CN113372663A - Bio-based preservative film and preparation method thereof - Google Patents
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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Abstract
The invention discloses a bio-based preservative film and a preparation method thereof. The bio-based preservative film comprises the following specific formula in parts by weight: 100 parts of PVC resin powder, 1-2 parts of stabilizer, 0.1-1 part of lubricant, 1-2 parts of antifogging agent, 30-40 parts of HM828-2 bio-based plasticizer and 10-18 parts of epoxidized soybean oil. The preparation method uses HM828-2 bio-based plasticizer with 25% bio-based content, and the prepared bio-based preservative film product meets the environmental protection requirement, is low temperature resistant, precipitation resistant, extraction resistant, harmless to human body, and suitable for the national requirement of recyclable green development, and does not pollute the packing materials.
Description
Technical Field
The invention relates to the technical field of packaging films, in particular to a bio-based preservative film and a preparation method thereof.
Background
Fruits and vegetables are rich in carbohydrates, and the physiological activities are still vigorous after picking. In transportation and storage process, because of the decline of oxygen content in the packing material, carbon dioxide increases along with the respiratory volume, and fruit and vegetable carries out anaerobic respiration, and the loss of aggravation rotten degree and moisture, fruit and vegetable has lost fresh gloss, and people's purchase desire descends to reduce its added value. The change of moisture permeability and ventilative volume can be adjusted to the plastic wrap, prolongs the fresh-keeping cycle of giving birth to the bright-colored bright of fresh-keeping article appearance to increase people's purchase desire, can separate the dust simultaneously, prevent that food from scurrying flavor in the refrigerator.
The preservative films used in the market at present are PVC, PE and PVDC, wherein the PVC preservative film is the accepted optimal moisture-permeable and air-permeable material and is the preservative film with the largest use amount. The PVC preservative film has wide application, such as wrapping in refrigerators, fresh packaging and packaging of various meats. PVC is a polar high molecular polymer, the intermolecular force is large, and a large amount of plasticizer can only be added to prepare a soft product, so that the plasticizer is inserted into the PVC molecules, the intermolecular force is changed, and the PVC preservative film has the possibility of toughness and flexibility.
At present, the disputes to PVC plastic wrap mainly reflect the precipitation of plasticizer and the non-extraction resistance. The plasticizer most used in the market is DOA (dioctyl adipate), which has low molecular weight, is in a linear structure, is easy to separate out under high-temperature and humid conditions, is easy to extract most of solvents, and is easy to extract in 95% ethanol or olive oil even if the using amount of the plasticizer is controlled, so that the plasticizer is transferred to a wrapped article to pollute food. The related national departments have proved that the excess of DOA (dioctyl adipate) can affect the health of the reproductive system and the fertility. DOA (dioctyl adipate) is forbidden in most countries internationally, and the DOA is released in 2016 and limited in use. At present, the development of bio-based degradable plastic products is vigorously advocated by the country, so that the resources are saved, and the green recyclable development is realized. The european union and the united states have established that biobased plastic products reach 25% with limited procurement rights. Therefore, the environment-friendly cold-resistant, precipitation-resistant and extraction-resistant bio-based preservative film is needed to be developed, and the market development is adapted.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the environment-friendly, cold-resistant, precipitation-resistant and extraction-resistant bio-based preservative film produced by using the HM828-2 bio-based plasticizer and the preparation method thereof.
The technical scheme of the invention is as follows:
the invention relates to a bio-based preservative film, which comprises the following specific formula in parts by weight: 100 parts of PVC resin powder, 1-2 parts of stabilizer, 0.1-1 part of lubricant, 1-2 parts of antifogging agent, 30-40 parts of HM828-2 bio-based plasticizer and 10-18 parts of epoxidized soybean oil.
Preferably, 100 parts of PVC resin powder, 1.5-2 parts of stabilizer, 0.5-1 part of lubricant, 1-1.5 parts of antifogging agent, 30-40 parts of HM828-2 bio-based plasticizer and 12-18 parts of epoxidized soybean oil.
In any of the above embodiments, preferably, the stabilizer is a calcium zinc stabilizer.
The second aspect of the present invention relates to the preparation method of the bio-based preservative film of the first aspect, comprising the following steps:
the first step is as follows: weighing 100 parts of PVC resin powder and 10-15 parts of HM828-2 bio-based plasticizer according to the weight ratio, and mixing the two to 100 ℃ to form a primary mixed material;
the second step is that: weighing the stabilizer, the lubricant, the antifogging agent, the epoxidized soybean oil and the residual HM828-2 bio-based plasticizer according to the weight ratio, and putting the mixture into the primary mixed material for the second time to stir at a high speed to 125 ℃;
the third step: and (2) putting the mixture into a cooling pot, uniformly stirring and cooling the mixture to 60 ℃, standing the mixture for 2 to 3 hours, and putting the mixture into an extruder for use, adding the mixture into the extruder for plasticizing and extruding, wherein the processing temperature of the extruder is 160 to 185 ℃, the plasticized material flows out through a die head to form a blank, the processing temperature of the die head is 185 to 195 ℃, cooling and shaping the blank, cutting and rolling the blank, and finishing the preparation of a semi-finished product of the preservative film.
Preferably, in the first step: weighing 100 parts of PVC resin powder and 10 parts of HM828-2 bio-based plasticizer according to the weight ratio, and mixing the two to 100 ℃ to form a primary mixed material;
the second step is that: weighing 1.5 parts of stabilizer, 0.1 part of lubricant, 1.5 parts of antifogging agent, 12 parts of epoxidized soybean oil and 23 parts of residual HM828-2 bio-based plasticizer according to the weight ratio, and adding the mixture into the primary mixture twice to stir at a high speed to 125 ℃.
Preferably, in the first step: weighing 100 parts of PVC resin powder and 10 parts of HM828-2 bio-based plasticizer according to the weight ratio, and mixing the two to 100 ℃ to form a primary mixed material;
the second step is that: weighing 1.8 parts of stabilizer, 0.15 part of lubricant, 1 part of antifogging agent, 12 parts of epoxidized soybean oil and 23 parts of residual HM828-2 bio-based plasticizer according to the weight ratio, and adding the mixture into the primary mixture twice to stir at a high speed to 125 ℃.
Preferably, in the first step: weighing 100 parts of PVC resin powder and 10 parts of HM828-2 bio-based plasticizer according to the weight ratio, and mixing the two to 100 ℃ to form a primary mixed material;
the second step is that: weighing 1.8 parts of stabilizer, 0.2 part of lubricant, 1 part of antifogging agent, 15 parts of epoxidized soybean oil and 25 parts of residual HM828-2 bio-based plasticizer according to the weight ratio, and putting the mixture into the primary mixture for secondary stirring at a high speed to 125 ℃.
Preferably, in the first step: weighing 100 parts of PVC resin powder and 10 parts of HM828-2 bio-based plasticizer according to the weight ratio, and mixing the two to 100 ℃ to form a primary mixed material;
the second step is that: weighing 1.8 parts of stabilizer, 0.2 part of lubricant, 1 part of antifogging agent, 18 parts of epoxidized soybean oil and 30 parts of residual HM828-2 bio-based plasticizer according to the weight ratio, and putting the mixture into the primary mixture for secondary stirring at a high speed to 125 ℃.
The preparation method of the bio-based preservative film provided by the invention uses HM828-2 bio-based plasticizer with 25% of bio-based content, and the prepared preservative film product meets the environmental protection requirement, is low temperature resistant, precipitation resistant, extraction resistant, does not pollute the package, is harmless to human body, and is suitable for the national requirement of recyclable green development.
Drawings
FIG. 1 is a process flow chart of the preparation method of the bio-based preservative film of the invention.
Fig. 2 is a table showing the formulation of each example of the method for preparing the base wrap of the present invention.
FIG. 3 is a table comparing elongation at break, low temperature elongation, and tensile strength data for the formulations of FIG. 2 of the present invention.
FIG. 4 is a table comparing the amount of extraction of bio-based plastic wrap of the present invention with that of dioctyl adipate in different simulations.
FIG. 5 is a table showing the total and specific yields of bio-based wrap films according to the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. 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.
The invention provides an environment-friendly, low-temperature-resistant, precipitation-resistant and extraction-resistant bio-based preservative film produced by using HM828-2 bio-based plasticizer as plasticizer and a preparation method thereof.
Example 1
The bio-based preservative film comprises the following specific formula in parts by weight: 100 parts of PVC resin powder, 1-2 parts of stabilizer, 0.1-1 part of lubricant, 1-2 parts of antifogging agent, 30-40 parts of HM828-2 bio-based plasticizer and 10-18 parts of epoxidized soybean oil.
Preferably, 100 parts of PVC resin powder, 1.5-2 parts of stabilizer, 0.5-1 part of lubricant, 1-1.5 parts of antifogging agent, 30-40 parts of HM828-2 bio-based plasticizer and 12-18 parts of epoxidized soybean oil.
Wherein the stabilizer is calcium zinc stabilizer, and CZ series calcium zinc composite stabilizer produced by Japan Holland company can be adopted.
The PVC resin powder, namely the polyvinyl chloride resin powder, has the characteristics of heat resistance and precipitation resistance, and can be made of a chemical food grade 3 material.
The lubricant may be produced by RIKEMAL series, japan research corporation.
The antifogging agent can be produced by RIKEMAL series, Nippon research company.
The HM828-2 bio-based plasticizer may be manufactured by Nantong sea Fang.
The epoxidized soybean oil is an epoxy plasticizer and can be produced by sea and sea silken marigold.
Example 2
A preparation method of a bio-based preservative film is shown in figure 1 and comprises the following steps:
the first step is as follows: weighing 100 parts of PVC resin powder and 10-15 parts of HM828-2 bio-based plasticizer according to the weight ratio, and mixing the two to 100 ℃ to form a primary mixed material;
the second step is that: weighing the stabilizer, the lubricant, the antifogging agent, the epoxidized soybean oil and the residual HM828-2 bio-based plasticizer according to the weight ratio, and putting the mixture into the primary mixed material for the second time to stir at a high speed to 125 ℃;
the third step: and (2) putting the mixture into a cooling pot, uniformly stirring and cooling the mixture to 60 ℃, standing the mixture for 2 to 3 hours, and putting the mixture into an extruder for use, adding the mixture into the extruder for plasticizing and extruding, wherein the processing temperature of the extruder is 160 to 185 ℃, the plasticized material flows out through a die head to form a blank, the processing temperature of the die head is 185 to 195 ℃, cooling and shaping the blank, cutting and rolling the blank, and finishing the preparation of a semi-finished product of the preservative film.
Example 3
A preparation method of a bio-based preservative film, see formula 2 in figures 1 and 2, comprises the following steps:
the first step is as follows: weighing 100 parts of PVC resin powder and 10 parts of HM828-2 bio-based plasticizer according to the weight ratio, and mixing the two to 100 ℃ to form a primary mixed material;
the second step is that: weighing 1.5 parts of stabilizer, 0.1 part of lubricant, 1.5 parts of antifogging agent, 12 parts of epoxidized soybean oil and 23 parts of residual HM828-2 bio-based plasticizer according to the weight ratio, and putting the mixture into the primary mixture for secondary stirring at a high speed to 125 ℃;
the third step: and (2) putting the mixture into a cooling pot, uniformly stirring and cooling the mixture to 60 ℃, standing the mixture for 2 to 3 hours, and putting the mixture into an extruder for use, adding the mixture into the extruder for plasticizing and extruding, wherein the processing temperature of the extruder is 160 to 185 ℃, the plasticized material flows out through a die head to form a blank, the processing temperature of the die head is 185 to 195 ℃, cooling and shaping the blank, cutting and rolling the blank, and finishing the preparation of a semi-finished product of the preservative film.
Example 4
A preparation method of a bio-based preservative film, see formula 3 in figures 1 and 2, comprises the following steps:
the first step is as follows: weighing 100 parts of PVC resin powder and 10 parts of HM828-2 bio-based plasticizer according to the weight ratio, and mixing the two to 100 ℃ to form a primary mixed material;
the second step is that: weighing 1.8 parts of stabilizer, 0.15 part of lubricant, 1 part of antifogging agent, 12 parts of epoxidized soybean oil and 23 parts of residual HM828-2 bio-based plasticizer according to the weight ratio, and putting the mixture into the primary mixture for secondary stirring at a high speed to 125 ℃;
the third step: and (2) putting the mixture into a cooling pot, uniformly stirring and cooling the mixture to 60 ℃, standing the mixture for 2 to 3 hours, and putting the mixture into an extruder for use, adding the mixture into the extruder for plasticizing and extruding, wherein the processing temperature of the extruder is 160 to 185 ℃, the plasticized material flows out through a die head to form a blank, the processing temperature of the die head is 185 to 195 ℃, cooling and shaping the blank, cutting and rolling the blank, and finishing the preparation of a semi-finished product of the preservative film.
Example 5
A preparation method of a bio-based preservative film, see formula 4 in figures 1 and 2, comprises the following steps:
the first step is as follows: weighing 100 parts of PVC resin powder and 10 parts of HM828-2 bio-based plasticizer according to the weight ratio, and mixing the two to 100 ℃ to form a primary mixed material;
the second step is that: weighing 1.8 parts of stabilizer, 0.2 part of lubricant, 1 part of antifogging agent, 15 parts of epoxidized soybean oil and 25 parts of residual HM828-2 bio-based plasticizer according to the weight ratio, and putting the mixture into the primary mixture for secondary stirring at a high speed to 125 ℃;
the third step: and (2) putting the mixture into a cooling pot, uniformly stirring and cooling the mixture to 60 ℃, standing the mixture for 2 to 3 hours, and putting the mixture into an extruder for use, adding the mixture into the extruder for plasticizing and extruding, wherein the processing temperature of the extruder is 160 to 185 ℃, the plasticized material flows out through a die head to form a blank, the processing temperature of the die head is 185 to 195 ℃, cooling and shaping the blank, cutting and rolling the blank, and finishing the preparation of a semi-finished product of the preservative film.
Example 6
A preparation method of a bio-based preservative film, see formula 5 in figures 1 and 2, comprises the following steps:
the first step is as follows: weighing 100 parts of PVC resin powder and 10 parts of HM828-2 bio-based plasticizer according to the weight ratio, and mixing the two to 100 ℃ to form a primary mixed material;
the second step is that: weighing 1.8 parts of stabilizer, 0.2 part of lubricant, 1 part of antifogging agent, 18 parts of epoxidized soybean oil and 30 parts of residual HM828-2 bio-based plasticizer according to the weight ratio, and putting the mixture into the primary mixture for the second time and stirring the mixture at a high speed to 125 ℃;
the third step: and (2) putting the mixture into a cooling pot, uniformly stirring and cooling the mixture to 60 ℃, standing the mixture for 2 to 3 hours, and putting the mixture into an extruder for use, adding the mixture into the extruder for plasticizing and extruding, wherein the processing temperature of the extruder is 160 to 185 ℃, the plasticized material flows out through a die head to form a blank, the processing temperature of the die head is 185 to 195 ℃, cooling and shaping the blank, cutting and rolling the blank, and finishing the preparation of a semi-finished product of the preservative film.
To more clearly demonstrate the beneficial effects of the examples of the present invention, the prior art embodiment using dioctyl adipate as the plasticizer (i.e., the formulation 1 embodiment in fig. 2) was used as the control group and was fully demonstrated by the test.
The formulation 1 embodiment employs the following steps:
the first step is as follows: weighing 100 parts of PVC resin powder and 10 parts of dioctyl adipate according to the weight ratio, and mixing the PVC resin powder and the dioctyl adipate to 100 ℃ to form a primary mixed material;
the second step is that: weighing 1.5 parts of stabilizer, 0.1 part of lubricant, 1.5 parts of antifogging agent, 12 parts of epoxidized soybean oil and 23 parts of residual dioctyl adipate according to the weight ratio, putting into the primary mixture for twice, and stirring at a high speed to 125 ℃;
the third step: and (2) putting the mixture into a cooling pot, uniformly stirring and cooling the mixture to 60 ℃, standing the mixture for 2 to 3 hours, and putting the mixture into an extruder for use, adding the mixture into the extruder for plasticizing and extruding, wherein the processing temperature of the extruder is 160 to 185 ℃, the plasticized material flows out through a die head to form a blank, the processing temperature of the die head is 185 to 195 ℃, cooling and shaping the blank, cutting and rolling the blank, and finishing the preparation of a semi-finished product of the preservative film.
Samples with the width of 15cm and the length of 10cm are cut by preparing the preservative films according to the 5 formulas of formulas 1 to 5, the low-temperature elongation is determined according to GB10457-2009 and T2-163-1965, the elongation at break of the 5 groups of samples is tested according to GB10457-2009 and GB/T1040.3-2006, and the test result is shown in figure 3: the elongation at break and the elongation at low temperature of the invention (formula 2-formula 5) are both lower than that of the prior art (formula 1), and the tensile strength is higher than that of the prior art (formula 1).
The extraction in the different simulants, i.e. the loss of the test sample, was tested according to GB 31604.1-2005 and GB 5009.156-2016, the results of which are shown in fig. 4: the cling film made using HM828-2 bio-based plasticizer of the present invention was used in different simulations with much less draw than cling film made from dioctyl adipate.
The total precipitation amount of the preservative film prepared from the HM828-2 bio-based plasticizer is detected according to GB4806.7-2016, and the specific precipitation amount is shown in figure 5, and the result shows that the preservative film prepared from the HM828-2 bio-based plasticizer meets the national detection standard.
In conclusion, the HM828-2 bio-based plasticizer used in the preparation method is an environment-friendly bio-based material, and the prepared bio-based preservative film has the characteristics of cold resistance, precipitation resistance and extraction resistance, and can keep the original physical properties under a low-temperature condition.
The epoxidized soybean oil and the HM828-2 bio-based plasticizer used in the preparation method are all bio-based materials, the content of the bio-based materials reaches more than 25% through American USDA certification, the bio-based materials have the priority purchasing right of the bio-based materials, and the national bio-based material standards are met. The used lubricant, antifogging agent and stabilizer have compliance statement and third party detection report, are all nontoxic substances, and can ensure the use safety.
The above-mentioned embodiments are only preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be covered by the scope of the present invention by the technical solutions and their equivalents and modifications within the technical scope of the present invention.
Claims (8)
1. The bio-based preservative film is characterized by comprising the following specific formula in parts by weight: 100 parts of PVC resin powder, 1-2 parts of stabilizer, 0.1-1 part of lubricant, 1-2 parts of antifogging agent, 30-40 parts of HM828-2 bio-based plasticizer and 10-18 parts of epoxidized soybean oil.
2. The bio-based preservative film according to claim 1, wherein 100 parts of PVC resin powder, 1.5-2 parts of stabilizer, 0.5-1 part of lubricant, 1-1.5 parts of antifogging agent, 30-40 parts of HM828-2 bio-based plasticizer and 12-18 parts of epoxidized soybean oil.
3. The bio-based preservative film according to claim 1, wherein the stabilizer is a calcium zinc stabilizer.
4. A method of making a bio-based cling film as claimed in any one of claims 1-3, comprising the steps of:
the first step is as follows: weighing 100 parts of PVC resin powder and 10-15 parts of HM828-2 bio-based plasticizer according to the weight ratio, and mixing the two to 100 ℃ to form a primary mixed material;
the second step is that: weighing the stabilizer, the lubricant, the antifogging agent, the epoxidized soybean oil and the residual HM828-2 bio-based plasticizer according to the weight ratio, and putting the mixture into the primary mixed material for the second time to stir at a high speed to 125 ℃;
the third step: and (2) putting the mixture into a cooling pot, uniformly stirring and cooling the mixture to 60 ℃, standing the mixture for 2 to 3 hours, and putting the mixture into an extruder for use, adding the mixture into the extruder for plasticizing and extruding, wherein the processing temperature of the extruder is 160 to 185 ℃, the plasticized material flows out through a die head to form a blank, the processing temperature of the die head is 185 to 195 ℃, cooling and shaping the blank, cutting and rolling the blank, and finishing the preparation of a semi-finished product of the preservative film.
5. The method for preparing a bio-based preservative film according to claim 4, wherein the first step: weighing 100 parts of PVC resin powder and 10 parts of HM828-2 bio-based plasticizer according to the weight ratio, and mixing the two to 100 ℃ to form a primary mixed material;
the second step is that: weighing 1.5 parts of stabilizer, 0.1 part of lubricant, 1.5 parts of antifogging agent, 12 parts of epoxidized soybean oil and 23 parts of residual HM828-2 bio-based plasticizer according to the weight ratio, and adding the mixture into the primary mixture twice to stir at a high speed to 125 ℃.
6. The method for preparing a bio-based preservative film according to claim 4, wherein the first step: weighing 100 parts of PVC resin powder and 10 parts of HM828-2 bio-based plasticizer according to the weight ratio, and mixing the two to 100 ℃ to form a primary mixed material;
the second step is that: weighing 1.8 parts of stabilizer, 0.15 part of lubricant, 1 part of antifogging agent, 12 parts of epoxidized soybean oil and 23 parts of residual HM828-2 bio-based plasticizer according to the weight ratio, and adding the mixture into the primary mixture twice to stir at a high speed to 125 ℃.
7. The method for preparing a bio-based preservative film according to claim 4, wherein the first step: weighing 100 parts of PVC resin powder and 10 parts of HM828-2 bio-based plasticizer according to the weight ratio, and mixing the two to 100 ℃ to form a primary mixed material;
the second step is that: weighing 1.8 parts of stabilizer, 0.2 part of lubricant, 1 part of antifogging agent, 15 parts of epoxidized soybean oil and 25 parts of residual HM828-2 bio-based plasticizer according to the weight ratio, and putting the mixture into the primary mixture for secondary stirring at a high speed to 125 ℃.
8. The method for preparing a bio-based preservative film according to claim 4, wherein the first step: weighing 100 parts of PVC resin powder and 10 parts of HM828-2 bio-based plasticizer according to the weight ratio, and mixing the two to 100 ℃ to form a primary mixed material;
the second step is that: weighing 1.8 parts of stabilizer, 0.2 part of lubricant, 1 part of antifogging agent, 18 parts of epoxidized soybean oil and 30 parts of residual HM828-2 bio-based plasticizer according to the weight ratio, and putting the mixture into the primary mixture for secondary stirring at a high speed to 125 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115612153A (en) * | 2022-10-14 | 2023-01-17 | 浙江中淬生物科技有限公司 | Preparation process of food fresh-keeping film with antibiotic coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115612153A (en) * | 2022-10-14 | 2023-01-17 | 浙江中淬生物科技有限公司 | Preparation process of food fresh-keeping film with antibiotic coating |
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Application publication date: 20210910 |