CN113912879A - Environment-friendly heat shrinkable film - Google Patents
Environment-friendly heat shrinkable film Download PDFInfo
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- CN113912879A CN113912879A CN202110964783.5A CN202110964783A CN113912879A CN 113912879 A CN113912879 A CN 113912879A CN 202110964783 A CN202110964783 A CN 202110964783A CN 113912879 A CN113912879 A CN 113912879A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- Processes Of Treating Macromolecular Substances (AREA)
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Abstract
The invention belongs to the technical field of packaging films, and particularly relates to an environment-friendly heat shrinkable film which is characterized by comprising the following raw materials in parts by mass; 50-100 parts of polyester, 0.5-1 part of edible hydrophobic substance, 0.5-1 part of emulsifier, 1.5-2 parts of antioxidant, 1.2-1.7 parts of light stabilizer and 1-6 parts of modified collagen. According to the technical scheme, the modified collagen prepared by grafting polyethylene glycol on the collagen, then carrying out esterification reaction with oxalic acid and then carrying out esterification reaction with ethylene glycol contains a large number of ester-based functional groups, and the ester-based functional groups in the modified collagen can realize better compounding with polyester, so that the dispersibility of polyester particles in the modified collagen is improved, and the polyester heat-shrinkable film is further provided with better contractility.
Description
Technical Field
The invention belongs to the technical field of packaging films, and particularly relates to an environment-friendly heat shrinkable film.
Background
Polyester heat-shrinkable film is a new type of heat-shrinkable packaging material. Because it has the characters of easy recovery, non-toxic, tasteless, good mechanical property, specially according with the environmental protection, etc., the polyester has become the ideal substitute for polyvinyl chloride heat-shrinkable film in developed countries, however, the common polyester is a crystalline high polymer, and the heat-shrinkable rate of the common film can only be obtained below 30% by special process treatment. If a polyester film with a higher heat shrinkage is to be obtained, modification is also necessary. That is, in order to prepare a polyester film having a high heat shrinkage rate, it is generally necessary to modify conventional polyesters by copolymerization or blending.
The animal collagen can shrink at the temperature of more than 60 ℃, the natural triple helical structure is irreversibly converted into a more random (curled) structure due to the breakage of hydrogen bonds and hydrophobic bonds between molecules and in molecules, and the animal collagen is used for modifying the polyester, so that the shrinkage rate of the polyester heat shrinkable film can be greatly improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an environment-friendly heat shrinkable film, which solves the problem of poor shrinkability of the traditional polyester heat shrinkable film and improves the shrinkability of the polyester heat shrinkable film.
In order to achieve the purpose, the invention is realized by the following scheme:
an environment-friendly heat shrinkable film is characterized by comprising the following raw materials in parts by mass; 50-100 parts of polyester, 1.5-2 parts of edible hydrophobic substance, emulsifier, antioxidant, 1.2-1.7 parts of light stabilizer and 1-6 parts of modified collagen.
Preferably, the polyester is composed of lactic acid-co-glycolic acid, polylactic acid and polycaprolactone, wherein the mass ratio of the lactic acid-co-glycolic acid to the polylactic acid to the polycaprolactone is 6-8: 1-3: 1.
Preferably, the edible hydrophobic substance is selected from one of stearic acid, palmitic acid and beeswax.
The environmentally friendly heat shrinkable film of claim 1, wherein: the edible emulsifier is at least one selected from sucrose fatty acid ester, citric acid glyceride and polyglycerol fatty acid ester.
Preferably, the preparation method of the environment-friendly heat shrinkable film is characterized in that: the method comprises the following steps:
(1) mixing collagen with polyethylene glycol, carrying out oil bath stirring reaction, dropwise adding oxalic acid after the reaction is finished, and dropwise adding ethylene glycol after the dropwise adding of oxalic acid is finished to obtain modified collagen;
(2) heating and dissolving an aqueous solution containing edible hydrophobic substances and edible emulsifiers, and then carrying out homogenizing and emulsifying treatment by using a tissue triturator to obtain a hydrophobic substance emulsion;
(3) and (3) mixing the modified collagen obtained in the step (1), the hydrophobic substance emulsion obtained in the step (2) and polyester, homogenizing and emulsifying, defoaming, uniformly coating on organic silicon resin, drying, cooling to room temperature, and removing the film to obtain a finished product.
Preferably, the mass ratio of the collagen to the polyethylene glycol, the oxalic acid and the ethylene glycol in the step (1) is 10-20: 1-5: 5-10: 1.
Preferably, the reaction temperature in the step (1) is 70-80 ℃, and the reaction time is 1-3 h.
Preferably, the temperature of heating in the step (2) is 50-60 ℃.
Preferably, the temperature for drying in the step (3) is 40-50 ℃.
Compared with the prior art, the method has the beneficial effects that:
(1) according to the technical scheme, the modified collagen prepared by grafting polyethylene glycol on the collagen, then carrying out esterification reaction with oxalic acid and then carrying out esterification reaction with ethylene glycol contains a large number of ester-based functional groups, and the ester-based functional groups in the modified collagen can realize better compounding with polyester, so that the dispersibility of polyester particles in the modified collagen is improved, and the polyester heat-shrinkable film is further provided with better contractility.
(2) In the technical scheme of the invention, the polyester is modified by the modified collagen, so that the contractility of the polyester heat-shrinkable film can be improved, in addition, raw materials such as polyethylene glycol, oxalic acid, ethylene glycol and the like used in the process of modifying the collagen have small pollution to the environment and can be degraded, and the modified collagen is used for the polyester heat-shrinkable film and can be degraded to meet the requirement of environmental protection.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
An environment-friendly heat shrinkable film comprises the following raw materials in parts by mass; 50 parts of polyester, 0.5 part of edible hydrophobic substance, 0.5 part of emulsifier, 1.5 parts of antioxidant, 1.2 parts of light stabilizer and 1 part of modified collagen.
The polyester is composed of lactic acid-co-glycolic acid, polylactic acid and polycaprolactone, wherein the mass ratio of the lactic acid-co-glycolic acid to the polylactic acid to the polycaprolactone is 7: 2: 1, the edible hydrophobic substance is stearic acid, and the emulsifier is sucrose fatty acid ester and polyglycerol fatty acid ester.
In this embodiment, a method for preparing an environmentally friendly heat shrinkable film includes the following steps:
(1) mixing collagen with polyethylene glycol, stirring in an oil bath for reaction at 75 ℃ for 2h, dropwise adding oxalic acid after the reaction is finished, and dropwise adding ethylene glycol after the oxalic acid is dropwise added, wherein the mass ratio of the collagen to the polyethylene glycol, the oxalic acid and the ethylene glycol is 15: 3: 7: 1, so as to obtain modified collagen;
(2) heating and dissolving an aqueous solution containing edible hydrophobic substances and an emulsifier, heating to 55 ℃, and carrying out homogenizing and emulsifying treatment by using a tissue triturator to obtain a hydrophobic substance emulsion;
(3) and (3) mixing the modified collagen obtained in the step (1), the hydrophobic substance emulsion obtained in the step (2) and polyester, homogenizing and emulsifying, defoaming, uniformly coating on organic silicon resin, drying, cooling to room temperature, and removing the film, wherein the drying temperature is 45 ℃, so that a finished product is obtained.
Example 2
An environment-friendly heat shrinkable film comprises the following raw materials in parts by mass; 60 parts of polyester, 0.6 part of edible hydrophobic substance, 0.6 part of emulsifier, 1.6 parts of antioxidant, 1.3 parts of light stabilizer and 2 parts of modified collagen.
The polyester is composed of lactic acid-co-glycolic acid, polylactic acid and polycaprolactone, wherein the mass ratio of the lactic acid-co-glycolic acid to the polylactic acid to the polycaprolactone is 7: 2: 1, the edible hydrophobic substance is stearic acid, and the emulsifier is sucrose fatty acid ester and polyglycerol fatty acid ester.
In this embodiment, a method for preparing an environmentally friendly heat shrinkable film includes the following steps:
(1) mixing collagen with polyethylene glycol, stirring in an oil bath for reaction at 75 ℃ for 2h, dropwise adding oxalic acid after the reaction is finished, and dropwise adding ethylene glycol after the oxalic acid is dropwise added, wherein the mass ratio of the collagen to the polyethylene glycol, the oxalic acid and the ethylene glycol is 15: 3: 7: 1, so as to obtain modified collagen;
(2) heating and dissolving an aqueous solution containing edible hydrophobic substance and edible emulsifier at 55 deg.C, and homogenizing and emulsifying with a tissue triturator to obtain hydrophobic substance emulsion;
(3) and (3) mixing the modified collagen obtained in the step (1), the hydrophobic substance emulsion obtained in the step (2) and polyester, homogenizing and emulsifying, defoaming, uniformly coating on organic silicon resin, drying, cooling to room temperature, and removing the film, wherein the drying temperature is 45 ℃, so that a finished product is obtained.
Example 3
An environment-friendly heat shrinkable film comprises the following raw materials in parts by mass; 70 parts of polyester, 0.7 part of edible hydrophobic substance, 0.7 part of emulsifier, 1.7 parts of antioxidant, 1.4 parts of light stabilizer and 3 parts of modified collagen.
The polyester is composed of lactic acid-co-glycolic acid, polylactic acid and polycaprolactone, wherein the mass ratio of the lactic acid-co-glycolic acid to the polylactic acid to the polycaprolactone is 7: 2: 1, the edible hydrophobic substance is stearic acid, and the emulsifier is sucrose fatty acid ester and polyglycerol fatty acid ester.
In this embodiment, a method for preparing an environmentally friendly heat shrinkable film includes the following steps:
(1) mixing collagen with polyethylene glycol, stirring in an oil bath for reaction at 75 ℃ for 2h, dropwise adding oxalic acid after the reaction is finished, and dropwise adding ethylene glycol after the oxalic acid is dropwise added, wherein the mass ratio of the collagen to the polyethylene glycol, the oxalic acid and the ethylene glycol is 15: 3: 7: 1, so as to obtain modified collagen;
(2) heating and dissolving an aqueous solution containing edible hydrophobic substances and an emulsifier, heating to 55 ℃, and carrying out homogenizing and emulsifying treatment by using a tissue triturator to obtain a hydrophobic substance emulsion;
(3) and (3) mixing the modified collagen obtained in the step (1), the hydrophobic substance emulsion obtained in the step (2) and polyester, homogenizing and emulsifying, defoaming, uniformly coating on organic silicon resin, drying, cooling to room temperature, and removing the film, wherein the drying temperature is 45 ℃, so that a finished product is obtained.
Example 4
An environment-friendly heat shrinkable film comprises the following raw materials in parts by mass; 80 parts of polyester, 0.8 part of edible hydrophobic substance, 0.8 part of emulsifier, 1.8 parts of antioxidant, 1.5 parts of light stabilizer and 4 parts of modified collagen.
The polyester is composed of lactic acid-co-glycolic acid, polylactic acid and polycaprolactone, wherein the mass ratio of the lactic acid-co-glycolic acid to the polylactic acid to the polycaprolactone is 7: 2: 1, the edible hydrophobic substance is stearic acid, and the emulsifier is sucrose fatty acid ester and polyglycerol fatty acid ester.
In this embodiment, a method for preparing an environmentally friendly heat shrinkable film includes the following steps:
(1) mixing collagen with polyethylene glycol, stirring in an oil bath for reaction at 75 ℃ for 2h, dropwise adding oxalic acid after the reaction is finished, and dropwise adding ethylene glycol after the oxalic acid is dropwise added, wherein the mass ratio of the collagen to the polyethylene glycol, the oxalic acid and the ethylene glycol is 15: 3: 7: 1, so as to obtain modified collagen;
(2) heating and dissolving an aqueous solution containing edible hydrophobic substance and edible emulsifier at 55 deg.C, and homogenizing and emulsifying with a tissue triturator to obtain hydrophobic substance emulsion;
(3) and (3) mixing the modified collagen obtained in the step (1), the hydrophobic substance emulsion obtained in the step (2) and polyester, homogenizing and emulsifying, defoaming, uniformly coating on organic silicon resin, drying, cooling to room temperature, and removing the film, wherein the drying temperature is 45 ℃, so that a finished product is obtained.
Example 5
An environment-friendly heat shrinkable film comprises the following raw materials in parts by mass; 90 parts of polyester, 0.9 part of edible hydrophobic substance, 0.9 part of emulsifier, 1.9 parts of antioxidant, 1.6 parts of light stabilizer and 5 parts of modified collagen.
The polyester is composed of lactic acid-co-glycolic acid, polylactic acid and polycaprolactone, wherein the mass ratio of the lactic acid-co-glycolic acid to the polylactic acid to the polycaprolactone is 7: 2: 1, the edible hydrophobic substance is stearic acid, and the edible emulsifier is at least one of sucrose fatty acid ester and polyglycerol fatty acid ester.
In this embodiment, a method for preparing an environmentally friendly heat shrinkable film includes the following steps:
(1) mixing collagen with polyethylene glycol, stirring in an oil bath for reaction at 75 ℃ for 2h, dropwise adding oxalic acid after the reaction is finished, and dropwise adding ethylene glycol after the oxalic acid is dropwise added, wherein the mass ratio of the collagen to the polyethylene glycol, the oxalic acid and the ethylene glycol is 15: 3: 7: 1, so as to obtain modified collagen;
(2) heating and dissolving an aqueous solution containing edible hydrophobic substances and an emulsifier, heating to 55 ℃, and carrying out homogenizing and emulsifying treatment by using a tissue triturator to obtain a hydrophobic substance emulsion;
(3) and (3) mixing the modified collagen obtained in the step (1), the hydrophobic substance emulsion obtained in the step (2) and polyester, homogenizing and emulsifying, defoaming, uniformly coating on organic silicon resin, drying, cooling to room temperature, and removing the film, wherein the drying temperature is 45 ℃, so that a finished product is obtained.
Example 6
An environment-friendly heat shrinkable film comprises the following raw materials in parts by mass; 100 parts of polyester, 1 part of edible hydrophobic substance, 1 part of emulsifier, 2 parts of antioxidant, 1.7 parts of light stabilizer and 6 parts of modified collagen.
The polyester is composed of lactic acid-co-glycolic acid, polylactic acid and polycaprolactone, wherein the mass ratio of the lactic acid-co-glycolic acid to the polylactic acid to the polycaprolactone is 7: 2: 1, the edible hydrophobic substance is stearic acid, and the emulsifier is sucrose fatty acid ester and polyglycerol fatty acid ester.
In this embodiment, a method for preparing an environmentally friendly heat shrinkable film includes the following steps:
(1) mixing collagen with polyethylene glycol, stirring in an oil bath for reaction at 75 ℃ for 2h, dropwise adding oxalic acid after the reaction is finished, and dropwise adding ethylene glycol after the oxalic acid is dropwise added, wherein the mass ratio of the collagen to the polyethylene glycol, the oxalic acid and the ethylene glycol is 15: 3: 7: 1, so as to obtain modified collagen;
(2) heating and dissolving an aqueous solution containing edible hydrophobic substances and an emulsifier, heating to 55 ℃, and carrying out homogenizing and emulsifying treatment by using a tissue triturator to obtain a hydrophobic substance emulsion;
(3) and (3) mixing the modified collagen obtained in the step (1), the hydrophobic substance emulsion obtained in the step (2) and polyester, homogenizing and emulsifying, defoaming, uniformly coating on organic silicon resin, drying, cooling to room temperature, and removing the film, wherein the drying temperature is 45 ℃, so that a finished product is obtained.
Comparative example
An environment-friendly heat shrinkable film comprises the following raw materials in parts by mass; 100 parts of polyester, 1 part of edible hydrophobic substance, 1 part of emulsifier, 2 parts of antioxidant, 1.7 parts of light stabilizer and 6 parts of collagen.
In this comparative example, a method for preparing an environmentally friendly heat shrinkable film comprises the steps of:
(1) heating and dissolving an aqueous solution containing edible hydrophobic substances and an emulsifier, heating to 55 ℃, and carrying out homogenizing and emulsifying treatment by using a tissue triturator to obtain a hydrophobic substance emulsion;
(2) mixing collagen, the hydrophobic substance emulsion obtained in the step (1) and polyester, homogenizing and emulsifying, defoaming, uniformly coating on organic silicon resin, drying, cooling to room temperature, and removing the film, wherein the drying temperature is 45 ℃, so as to obtain the finished product.
The finished products from examples 1-6 and comparative examples were tested for properties and the results are shown in Table 1 below:
TABLE 1
As can be seen from table 1, the environmentally friendly heat shrinkable film prepared according to the technical scheme of the present invention has better tensile strength, elongation at break and hydrothermal shrinkage than the comparative example.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (9)
1. An environment-friendly heat shrinkable film is characterized by comprising the following raw materials in parts by mass; 50-100 parts of polyester, 0.5-1 part of edible hydrophobic substance, 0.5-1 part of emulsifier, 1.5-2 parts of antioxidant, 1.2-1.7 parts of light stabilizer and 1-6 parts of modified collagen;
the modified collagen is prepared by grafting polyethylene glycol on the collagen, then carrying out esterification reaction with oxalic acid, and then carrying out esterification reaction with ethylene glycol.
2. The environmentally friendly heat shrinkable film of claim 1, wherein: the polyester is composed of lactic acid-co-glycolic acid, polylactic acid and polycaprolactone, wherein the mass ratio of the lactic acid-co-glycolic acid to the polylactic acid to the polycaprolactone is 6-8: 1-3: 1.
3. The environmentally friendly heat shrinkable film of claim 1, wherein: the edible hydrophobic substance is one selected from stearic acid, palmitic acid and beeswax.
4. The environmentally friendly heat shrinkable film of claim 1, wherein: the edible emulsifier is at least one selected from sucrose fatty acid ester, citric acid glyceride and polyglycerol fatty acid ester.
5. The method for preparing an environmentally friendly heat shrinkable film according to any one of claims 1 to 4, wherein: the method comprises the following steps:
(1) mixing collagen with polyethylene glycol, carrying out oil bath stirring reaction, dropwise adding oxalic acid after the reaction is finished, and dropwise adding ethylene glycol after the dropwise adding of oxalic acid is finished to obtain modified collagen;
(2) heating and dissolving an aqueous solution containing edible hydrophobic substances and edible emulsifiers, and then carrying out homogenizing and emulsifying treatment by using a tissue triturator to obtain a hydrophobic substance emulsion;
(3) and (3) mixing the modified collagen obtained in the step (1), the hydrophobic substance emulsion obtained in the step (2) and polyester, homogenizing and emulsifying, defoaming, uniformly coating on organic silicon resin, drying, cooling to room temperature, and removing the film to obtain a finished product.
6. The method for preparing environment-friendly heat shrinkable film according to claim 5, wherein: the mass ratio of the collagen to the polyethylene glycol, the oxalic acid and the ethylene glycol in the step (1) is 10-20: 1-5: 5-10: 1.
7. The method for preparing environment-friendly heat shrinkable film according to claim 5, wherein the reaction temperature in the step (1) is 70-80 ℃ and the reaction time is 1-3 h.
8. The method for preparing environment-friendly heat shrinkable film according to claim 5, wherein the heating temperature in the step (2) is 50-60 ℃.
9. The method for preparing environment-friendly heat shrinkable film according to claim 5, wherein the temperature for drying in the step (3) is 40-50 ℃.
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