CN111019171B - Preparation method of antibacterial barrier PET (polyethylene terephthalate) protective film prepared by doping modified aluminosilicate with carboxylated chitosan - Google Patents
Preparation method of antibacterial barrier PET (polyethylene terephthalate) protective film prepared by doping modified aluminosilicate with carboxylated chitosan Download PDFInfo
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Abstract
The invention provides a preparation method of a hybrid antibacterial barrier PET (polyethylene terephthalate) protective film of modified aluminosilicate doped with carboxylated chitosan, which comprises the following steps: preparing aluminosilicate sol by kaolin fusion, then carrying out screening and KH-550 modification, adding the modified aluminosilicate sol into a carboxylated chitosan solution to prepare modified aluminosilicate doped carboxylated chitosan, then mixing the modified aluminosilicate doped carboxylated chitosan with ethylene glycol to obtain a carboxylated chitosan/aluminosilicate/ethylene glycol blend, carrying out in-situ polymerization with terephthalic acid to obtain PET modified master batch, and finally carrying out injection molding on the PET modified master batch and PET resin. The PET protective film prepared by the method can make up the defects of soft structure and reduced mechanical property of chitosan, and meanwhile, the prepared PET composite material has excellent water vapor barrier capability and becomes a substitute with more excellent performance in the fields of biomedical packaging, food preservation and the like.
Description
Technical Field
The invention belongs to the technical field of synthesis of high polymer composite materials, and particularly relates to a preparation method of a hybrid antibacterial barrier PET (polyethylene terephthalate) protective film of modified aluminosilicate doped carboxylated chitosan.
Background
In daily life, people often use materials with high barrier property, which generally refers to materials with high barrier effect on gas-liquid permeants, namely, materials for preventing oxygen from invading so as to prevent the oxidation and deterioration of commodities, in order to prolong the shelf life of products and protect the products from the influence of external environment; preventing water or water vapor from penetrating to prevent the commodity from becoming damp and mildewed; prevent the fragrance, the fragrance and the carbon dioxide from escaping, so as to prevent the commodity from changing the taste, deteriorating the quality and the like. High molecular materials with high barrier properties are becoming more and more popular because of their light weight, good flexibility, easy flexibility, transparency and low cost. The high polymer material with high barrier property widens the selection range of the material, and gradually changes the traditional packaging material from high consumption and high quality to portability, corrosion resistance, low cost, easy degradation and environmental protection.
Polyethylene terephthalate (PET) is prepared by synthesizing dihydroxy ethyl terephthalate (BHET) from terephthalic acid and ethylene glycol and then performing polycondensation reaction, belongs to crystalline saturated resin, and has smooth and glossy surface. PET has excellent barrier property due to the characteristics of symmetrical chemical structure, better molecular chain planarity, tight molecular chain stacking and easy crystallization orientation. The material has excellent physical performance, chemical performance, size stability, transparency and recoverability, and can be widely applied to the fields of magnetic recording, photosensitive materials, electronics, electrical insulation, industrial films, package decoration, screen protection, optical mirror surface protection and the like.
Chitosan is a natural polysaccharide biological macromolecule, wherein the most remarkable characteristics are film-forming property and antibacterial and antiseptic effects, and the two unique properties enable the chitosan to be widely applied to the fields of edible film carriers, biodegradable films and the like. Chitosan is the only natural weakly basic polysaccharide, which is easily dissolved in a weak acid solvent, and particularly, the dissolved solution contains amino (C)NH2 +) The surface of the fungal cell is provided with negative electricity groups, the amino in the chitosan solution inhibits the bacterial activity through the negative electricity groups on the surface of the fungal cell, and the PET protective film prepared by adding the chitosan has a sanitary self-cleaning function, so that a lot of cleaning labor can be saved. In addition, the chitosan has strong adsorption capacity, the adsorption activity of the chitosan can selectively play a role, magnesium and potassium can be adsorbed, zinc, calcium, mercury and uranium can be adsorbed, and the concentration of metal ions in a human body is too high and harmful to the human body. The chitosan derivative has many active hydrophilic polar groups such as-OH, -COOH and-NH2These groups can make it hygroscopic, with carboxylated chitosan, the hydroxyl content is much greater than other derivatives, and the hydrophilic nature of the carboxyl groups allows more moisture to be bound. However, the intermolecular hydrogen bond interaction exists in chitosan, and-NH is limited2And the mechanical strength, thermal stability and chemical stability of chitosan are also to be further improved, so when chitosan is used to prepare composite materials, the chitosan needs to be modified.
The hydrated aluminosilicate is a three-dimensional framework structure compound consisting of silicon oxygen and aluminum oxide tetrahedron, and has a plurality of pore passages with uniform pore diameters and regularly arranged holes in the structure. The aluminosilicate has unique adsorption performance due to the open framework structure, the large internal surface area, and the strong coulomb field and polarity effect in crystal cavities. In addition, alumina in aluminosilicate has strong water adsorption capacity and is a common adsorption material.
Disclosure of Invention
The invention aims to develop a synthetic method of PET with high barrier property aiming at the problems that the barrier property of the existing PET packaging film and protective film can not meet the pursuit of people for high-quality life, the mechanical property of a PET composite material is reduced due to the addition of carboxylated chitosan, the single carboxylated chitosan can not well prevent water vapor from entering and the like. The modified aluminosilicate doped carboxylated chitosan hybrid barrier PET protective film prepared by the method has high barrier property and certain antibacterial capacity, and can become a more excellent substitute in the fields of biomedical packaging, food preservation and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the modified aluminosilicate-doped carboxylated chitosan hybrid antibacterial barrier PET protective film comprises the following raw materials in parts by weight: PET resin: 100 parts of PET modified master batch: 10-30 parts.
The PET resin is polyethylene terephthalate, and the molecular weight of the monomer terephthalic acid used for synthesizing the PET resin is 166.13, and the density of the monomer terephthalic acid is 1.55g/cm3(ii) a The ethylene glycol has a molecular weight of 62.068 and a density of 1.12g/cm3. The PET resin has an intrinsic viscosity of 0.800-0.840 dl/g, a melting point of 240 ℃ or higher and a density of 1.38g/cm3。
The preparation method of the PET modified master batch comprises the following steps: preparing aluminosilicate sol by kaolin fusion, then carrying out screening and KH-550 modification, adding the modified aluminosilicate sol into a carboxylated chitosan solution to prepare modified aluminosilicate doped carboxylated chitosan, then mixing the modified aluminosilicate doped carboxylated chitosan with ethylene glycol to obtain a carboxylated chitosan/aluminosilicate/ethylene glycol blend, and then carrying out in-situ polymerization with terephthalic acid to obtain PET modified master batch.
The preparation method of the PET modified master batch comprises the following specific steps:
1) preparation of aluminosilicate sol: weighing 10g of kaolin and 10g of NaOH, uniformly mixing, activating for 2 hours in a tubular furnace at 550 ℃, and removing organic impurities in the kaolin to obtain aluminosilicate sol;
2) screening of aluminosilicate: grinding and crushing aluminosilicate sol, screening by using a 200-mesh sieve, dissolving the screened sol by using deionized water, adding excessive NaOH into the solution to remove impurity Fe in kaolin, finally dropwise adding excessive ammonia water, and drying the product to obtain aluminosilicate;
3) preparation of modified aluminosilicate sol: dissolving the aluminosilicate obtained in the step 2) in 75ml of absolute ethyl alcohol, and dropwise adding a certain amount of aluminosilicate into the mixture under the stirring of water bath at the temperature of 80 DEG CKH-550, reacting for 2h to obtain SiO in aluminosilicate2Surface amination;
4) preparing modified aluminosilicate doped carboxylated chitosan: weighing 2g of carboxylated chitosan, dissolving the 2g of carboxylated chitosan in a mixed solution of 100ml of deionized water and 1ml of glacial acetic acid, adding the modified aluminosilicate sol obtained in the step 3) into the carboxylated chitosan solution, stirring at room temperature for 4h, precipitating overnight to enable the aminated aluminosilicate sol to react with carboxyl on the surface of the carboxylated chitosan, and then drying the product to obtain the modified aluminosilicate doped carboxylated chitosan;
5) preparation of carboxylated chitosan/aluminosilicate/ethylene glycol blend: adding the modified aluminosilicate doped carboxylated chitosan obtained in the step 4) into 59.9ml of ethylene glycol, and performing ultrasonic treatment until the solution is uniformly mixed to obtain a carboxylated chitosan/aluminosilicate/ethylene glycol blend;
6) adding 40.0g of terephthalic acid, 0.05g of antimony trioxide and 0.05g of ammonium phosphate into a three-neck flask, finally adding a carboxylated chitosan/aluminosilicate/ethylene glycol blend, introducing nitrogen to provide an oxygen-free environment, starting a mechanical stirrer, esterifying the mixed solution at 180-220 ℃ for 90min, heating to 260-280 ℃ for polycondensation, stopping the reaction until no water is discharged in the system, pouring into a mold, curing in a 160 ℃ vacuum drying oven for 12h, and extruding and granulating the obtained product to obtain the PET modified master batch.
The preparation method of the PET protective film comprises the following steps: and (3) mixing the PET modified master batch and PET resin at a high speed, drying for 4-6 h at 120-150 ℃, and performing injection molding by using an injection machine at the temperature of 245-255 ℃. The mixing conditions of the PET modified master batch and the PET resin are as follows: the mixing temperature is 35-60 ℃, and the mixing time is 5-10 min.
The invention realizes the barrier property of the PET material to water molecules through the synergistic effect of the hydrophilic and hydrophobic structures on the surfaces of the carboxylated chitosan and the aluminosilicate. The unmodified carboxylated chitosan is an amorphous structure with a compact surface, and becomes a fluffy structure with a loose and porous surface after being modified by active aluminosilicate. After kaolin is activated and surface modified by amino functionalization, the surface of the kaolin is mixed with the surface of the carboxyl chitosanCarboxyl and hydroxyl and other active groups are condensed to form amido bond, so that kaolin is doped into the carboxylated chitosan to enable the carboxylated chitosan to form a pore structure (Al in the pores has hydrophilic property). The hydrophobic structure on the outer side of the carboxylated chitosan can effectively prevent water vapor in the air from entering, and the huge hydrophilic holes on the inner side can absorb the water vapor remained in the protective film, so that the carboxylated chitosan-kaolin composite material can effectively enhance the barrier property of the PET film to water molecules. Different from the common method that the water barrier property is improved by adding single carboxylated chitosan or chitosan into PET through physical blending, the invention has the advantage that the surface of the PET contains a large amount of active hydroxyl (-OH) and amino (-NH)2) The modified aluminosilicate contains a large number of active hydroxyl (-OH), carboxyl (-COOH) and amino (-NH) groups on the surface2) The carboxylated chitosan solution is combined together through chemical bonding, the defects of insufficient mechanical strength, thermal stability and chemical stability of chitosan are overcome, and the PET protective film prepared by the method not only can show higher barrier property to water vapor, but also can have certain antibacterial capacity. In addition, hydroxyl (-OH), carboxyl (-COOH) and amino (-NH 2) which are not completely reacted are chemically bonded with terminal hydroxyl and terminal carboxyl at the end of the PET, so that the aluminosilicate modified carboxylated chitosan is more tightly combined with the PET, and the distribution of the aluminosilicate modified carboxylated chitosan is more uniform, thereby being an environment-friendly composite material.
The invention has the beneficial effects that:
the hybrid antibacterial barrier PET protective film prepared by the invention and doped with the modified aluminosilicate and the carboxylated chitosan can be used as a protective film in the aspect of biomedical use: the medical apparatus is mostly composed of a high polymer material and a metal material, the high polymer material absorbs water and is easy to yellow, the metal material is easy to corrode and rust when contacting with water, and the medical apparatus generally requires sterility.
Drawings
FIG. 1 is a scanning electron microscope image of a modified aluminosilicate doped carboxylated chitosan prepared in accordance with the present invention;
FIG. 2 is a scanning electron micrograph of unmodified carboxylated chitosan;
FIG. 3 is an infrared test chart of the modified aluminosilicate doped carboxylated chitosan prepared in the present invention.
Detailed Description
In order to facilitate understanding of the present invention, the technical solutions of the present invention are further described below with reference to the specific embodiments, but the present invention is not limited thereto.
The preparation method of the PET modified master batch comprises the following specific steps:
1) preparation of aluminosilicate sol: weighing 10g of kaolin and 10g of NaOH, uniformly mixing, activating for 2 hours in a tubular furnace at 550 ℃, and removing organic impurities in the kaolin to obtain aluminosilicate sol;
2) screening of aluminosilicate: grinding and crushing aluminosilicate sol, screening by using a 200-mesh sieve, dissolving the screened sol by using deionized water, adding excessive NaOH into the solution to remove impurity Fe in kaolin, finally dropwise adding excessive ammonia water, and drying the product to obtain aluminosilicate;
3) preparation of modified aluminosilicate sol: dissolving the aluminosilicate obtained in the step 2) in 75ml of absolute ethyl alcohol, dripping 2ml of KH-550 into the aluminosilicate under the stirring of water bath at the temperature of 80 ℃, and reacting for 2 hours to ensure that SiO in the aluminosilicate2Surface amination;
4) preparing modified aluminosilicate doped carboxylated chitosan: weighing 2g of carboxylated chitosan, dissolving the 2g of carboxylated chitosan in a mixed solution of 100ml of deionized water and 1ml of glacial acetic acid, adding the modified aluminosilicate sol obtained in the step 3) into the carboxylated chitosan solution, stirring at room temperature for 4h, precipitating overnight to enable the aminated aluminosilicate sol to react with carboxyl on the surface of the carboxylated chitosan, and then drying the product to obtain the modified aluminosilicate doped carboxylated chitosan;
5) preparation of carboxylated chitosan/aluminosilicate/ethylene glycol blend: adding the modified aluminosilicate doped carboxylated chitosan obtained in the step 4) into 59.9ml of ethylene glycol, and performing ultrasonic treatment until the solution is uniformly mixed to obtain a carboxylated chitosan/aluminosilicate/ethylene glycol blend;
6) adding 40.0g of terephthalic acid, 0.05g of antimony trioxide and 0.05g of ammonium phosphate into a three-neck flask, finally adding a carboxylated chitosan/aluminosilicate/ethylene glycol blend, introducing nitrogen to provide an oxygen-free environment, starting a mechanical stirrer, esterifying the mixed solution at 220 ℃ for 90min, heating to 280 ℃ for polycondensation, stopping the reaction until no water is discharged in the system, pouring into a mold, curing in a 160 ℃ vacuum drying oven for 12h, and extruding and granulating the obtained product to obtain the PET modified master batch.
Example 1
The modified aluminosilicate-doped carboxylated chitosan hybrid antibacterial barrier PET protective film comprises the following raw materials in parts by weight:
PET resin: 100 parts of (A);
PET modified master batch: 10 parts.
The preparation method of the PET protective film comprises the following steps: mixing the PET modified master batch and PET resin at high speed, drying at 120 ℃ for 4h, and performing injection molding by an injection machine at 245 ℃.
The mixing conditions of the PET modified master batch and the PET resin are as follows: the mixing temperature was 35 ℃ and the mixing time was 5 min.
Example 2
The modified aluminosilicate-doped carboxylated chitosan hybrid antibacterial barrier PET protective film comprises the following raw materials in parts by weight:
PET resin: 100 parts of (A);
PET master batch: and 20 parts.
The preparation method of the PET protective film comprises the following steps: mixing the PET modified master batch and PET resin at high speed, drying at 120 ℃ for 4h, and performing injection molding by an injection machine at 245 ℃.
The mixing conditions of the PET modified master batch and the PET resin are as follows: the mixing temperature was 35 ℃ and the mixing time was 5 min.
Example 3
The modified aluminosilicate-doped carboxylated chitosan hybrid antibacterial barrier PET protective film comprises the following raw materials in parts by weight:
PET resin: 100 parts of (A);
PET master batch: 30 parts of.
The preparation method of the PET protective film comprises the following steps: mixing the PET modified master batch and PET resin at high speed, drying at 120 ℃ for 4h, and performing injection molding by an injection machine at 245 ℃.
The mixing conditions of the PET modified master batch and the PET resin are as follows: the mixing temperature was 35 ℃ and the mixing time was 5 min.
Comparative example 1
Drying 100wt% pure PET at 120 deg.C for 4h, and injection molding with injection machine at 245 deg.C. Cutting into 80 × 10 × 4mm3、125×13×4mm3And 150X 20X 4mm3The standard size of the dumbbell type of (1) was measured.
Comparative example 2
PET resin and kaolin are mixed according to the weight ratio of 100: 30 at 35 deg.C for 5min, oven drying at 120 deg.C for 4h, and injection molding with 245 deg.C injection machine. Cutting into 80 × 10 × 4mm3、125×13×4mm3And 150X 20X 4mm3The standard size of the dumbbell type of (1) was measured.
Comparative example 3
Adding 40.0g of terephthalic acid, 0.05g of antimony trioxide, 0.05g of ammonium phosphate and 2.0g of carboxylated chitosan into a three-neck flask, finally adding 59.9ml of ethylene glycol, introducing nitrogen to provide an oxygen-free environment, starting a mechanical stirrer, esterifying the mixed solution at 220 ℃ for 90min, heating to 280 ℃ for polycondensation, stopping the reaction until no water is discharged in the system, pouring into a mold, aging in a 160 ℃ vacuum drying box for 12h, and extruding and granulating the obtained product to obtain the carboxylated chitosan/PET modified master batch.
30 parts of carboxylated chitosan/PET modified master batch and 100 parts of PET resin are mixed at high speed, dried for 4 hours at the temperature of 120 ℃, and injection molded by an injection machine at the temperature of 245 ℃.
The mixing conditions of the PET modified master batch and the PET resin are as follows: the mixing temperature was 35 ℃ and the mixing time was 5 min.
Scanning test is carried out on the modified aluminosilicate doped carboxylated chitosan prepared by the invention, and the result is shown in figure 1;
scanning unmodified carboxylated chitosan and the result is shown in figure 2;
the modified aluminosilicate doped carboxylated chitosan prepared by the invention is subjected to infrared test, and the result is shown in figure 3.
As can be seen from the comparison between the figure 1 and the figure 2, the unmodified carboxylated chitosan is of a surface-dense amorphous structure, while the surface of the carboxylated chitosan doped with the modified aluminosilicate is in a loose and porous fluffy state, and the loose and porous fluffy structure and the Al doped in the hollow holes can play a role in blocking water vapor.
As can be seen from FIG. 3, at 1750cm-1Left and right and 1300cm-1Two strong absorption peaks are arranged on the left and the right, which are stretching vibration peaks of ester bonds formed by chemical bonding of hydroxyl on the surface of the modified aluminosilicate and the carboxylated chitosan; at 3000cm-1The left and right have two strong absorption peaks, which are stretching vibration peaks of amido bonds formed by chemical bonding of amino groups on the surface of the modified aluminosilicate and carboxyl groups of the carboxylated chitosan.
The performance comparison test was performed on the hybrid antibacterial barrier PET protective film of the modified aluminosilicate-doped carboxylated chitosan obtained in examples 1 to 3 and the PET films prepared in comparative examples 1 to 3, and the results are shown in table 1.
TABLE 1 sample Performance test
The above description is only for the best mode of the invention, and all equivalent changes and modifications made in accordance with the claims of the invention should be covered by the present invention.
Claims (5)
1. A preparation method of a hybrid antibacterial barrier PET protective film of modified aluminosilicate doped carboxylated chitosan is characterized by comprising the following steps: the PET protective film comprises the following raw materials in parts by weight: 100 parts of PET resin and 10-30 parts of PET modified master batch;
the preparation method of the PET modified master batch comprises the following steps: preparing aluminosilicate sol by kaolin fusion, then carrying out screening and KH-550 modification, adding the modified aluminosilicate sol into a carboxylated chitosan solution to prepare modified aluminosilicate doped carboxylated chitosan, then mixing the modified aluminosilicate doped carboxylated chitosan with ethylene glycol to obtain a carboxylated chitosan/aluminosilicate/ethylene glycol blend, and then carrying out in-situ polymerization with terephthalic acid to obtain PET modified master batch.
2. The preparation method of the modified aluminosilicate doped carboxylated chitosan hybrid antibacterial barrier PET protective film according to claim 1, which is characterized in that: the preparation method of the PET modified master batch comprises the following specific steps:
1) preparation of aluminosilicate sol: weighing 10g of kaolin and 10g of NaOH, uniformly mixing, activating for 2 hours in a tubular furnace at 550 ℃, and removing organic impurities in the kaolin to obtain aluminosilicate sol;
2) screening of aluminosilicate: grinding and crushing aluminosilicate sol, screening by using a 200-mesh sieve, dissolving the screened sol by using deionized water, adding excessive NaOH into the solution to remove impurity Fe in kaolin, finally dropwise adding excessive ammonia water, and drying the product to obtain aluminosilicate;
3) preparation of modified aluminosilicate sol: dissolving the aluminosilicate obtained in the step 2) in 75ml of absolute ethyl alcohol, dropwise adding a certain amount of KH-550 under the stirring of water bath at the temperature of 80 ℃, and reacting for 2 hours to ensure that SiO in the aluminosilicate2Surface amination;
4) preparing modified aluminosilicate doped carboxylated chitosan: weighing 2g of carboxylated chitosan, dissolving the 2g of carboxylated chitosan in a mixed solution of 100ml of deionized water and 1ml of glacial acetic acid, adding the modified aluminosilicate sol obtained in the step 3) into the carboxylated chitosan solution, stirring at room temperature for 4h, precipitating overnight to enable the aminated aluminosilicate sol to react with carboxyl on the surface of the carboxylated chitosan, and then drying the product to obtain the modified aluminosilicate doped carboxylated chitosan;
5) preparation of carboxylated chitosan/aluminosilicate/ethylene glycol blend: adding the modified aluminosilicate doped carboxylated chitosan obtained in the step 4) into 59.9ml of ethylene glycol, and performing ultrasonic treatment until the solution is uniformly mixed to obtain a carboxylated chitosan/aluminosilicate/ethylene glycol blend;
6) adding 40.0g of terephthalic acid, 0.05g of antimony trioxide and 0.05g of ammonium phosphate into a three-neck flask, finally adding a carboxylated chitosan/aluminosilicate/ethylene glycol blend, introducing nitrogen to provide an oxygen-free environment, starting a mechanical stirrer, esterifying the mixed solution at 180-220 ℃ for 90min, heating to 260-280 ℃ for polycondensation, stopping the reaction until no water is discharged in the system, pouring into a mold, curing in a 160 ℃ vacuum drying oven for 12h, and extruding and granulating the obtained product to obtain the PET modified master batch.
3. The preparation method of the modified aluminosilicate doped carboxylated chitosan hybrid antibacterial barrier PET protective film according to claim 1, which is characterized in that: the PET resin is polyethylene terephthalate, the intrinsic viscosity of the PET resin is 0.800-0.840 dl/g, the melting point is more than or equal to 240 ℃, and the density is 1.38g/cm3。
4. The preparation method of the modified aluminosilicate doped carboxylated chitosan hybrid antibacterial barrier PET protective film according to claim 1, which is characterized in that: the preparation method of the PET protective film comprises the following steps: and (3) mixing the PET modified master batch and PET resin at a high speed, drying for 4-6 h at 120-150 ℃, and performing injection molding by using an injection machine at the temperature of 245-255 ℃.
5. The preparation method of the modified aluminosilicate doped carboxylated chitosan hybrid antibacterial barrier PET protective film according to claim 4, which is characterized in that: the mixing conditions of the PET modified master batch and the PET resin are as follows: the mixing temperature is 35-60 ℃, and the mixing time is 5-10 min.
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