps: respectively dissolving 5-amino isophthalic Acid (AIP) and 2, 3-diamino-5-bromopyridine (APY) in ethanol to prepare a solution of 0.133 mmol/L5-amino isophthalic Acid (AIP) and a solution of 0.066 mmol/L2, 3-diamino-5-bromopyridine (APY); pouring 15mL of 5-amino isophthalic Acid (AIP) solution and 15mL of 2, 3-diamino-5-bromopyridine (APY) solution into a round-bottom flask, stirring for 1h, uniformly mixing, placing in a constant-temperature water bath kettle at 80 ℃, stirring and refluxing for 1h to obtain a mixed solution; and then, dropwise adding 15mL of 0.133mmol/L copper chloride ethanol solution into the mixed solution at room temperature, stirring for 15min at room temperature, placing the obtained mixed solution in a 80 ℃ constant-temperature water bath kettle, stirring and refluxing for 1h, then placing the mixed solution at room temperature for 30min, and then carrying out centrifugal separation, washing with water and drying to obtain the copper metal organic framework.
Example 1
A copper metal organic framework modified starch-based composite film comprises the following components in parts by weight: 100 parts of starch, 30 parts of glycerol and 1 part of copper metal organic framework.
The preparation method comprises the following steps:
(1) adding 100 parts of starch and 30 parts of glycerol into 1600 parts of deionized water, stirring for 30 minutes at room temperature, and stirring and dissolving at 85 ℃ to obtain a starch solution for later use;
(2) dispersing 1 part of a copper metal organic frame in 1200 parts of deionized water, and stirring for 1 hour to obtain a uniform dispersion liquid for later use;
(3) adding the dispersion liquid obtained in the step (2) into the starch solution obtained in the step (1), and stirring for 1h at 85 ℃ to obtain uniform film forming liquid;
(4) and (4) pouring the film forming liquid in the step (3) onto an organic glass dish, and drying in a vacuum oven at 50 ℃ for 24 hours to obtain the copper metal organic framework modified starch-based composite film.
Example 2
A copper metal organic framework modified starch-based composite film comprises the following components in parts by weight: 100 parts of starch, 30 parts of glycerol and 3 parts of copper metal organic framework.
The preparation method comprises the following steps:
(1) adding 100 parts of starch and 30 parts of glycerol into 1600 parts of deionized water, stirring for 30 minutes at room temperature, and stirring and dissolving at 85 ℃ to obtain a starch solution for later use;
(2) dispersing 3 parts of a copper metal organic frame in 1200 parts of deionized water, and stirring for 1 hour to obtain a uniform dispersion liquid for later use;
(3) adding the dispersion liquid obtained in the step (2) into the starch solution obtained in the step (1), and stirring for 1h at 85 ℃ to obtain uniform film forming liquid;
(4) and (4) pouring the film forming liquid in the step (3) onto an organic glass dish, and drying in a vacuum oven at 50 ℃ for 24 hours to obtain the copper metal organic framework modified starch-based composite film.
Example 3
A copper metal organic framework modified starch-based composite film comprises the following components in parts by weight: 100 parts of starch, 30 parts of glycerol and 5 parts of copper metal organic framework.
The preparation method comprises the following steps:
(1) adding 100 parts of starch and 30 parts of glycerol into 1600 parts of deionized water, stirring for 30 minutes at room temperature, and stirring and dissolving at 85 ℃ to obtain a starch solution for later use;
(2) dispersing 5 parts of a copper metal organic frame in 1200 parts of deionized water, and stirring for 1 hour to obtain a uniform dispersion liquid for later use;
(3) adding the dispersion liquid obtained in the step (2) into the starch solution obtained in the step (1), and stirring for 1h at 85 ℃ to obtain uniform film forming liquid;
(4) and (4) pouring the film forming liquid in the step (3) onto an organic glass dish, and drying in a vacuum oven at 50 ℃ for 24 hours to obtain the copper metal organic framework modified starch-based composite film.
Example 4
A copper metal organic framework modified starch-based composite film comprises the following components in parts by weight: 100 parts of starch, 30 parts of glycerol and 7 parts of copper metal organic framework.
The preparation method comprises the following steps:
(1) adding 100 parts of starch and 30 parts of glycerol into 1600 parts of deionized water, stirring for 30 minutes at room temperature, and stirring and dissolving at 85 ℃ to obtain a starch solution for later use;
(2) dispersing 7 parts of copper metal organic frame in 1200 parts of deionized water, and stirring for 1 hour to obtain uniform dispersion liquid for later use;
(3) adding the dispersion liquid obtained in the step (2) into the starch solution obtained in the step (1), and stirring for 1h at 85 ℃ to obtain uniform film forming liquid;
(4) and (4) pouring the film forming liquid in the step (3) onto an organic glass dish, and drying in a vacuum oven at 50 ℃ for 24 hours to obtain the copper metal organic framework modified starch-based composite film.
Comparative example
As a comparative standard to the above examples, the present invention provides a thermoplastic starch material prepared without the copper metal organic framework, comprising the steps of:
(1) adding 100 parts of starch and 30 parts of glycerol into 1600 parts of deionized water, stirring for 30 minutes at room temperature, and stirring and dissolving at 85 ℃ to obtain a starch solution for later use;
(2) adding 1200 parts of deionized water into the starch solution obtained in the step (1), and stirring for 1h at 85 ℃ to obtain uniform film forming liquid;
(3) and (3) pouring the film forming liquid in the step (2) onto an organic glass dish, and drying in a vacuum oven at 50 ℃ for 24 hours to obtain the thermoplastic starch film material.
And (3) performance testing:
the thermoplastic starch film material prepared in the comparative example and the starch-based composite film material prepared in the example were subjected to performance tests, wherein the tensile properties were tested according to GB/T1040-2006, the water vapor transmission coefficient was tested according to astm e96, the ultraviolet-visible properties were tested using an ultraviolet spectrophotometer (Lambda750, perkin elmer instruments) and the average ultraviolet (UVA, UVB and UVC) transmittance was calculated with reference to GB/T18830-2009.
The hygroscopicity test method is as follows:
a film sample having dimensions of 20mm by 0.1mm was placed in a vacuum drying oven at 105 ℃ and, after drying for 3 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 75% 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(ii) a The above performance test data are shown in table 1.
Table 1 performance test data
As can be seen from table 1, after the copper metal organic framework nanoparticles are added into the starch-based composite film, the ultraviolet shielding performance, the high-energy short-wave blue light blocking performance, the mechanical properties and the water vapor blocking performance of the starch-based film material can be effectively improved, and the modified film material has lower hygroscopicity.
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.