CN112876828A - Degradable electronic film and preparation method thereof - Google Patents

Degradable electronic film and preparation method thereof Download PDF

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CN112876828A
CN112876828A CN202110196277.6A CN202110196277A CN112876828A CN 112876828 A CN112876828 A CN 112876828A CN 202110196277 A CN202110196277 A CN 202110196277A CN 112876828 A CN112876828 A CN 112876828A
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zones
film
degradable
electronic film
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唐健
王帮新
张复宝
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Anhui Shuangjin Co ltd
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Anhui Shuangjin Co ltd
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K7/00—Use of ingredients characterised by shape
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    • C08K7/24—Expanded, porous or hollow particles inorganic
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention discloses a degradable electronic film and a preparation method thereof, wherein the degradable electronic film is prepared from the following raw materials: 40-60 parts of polylactic acid, 4-8 parts of epoxy furan resin, 62-3 parts of nylon, 0.06-0.09 part of potassium chloride, 0.3-0.7 part of modified graphite, 0.005-0.008 part of dicumyl peroxide, 0.5-1 part of ethylene bis stearamide, 0.1-0.5 part of erucamide, 4-10 parts of plasticizer, 0.2-0.6 part of heat stabilizer and 0.2-0.6 part of antioxidant. The degradable electronic film can be completely biodegraded, can well replace materials such as PE, PP, PVC and the like, is applied to electronic product packaging, has the antistatic property, can effectively eliminate the damage of electronic equipment caused by static electricity, is simple in use process, low in price, environment-friendly and practical as the electronic product packaging film, and has good economic and social benefits.

Description

Degradable electronic film and preparation method thereof
Technical Field
The invention belongs to the technical field of high polymer film materials, and particularly relates to a degradable electronic film and a preparation method thereof.
Background
Environmental problems caused by the widespread use of plastic products, particularly plastic film products, and the increasing shortage of petroleum energy have attracted extensive attention worldwide. Therefore, the development and use of biomass resources and completely biodegradable polymer film materials to replace petroleum-based plastics have become a hot spot of current research.
The polylactic acid is a polymer obtained by polymerizing lactic acid serving as a main raw material, the raw material source is sufficient and can be regenerated, the production process of the polylactic acid is pollution-free, and the product can be biodegraded to realize circulation in nature, so that the polylactic acid is an ideal green high polymer material. Polylactic acid has good thermal stability and good solvent resistance, can be processed in various modes, such as extrusion, spinning, biaxial stretching and injection blow molding, and products prepared from the polylactic acid can be biodegraded, have good biocompatibility, glossiness, transparency, hand feeling and heat resistance, and have certain antibacterial property, flame retardance and ultraviolet resistance, so the polylactic acid has wide application. However, the toughness of polylactic acid is poor, which limits the application of polylactic acid, while the traditional modified blending is expected to improve the toughness of materials, the compatibility among materials is difficult, and the simple physical blending modification effect is not obvious.
Meanwhile, in the aspect of electronic film products, in addition to the traditional film strength such as stretching and impact, the antistatic performance is also important, various electronic components are easy to damage or explode due to electrostatic aggregation, and other serious consequences are serious.
Disclosure of Invention
The invention aims to make up the defects of the prior art and provides a degradable electronic film and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
a degradable electronic film is prepared from the following raw materials: 40-60 parts of polylactic acid, 4-8 parts of epoxy furan resin, 62-3 parts of nylon, 0.06-0.09 part of potassium chloride, 0.3-0.7 part of modified graphite, 0.005-0.008 part of dicumyl peroxide, 0.5-1 part of ethylene bis stearamide, 0.1-0.5 part of erucamide, 4-10 parts of plasticizer, 0.2-0.6 part of heat stabilizer and 0.2-0.6 part of antioxidant.
Preferably, the degradable electronic film is prepared from the following raw materials: 50 parts of polylactic acid, 6 parts of epoxy furan resin, 62.5 parts of nylon, 0.07 part of potassium chloride, 0.5 part of modified graphite, 0.006 part of dicumyl peroxide, 0.8 part of ethylene bis stearamide, 0.3 part of erucamide, 7 parts of plasticizer, 0.4 part of heat stabilizer and 0.4 part of antioxidant.
Further, the preparation method of the modified graphite comprises the following steps: taking the expandable graphite, expanding the expandable graphite at 850-950 ℃ for 30-60 seconds, and taking out the expandable graphite, wherein the mass ratio of the obtained expanded graphite to 75% ethanol solution is 1: (50-100), stirring for 4-6 hours at 55-65 ℃, adding a 5% hexadecyl trimethyl ammonium bromide ethanol solution with the mass ratio of 2% in the stirring period, performing suction filtration and cleaning after the stirring is finished, adding a titanate coupling agent with the mass ratio of 1% in the obtained graphite, stirring for 5-10 minutes, and performing vacuum drying after the stirring is finished to obtain the modified graphite.
Further, the plasticizer is selected from any one of acetyl tributyl citrate, diacetyl epoxy glycerol vegetable oleate and glycerol monostearate.
Further, the heat stabilizer is dibutyltin dilaurate.
Further, the antioxidant is pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate.
A preparation method of the degradable electronic film comprises the following steps:
(1) feeding polylactic acid, epoxy furan resin and an antioxidant into a high-speed mixer, uniformly mixing, extruding the mixed material on a double-screw extruder, and drawing the extruded material onto a granulator for granulation to obtain granules 1;
(2) feeding nylon 6 and potassium chloride into a high-speed mixer, uniformly mixing, extruding the mixed material on a double-screw extruder, and drawing the extruded material on a granulator for granulation to obtain granules 2;
(3) mechanically blending the granules 1, the granules 2, the modified graphite, the dicumyl peroxide, the ethylene bis-stearic acid amide, the erucamide, the plasticizer and the heat stabilizer, and performing melt extrusion on the obtained mixture by a double-screw extruder to obtain a resin material;
(4) and (3) carrying out blow molding on the obtained resin material by a film blowing machine to form a film, thus obtaining the resin.
Further, the set temperature of the twin-screw extruder in the step 3 is as follows: a first area: 130 ℃ and 140 ℃, and the second zone: 150 ℃ and 160 ℃, and a three-zone: 160 ℃ and 170 ℃, four zones: 165-175 ℃, five zones: 165-175 ℃ and six zones: 165-175 ℃, seven zones: 170 ℃ and 180 ℃, eight zones: 170 ℃ and 180 ℃, screw rotation speed: 150 and 300 rpm.
Further, the set temperature of the film blowing machine in the step 4 is as follows: a first area: 145-150 ℃, two zones: 150 ℃ and 160 ℃, and a three-zone: 155 ℃ and 165 ℃, four zones: 160-165 ℃, five zones: 165 ℃ and 170 ℃, the traction speed is 3-7m/min, and the blow-up ratio is 2-6.
Use of a degradable electronic film as described above for electronic product packaging.
The invention has the advantages that:
the polylactic acid is used as a main raw material, is produced by renewable resources such as corn, beet and cane sugar, has good biodegradability and has no pollution to the environment.
The low-melting-point nylon 6 is formed by adding nylon 6 and Lewis acid potassium chloride and performing melt extrusion, and the toughness of the polylactic acid is reinforced by utilizing the toughness, wear resistance, impact resistance and heat resistance of the low-melting-point nylon 6.
In order to improve the compatibility of the polylactic acid and the nylon 6, the epoxy furan resin is also used, and through an epoxy structure and a furan rigid ring structure contained in the epoxy furan resin, the epoxy furan resin can perform a grafting reaction with a terminal carboxyl group in a polylactic acid molecular chain and a terminal amino group in a nylon 6 molecular chain in a melt extrusion process to enhance the interaction force between the two phases, so that the compatibility between the polylactic acid molecular chain and the nylon 6 molecular chain is improved, and the tensile strength and the impact strength of the whole system are further improved.
The modified graphite component is added into the raw materials, and the polylactic acid polymer material has excellent conductivity and nano effect, can realize low filling and high conductivity, and has ideal antistatic performance.
The degradable electronic film can be completely biodegraded, can well replace materials such as PE, PP, PVC and the like, is applied to electronic product packaging, has the antistatic property, can effectively eliminate the damage of electronic equipment caused by static electricity, is simple in use process, low in price, environment-friendly and practical as the electronic product packaging film, and has good economic and social benefits.
Detailed Description
The technical scheme of the invention is further explained by combining the specific examples as follows:
example 1
A degradable electronic film is prepared from the following raw materials: 50 parts of polylactic acid, 6 parts of epoxy furan resin, 62.5 parts of nylon, 0.07 part of potassium chloride, 0.5 part of modified graphite, 0.006 part of dicumyl peroxide, 0.8 part of ethylene bis stearamide, 0.3 part of erucamide, 7 parts of acetyl tributyl citrate, 0.4 part of dibutyltin dilaurate and 0.4 part of tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionic acid pentaerythritol ester.
The preparation method of the modified graphite comprises the following steps: taking expandable graphite, expanding for 45 seconds at 900 ℃, taking out, and mixing the obtained expandable graphite with a 75% ethanol solution according to a mass ratio of 1: 80 and stirring for 5 hours at 60 ℃, adding a 5% hexadecyl trimethyl ammonium bromide ethanol solution with the mass ratio of 2% in the stirring period, performing suction filtration and cleaning after the stirring is finished, adding a titanate coupling agent with the mass ratio of 1% in the obtained graphite, stirring for 8 minutes, and performing vacuum drying after the stirring is finished to obtain the modified graphite.
A preparation method of the degradable electronic film comprises the following steps:
(1) feeding polylactic acid, epoxy furan resin and tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionic acid pentaerythritol ester into a high-speed mixer for uniform mixing, extruding the mixed material on a double-screw extruder, and drawing the material to a granulator for granulation to obtain granules 1;
(2) feeding nylon 6 and potassium chloride into a high-speed mixer, uniformly mixing, extruding the mixed material on a double-screw extruder, and drawing the extruded material on a granulator for granulation to obtain granules 2;
(3) mechanically blending the granular material 1, the granular material 2, the modified graphite, dicumyl peroxide, ethylene bis-stearamide, erucamide, acetyl tributyl citrate and dibutyltin dilaurate, and performing melt extrusion on the obtained mixture by using a double-screw extruder to obtain a resin material, wherein the set temperature of the double-screw extruder is as follows: a first area: 135 ℃, zone two: 155 ℃, three zones: 165 ℃, four zones: 170 ℃, five zones: 170 ℃, six zones: 170 ℃, seven zones: 175 ℃, eight zones: 175 ℃, screw speed: 240 rpm;
(4) and (3) carrying out blow molding on the obtained resin material through a film blowing machine to form a film, wherein the set temperature of the film blowing machine is as follows: a first area: 147 ℃, zone two: 155 ℃, three zones: 160 ℃, four zones: 163 ℃, five zones: the drawing speed is 5m/min at 167 ℃, and the blowing ratio is 4.
Example 2
A degradable electronic film is prepared from the following raw materials: 40 parts of polylactic acid, 4 parts of epoxy furan resin, 62 parts of nylon, 0.06 part of potassium chloride, 0.3 part of modified graphite, 0.005 part of dicumyl peroxide, 0.5 part of ethylene bis stearamide, 0.1 part of erucamide, 4 parts of diacetyl epoxy vegetable olein, 0.2 part of dibutyltin dilaurate and 0.2 part of tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionic acid pentaerythritol ester.
The preparation method of the modified graphite comprises the following steps: taking expandable graphite, expanding for 60 seconds at 850 ℃, taking out, and mixing the obtained expanded graphite with a 75% ethanol solution according to a mass ratio of 1: and (3) stirring for 6 hours at 55 ℃ after 50 mixing, adding a 5% hexadecyl trimethyl ammonium bromide ethanol solution with the mass ratio of 2% in the stirring period, performing suction filtration and cleaning after the stirring is finished, adding a titanate coupling agent with the mass ratio of 1% in the obtained graphite, stirring for 5 minutes, and performing vacuum drying after the stirring is finished to obtain the modified graphite.
A preparation method of the degradable electronic film comprises the following steps:
(1) feeding polylactic acid, epoxy furan resin and tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionic acid pentaerythritol ester into a high-speed mixer for uniform mixing, extruding the mixed material on a double-screw extruder, and drawing the material to a granulator for granulation to obtain granules 1;
(2) feeding nylon 6 and potassium chloride into a high-speed mixer, uniformly mixing, extruding the mixed material on a double-screw extruder, and drawing the extruded material on a granulator for granulation to obtain granules 2;
(3) mechanically blending the granular material 1, the granular material 2, the modified graphite, dicumyl peroxide, ethylene bis-stearic acid amide, erucamide, diacetyl epoxy vegetable oil acid glyceride and dibutyltin dilaurate, and performing melt extrusion on the obtained mixture by using a double-screw extruder to obtain a resin material, wherein the set temperature of the double-screw extruder is as follows: a first area: 130 ℃, two zones: 150 ℃, three zones: 160 ℃, four zones: 165 ℃, five zones: 165 ℃, six zones: 165 ℃, seven zones: 170 ℃, eight zones: 170 ℃, screw speed: 150 rpm;
(4) and (3) carrying out blow molding on the obtained resin material through a film blowing machine to form a film, wherein the set temperature of the film blowing machine is as follows: a first area: 145 ℃, zone two: 150 ℃, three zones: 155 ℃, four zones: 160 ℃, five zones: 165 ℃, the traction speed is 3m/min, and the blow-up ratio is 2.
Example 3
A degradable electronic film is prepared from the following raw materials: 60 parts of polylactic acid, 8 parts of epoxy furan resin, 63 parts of nylon, 0.09 part of potassium chloride, 0.7 part of modified graphite, 0.008 part of dicumyl peroxide, 1 part of ethylene bis stearamide, 0.5 part of erucamide, 10 parts of glycerol monostearate, 0.6 part of dibutyltin dilaurate and 0.6 part of pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate.
The preparation method of the modified graphite comprises the following steps: taking expandable graphite, expanding the expandable graphite at 950 ℃ for 30 seconds, taking out the expandable graphite, and mixing the obtained expanded graphite with a 75% ethanol solution according to a mass ratio of 1: 100, stirring for 4 hours at 65 ℃, adding a 5% hexadecyl trimethyl ammonium bromide ethanol solution with the mass ratio of 2% in the stirring period, performing suction filtration and cleaning after the stirring is finished, adding a titanate coupling agent with the mass ratio of 1% in the obtained graphite, stirring for 10 minutes, and performing vacuum drying after the stirring is finished to obtain the modified graphite.
A preparation method of the degradable electronic film comprises the following steps:
(1) feeding polylactic acid, epoxy furan resin and tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionic acid pentaerythritol ester into a high-speed mixer for uniform mixing, extruding the mixed material on a double-screw extruder, and drawing the material to a granulator for granulation to obtain granules 1;
(2) feeding nylon 6 and potassium chloride into a high-speed mixer, uniformly mixing, extruding the mixed material on a double-screw extruder, and drawing the extruded material on a granulator for granulation to obtain granules 2;
(3) mechanically blending the granular material 1, the granular material 2, the modified graphite, the dicumyl peroxide, the ethylene bis-stearic acid amide, the erucamide, the glycerol monostearate and the dibutyltin dilaurate, and performing melt extrusion on the obtained mixture by using a double-screw extruder to obtain a resin material, wherein the set temperature of the double-screw extruder is as follows: a first area: 140 ℃, zone two: 160 ℃, three zones: 170 ℃, four zones: 175 ℃, five zones: 175 ℃, six zones: 175 ℃, seven zones: 180 ℃, eight zones: 180 ℃, screw speed: 300 rpm;
(4) and (3) carrying out blow molding on the obtained resin material through a film blowing machine to form a film, wherein the set temperature of the film blowing machine is as follows: a first area: 150 ℃, zone two: 160 ℃, three zones: 165 ℃, four zones: 165 ℃, five zones: the drawing speed is 7m/min and the blowing ratio is 6 at 170 ℃.
The film products obtained in examples 1, 2 and 3 were tested to have a tensile strength of 42MPa or more, an elongation at break of 360% or more, and a surface resistivity of 3.0X 10 or less7Omega cm, and has good antistatic performance.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A degradable electronic film is characterized by being prepared from the following raw materials: 40-60 parts of polylactic acid, 4-8 parts of epoxy furan resin, 62-3 parts of nylon, 0.06-0.09 part of potassium chloride, 0.3-0.7 part of modified graphite, 0.005-0.008 part of dicumyl peroxide, 0.5-1 part of ethylene bis stearamide, 0.1-0.5 part of erucamide, 4-10 parts of plasticizer, 0.2-0.6 part of heat stabilizer and 0.2-0.6 part of antioxidant.
2. The degradable electronic film of claim 1, made from raw materials comprising: 50 parts of polylactic acid, 6 parts of epoxy furan resin, 62.5 parts of nylon, 0.07 part of potassium chloride, 0.5 part of modified graphite, 0.006 part of dicumyl peroxide, 0.8 part of ethylene bis stearamide, 0.3 part of erucamide, 7 parts of plasticizer, 0.4 part of heat stabilizer and 0.4 part of antioxidant.
3. The degradable electronic film of claim 1, wherein the modified graphite is prepared by the following steps: taking the expandable graphite, expanding the expandable graphite at 850-950 ℃ for 30-60 seconds, and taking out the expandable graphite, wherein the mass ratio of the obtained expanded graphite to 75% ethanol solution is 1: (50-100), stirring for 4-6 hours at 55-65 ℃, adding a 5% hexadecyl trimethyl ammonium bromide ethanol solution with the mass ratio of 2% in the stirring period, performing suction filtration and cleaning after the stirring is finished, adding a titanate coupling agent with the mass ratio of 1% in the obtained graphite, stirring for 5-10 minutes, and performing vacuum drying after the stirring is finished to obtain the modified graphite.
4. The degradable electronic film of claim 1, wherein the plasticizer is selected from any one of acetyl tributyl citrate, diacetyl epoxy glycerol vegetable oleate, and glycerol monostearate.
5. The degradable electronic film of claim 1, wherein the thermal stabilizer is dibutyltin dilaurate.
6. The degradable electronic film of claim 1, wherein the antioxidant is pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate.
7. A method of preparing a degradable electronic film according to any one of claims 1 to 5, comprising the steps of:
(1) feeding polylactic acid, epoxy furan resin and an antioxidant into a high-speed mixer, uniformly mixing, extruding the mixed material on a double-screw extruder, and drawing the extruded material onto a granulator for granulation to obtain granules 1;
(2) feeding nylon 6 and potassium chloride into a high-speed mixer, uniformly mixing, extruding the mixed material on a double-screw extruder, and drawing the extruded material on a granulator for granulation to obtain granules 2;
(3) mechanically blending the granules 1, the granules 2, the modified graphite, the dicumyl peroxide, the ethylene bis-stearic acid amide, the erucamide, the plasticizer and the heat stabilizer, and performing melt extrusion on the obtained mixture by a double-screw extruder to obtain a resin material;
(4) and (3) carrying out blow molding on the obtained resin material by a film blowing machine to form a film, thus obtaining the resin.
8. The method for preparing the degradable electronic film according to claim 7, wherein the set temperature of the twin-screw extruder in the step 3 is as follows: a first area: 130 ℃ and 140 ℃, and the second zone: 150 ℃ and 160 ℃, and a three-zone: 160 ℃ and 170 ℃, four zones: 165-175 ℃, five zones: 165-175 ℃ and six zones: 165-175 ℃, seven zones: 170 ℃ and 180 ℃, eight zones: 170 ℃ and 180 ℃, screw rotation speed: 150 and 300 rpm.
9. The method for preparing the degradable electronic film according to claim 7, wherein the set temperature of the film blowing machine in the step 4 is as follows: a first area: 145-150 ℃, two zones: 150 ℃ and 160 ℃, and a three-zone: 155 ℃ and 165 ℃, four zones: 160-165 ℃, five zones: 165 ℃ and 170 ℃, the traction speed is 3-7m/min, and the blow-up ratio is 2-6.
10. Use of the degradable electronic film of claim 1 for packaging electronic products.
CN202110196277.6A 2021-02-22 2021-02-22 Degradable electronic film and preparation method thereof Pending CN112876828A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115403909A (en) * 2022-10-17 2022-11-29 安徽双津实业有限公司 Biodegradable film and preparation method thereof

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