CN113563702A - Degradable plastic bag and preparation method thereof - Google Patents
Degradable plastic bag and preparation method thereof Download PDFInfo
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- CN113563702A CN113563702A CN202110809261.8A CN202110809261A CN113563702A CN 113563702 A CN113563702 A CN 113563702A CN 202110809261 A CN202110809261 A CN 202110809261A CN 113563702 A CN113563702 A CN 113563702A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a degradable plastic bag and a preparation method thereof. A degradable plastic bag is prepared from the following raw materials in parts by weight: 80-120 parts of polylactic acid, 30-40 parts of rosin ester, 15-35 parts of silane coupling agent modified starch, 10-30 parts of kaolin and 5-15 parts of coffee grounds; this application improves the toughness of degradable plastic bag through rosin ester, silane coupling agent modified starch, and kaolin and coffee grounds can promote the dispersibility between each polymer, reduce the mechanical weak point of degradable plastic bag, improve the tensile strength of degradable plastic bag, improve the mechanical properties of degradable plastic bag, and simultaneously kaolin and coffee grounds provide nutrient composition for the microorganism, accelerate the degradation rate of degradable plastic bag, improve the degradation degree of degradable plastic bag.
Description
Technical Field
The invention relates to the technical field of plastic bags, in particular to a degradable plastic bag and a preparation method thereof.
Background
The traditional PE plastic bag brings convenience to our life, but the PE plastic bag is stable in structure, is not easy to degrade, is not decomposed for a long time in the natural environment, and can cause great harm to the environment. With the development of science and technology and the development of the Chinese environmental protection industry, the degradable plastic bag has gradually replaced the traditional PE plastic bag. The degradable plastic bag is a plastic bag which has various properties meeting the use requirements, has unchanged performance in the storage period and can be degraded to be harmless to the environment under the natural environment condition after being used.
The degradable plastic bag is mainly composed of polylactic acid (PLA), regenerated cellulose, starch plastic, polyhydroxyalkanoate polymer, polybutylene succinate, polycaprolactone, polyethanol, polybutylene adipate/terephthalate, a polybutylene adipate/succinate copolymer and other degradable plastics. Among them, polylactic acid is a polyester synthesized from plant resources, has characteristics of biodegradability, good biocompatibility, easy processing, and the like, and is widely used for degradable plastic bags.
The patent with the application number of CN201810626539.6 discloses an easily degradable environment-friendly plastic bag, which comprises the following components in parts by weight: 60-80 parts of plant starch, 10-15 parts of hydroxyethyl cellulose, 30-40 parts of PCL composite material, 10-20 parts of polylactic acid composite material and 5-10 parts of auxiliary agent; the plant starch comprises the following components in parts by weight: 15-30 parts of cassava starch, 10-20 parts of corn starch and 5-15 parts of potato powder. This patent has reduced the cost of degradable plastic bag, has improved the degradation rate. However, the inventor finds that polylactic acid has the defects of too hard texture, poor flexibility and the like, and the defects of too hard texture and poor flexibility of polylactic acid can be improved by compounding plant starch, hydroxyethyl cellulose and polylactic acid, but plant starch and hydroxyethyl cellulose are hydrophilic substances, polylactic acid is a hydrophobic substance, and the interface compatibility of plant starch, hydroxyethyl cellulose and polylactic acid is poor, so that the mechanical property of the degradable plastic bag is poor.
Disclosure of Invention
In order to improve the mechanical property of the degradable plastic bag, the application provides the degradable plastic bag and a preparation method thereof.
In a first aspect, the present application provides a degradable plastic bag, which is implemented by the following technical scheme:
a degradable plastic bag is prepared from the following raw materials in parts by weight:
by adopting the technical scheme, the rosin ester contains a flexible fatty chain, has certain hydrophobicity, has certain compatibility with polylactic acid, and improves the toughness of the polylactic acid, the silane coupling agent modified starch surface is covered with the silane coupling agent, the silane coupling agent improves the hydrophobicity of the starch, so that the silane coupling agent modified starch and the polylactic acid have better compatibility, and the rosin ester and the silane coupling agent modified starch both contain flexible chain segments, so that the toughness of the degradable plastic bag can be effectively improved;
the surface of the coffee grounds contains certain hydrophobic coffee oil, the polar part of the coffee oil and the residual hydroxyl groups after coupling form hydrogen bonds, and the non-polar part is entangled with the long chain of the coupling agent to promote the compatibility between the coffee grounds and the polylactic acid; the kaolin has a special layered structure, molecular chains of polylactic acid, rosin ester and silane coupling agent modified starch can be wound in the kaolin in a crossed manner, so that the tensile strength of the degradable plastic bag is improved, the mechanical weakness of the degradable plastic bag due to polymer agglomeration is reduced, and the mechanical property of the degradable plastic bag is improved;
the polylactic acid, the rosin ester and the silane coupling agent modified starch all contain ester groups, and can be quickly degraded after being buried, and active substances contained in the coffee grounds and the kaolin provide nutrients for microorganisms, so that the burying degradation rate of the degradable plastic bag is accelerated, and the degradation degree is increased;
in addition, all the raw materials used in the application are safe and non-toxic, and the use safety is high; and the waste coffee grounds are recycled, so that the coffee machine is green and environment-friendly.
Preferably, the acid value of the rosin ester is not higher than 10 mgKOH/g.
Through adopting above-mentioned technical scheme, rosin ester includes but not limited to polymerized rosin glyceride, rosin pentaerythritol, preferably adopts polymerized rosin glyceride in this application to control rosin ester's acid value and be not higher than 10mgKOH/g, increased the compatibility between polymerized rosin glyceride and the polylactic acid, exist the davit structure in by polymerized rosin glyceride simultaneously, make the toughness of degradable plastic bag obtain further promotion.
Preferably, the preparation steps of the silane coupling agent modified starch are as follows: and (3) carrying out ultrasonic oscillation on the dried starch, stirring and blending the starch and the silane coupling agent according to the weight ratio of 1 (0.1-0.3), heating to 70-90 ℃, carrying out heat preservation reaction for 10-20 min, drying and cooling to obtain the silane coupling agent modified starch.
By adopting the technical scheme, the starch is degraded under the action of ultrasonic waves, the particle size of starch particles is reduced, the starch is coated by the silane coupling agent, a hydrophobic layer is formed on the surface of the starch, the silane coupling agent modified starch has good compatibility with polylactic acid, and the waterproof performance of the degradable plastic bag is improved.
Preferably, the weight ratio of the starch to the silane coupling agent is 1: 0.2.
Preferably, in the preparation step of the silane coupling agent modified starch, the ultrasonic frequency is 30-40 kHz, and the ultrasonic oscillation time is 10-20 min.
Preferably, the coffee grounds are dried and then subjected to heat treatment at 230-300 ℃.
By adopting the technical scheme, part of hemicellulose of the coffee grounds is decomposed after high-temperature treatment, the content of hydroxyl in the coffee grounds is reduced, the hydrophobicity is enhanced, the compatibility between the coffee grounds and the polylactic acid is improved, meanwhile, coffee oil contained in the coffee grounds is fully separated out after the high-temperature treatment, the coffee oil has a certain plasticizing effect on the degradable plastic bag, and the toughness of the degradable plastic bag is further improved.
Preferably, the heat treatment temperature of the coffee grounds is 250 ℃.
By adopting the technical scheme, the degradation degree of hemicellulose contained in the coffee grounds is high at the treatment temperature, the hydroxyl content is gradually reduced, and the volatilization amount of coffee oil is small.
Preferably, the particle size of the coffee grounds is in a range of 0.01-0.1 mm.
Preferably, the particle size range of the kaolin is 0.01-0.1 mm.
By adopting the technical scheme, the coffee grounds and the kaolin in the particle size range can be fully dispersed in the polylactic acid, so that the possibility of agglomeration of the coffee grounds and the kaolin is reduced.
In a second aspect, the present application provides a method for preparing a degradable plastic bag, which adopts the following technical scheme:
a preparation method of a degradable plastic bag comprises the following steps: weighing polylactic acid, rosin ester, silane coupling agent modified starch, kaolin and coffee grounds according to the formula ratio, drying in vacuum, heating to 190-210 ℃, and stirring for reaction to obtain a mixed material; and extruding and cooling the mixture to form the degradable plastic bag.
By adopting the technical scheme, the degradable plastic bag with better mechanical property, waterproof property and high degradation rate and degree is prepared.
In summary, the present application has the following beneficial effects:
1. this application improves the toughness of degradable plastic bag through rosin ester, silane coupling agent modified starch, and kaolin and coffee grounds can promote the dispersibility between each polymer, reduce the mechanical weak point of degradable plastic bag, improve the tensile strength of degradable plastic bag, improve the mechanical properties of degradable plastic bag, and simultaneously kaolin and coffee grounds provide nutrient composition for the microorganism, accelerate the degradation rate of degradable plastic bag, improve the degradation degree of degradable plastic bag.
2. All the raw materials used in the application are safe and non-toxic, and the use safety is high; and the waste coffee grounds are recycled, so that the coffee machine is green and environment-friendly.
3. Carry out heat treatment to the coffee sediment in this application, control heat treatment's temperature makes the hemicellulose degradation degree grow that wherein contains, and hydroxyl content reduces, and the volatile volume of coffee oil is less simultaneously, further improves the mechanical properties of degradable plastic bag.
Detailed Description
Unless otherwise specified, the raw material sources of the following preparation examples, examples and comparative examples are shown in table 1 below.
TABLE 1 sources of raw materials
Preparation example of silane coupling agent-modified starch
Preparation example 1
A silane coupling agent modified starch is prepared by the following steps: weighing 1kg of corn starch, placing in an oven, drying at 130 deg.C for 1.5h, cooling to room temperature (room temperature in the application is 25 deg.C), and ultrasonically oscillating the corn starch at 30kHz ultrasonic frequency for 20 min; adding 1kg of silane coupling agent KH-550, heating to 70 ℃, carrying out heat preservation reaction for 1h at the stirring speed of 1200rpm, obtaining silane coupling agent modified starch after the reaction is finished, putting the modified starch in a sealed bag, and cooling in a dryer for later use.
Preparation examples 2 to 3
A silane coupling agent modified starch was different from that of preparation example 1 in the weight ratio of the silane coupling agent to the starch, and the specific weight ratio was as shown in Table 2 below.
TABLE 2 weight ratio of silane coupling agent to starch
| Preparation example | Weight ratio of starch to silane coupling agent |
| Preparation example 1 | 1:0.1 |
| Preparation example 2 | 1:0.2 |
| Preparation example 3 | 1:0.3 |
Preparation examples 4 to 5
A silane coupling agent modified starch is different from the preparation example 2 in the preparation process parameters, and the specific parameters are shown in the following table 3.
TABLE 3 weight ratio of silane coupling agent to starch
| Preparation example | Ultrasonic frequency/kHz | Ultrasonic time/min | Reaction temperature/deg.C of starch and silane coupling agent | Reaction time/h of heat preservation |
| Preparation example 1 | 30 | 20 | 70 | 1 |
| Preparation example 4 | 40 | 10 | 70 | 1 |
| Preparation example 5 | 40 | 10 | 90 | 2 |
Preparation example of coffee grounds
Preparation example 6
Coffee grounds are prepared by the following steps: putting 10kg of coffee grounds into an electric heating blast drying box, and drying for 24h at the temperature of 100 ℃ to remove water in the coffee grounds; and (3) heating the dried coffee grounds by using a tubular furnace, wherein the whole heating process is carried out in a nitrogen atmosphere, firstly, the coffee grounds are continuously dried for 1h at the temperature of 100 ℃, then, the temperature is increased from 105 ℃ to 230 ℃ at the temperature increasing rate of 5 ℃/min, the heating is stopped after the heat preservation reaction is carried out for 2h, and the coffee grounds are obtained.
Preparation example 7
A coffee grounds which is different from that of preparation example 6 in that the coffee grounds after drying are heated from 105 ℃ to 250 ℃ at a heating rate of 5 ℃/min.
Preparation example 8
A coffee grounds which is different from that of preparation example 6 in that the coffee grounds after drying are heated from 105 ℃ to 300 ℃ at a heating rate of 5 ℃/min.
Examples
Examples 1-21 provide a degradable plastic bag, and are described below with example 1 as an example.
Example 1 provides a degradable plastic bag, which is prepared by the following steps:
weighing 80g of polylactic acid, 30g of rosin pentaerythritol ester, 15g of silane coupling agent modified starch prepared in preparation example 1, 10g of kaolin and 5g of coffee grounds prepared in preparation example 6;
grinding the coffee grounds and the kaolin in a grinder, and sieving the coffee grounds and the kaolin to obtain coffee grounds and kaolin with the particle size of less than 0.01 mm;
putting polylactic acid, silane coupling agent modified starch, kaolin and coffee grounds into an oven, drying for 1h at 100 ℃, stirring and heating to 190 ℃, adding rosin pentaerythritol ester, continuously stirring, and carrying out heat preservation reaction for 1h to obtain a mixture;
and transferring the blend into an extruder for extrusion, cooling to room temperature, and forming into the degradable plastic bag.
Examples 2-10, which differ from example 1 only in that: the mass of each raw material was different, and specific mass of each raw material is shown in table 4.
TABLE 4 quality of raw materials of degradable plastic bags of examples 1-10
Examples 11 to 14
A degradable plastic bag, which is different from example 10 in that a silane coupling agent modified starch is used from a different source, wherein the silane coupling agent modified starch of example 11 is derived from preparation example 2;
the silane coupling agent modified starch of example 12 was derived from preparation example 3;
the silane coupling agent modified starch of example 13 was derived from preparation example 4;
the silane coupling agent modified starch of example 14 was derived from preparation example 5.
Examples 15 to 16
A degradable plastic bag, which is different from the degradable plastic bag in example 14 in that the coffee grounds used are from different sources, wherein the coffee grounds of example 15 are from preparation example 7; the coffee grounds of example 16 were derived from preparation example 8.
Example 17
A degradable plastic bag, which is different from the degradable plastic bag in example 15 in that the polymerized rosin glycerol ester with the model number WPR 5105 and the like are used for replacing the rosin pentaerythritol ester in example 17.
Example 18
A degradable plastic bag, which is different from the degradable plastic bag in example 15 in that the polymerized rosin glycerol ester with the model number WPR 9115 and the like are used for replacing the rosin pentaerythritol ester in example 17.
Example 19
A degradable plastic bag is different from the degradable plastic bag in example 18 in that coffee grounds and kaolin are put into a grinder to be ground and sieved to screen out the coffee grounds and the kaolin with the particle size of 0.01-0.1 mm.
Example 20
The degradable plastic bag is different from the embodiment 18 in that polylactic acid, silane coupling agent modified starch, kaolin and coffee grounds are placed in an oven, after drying for 1 hour at 100 ℃, the temperature is raised to 200 ℃ while stirring, polymerized rosin glyceride with the model number of WPR 9115 is added, stirring is continued, and heat preservation reaction is carried out for 1.5 hours, so that a blend is obtained.
Example 21
The degradable plastic bag is different from the embodiment 18 in that polylactic acid, silane coupling agent modified starch, kaolin and coffee grounds are placed in an oven, after drying for 1 hour at 100 ℃, the temperature is raised to 210 ℃ while stirring, polymerized rosin glyceride with the model number of WPR 9115 is added, stirring is continued, and heat preservation reaction is carried out for 2 hours, so that a blend is obtained.
Comparative example
Comparative examples 1 to 4
A degradable plastic bag, which is different from example 1 in the quality of each raw material, and the specific quality of each raw material is shown in table 5.
TABLE 5 quality of raw materials of degradable plastic bags of comparative examples 1 to 4
Performance test the following performance test was performed on the degradable plastic bags provided in examples 1 to 21 of the present application and comparative examples 1 to 4.
Tensile strength: the tensile strength of the degradable plastic bags of examples 1 to 21 and comparative examples 1 to 4 was measured according to GB/T1040;
elongation at break: the elongation at break of the degradable plastic bags of examples 1 to 21 and comparative examples 1 to 4 was measured according to GB/T1040;
the biodegradation rate is as follows: the biodegradation rates of the degradable plastic bags 90d and 120d of examples 1-21 and comparative examples 1-4 were tested according to GB/T20197-2006.
TABLE 6 test results of Properties of examples 1 to 21 and comparative examples 1 to 4
The toughness is embodied by the elongation at break, and the larger the elongation at break, the better the toughness.
The present application is described in detail below with respect to the test data of table 6.
Combining example 1 and comparative examples 1-2, and combining the data in table 6, it can be seen that the tensile strength of comparative example 1 is reduced from 34.3MPa to 26.9MPa and the elongation at break is reduced from 427% to 319% compared to example 1 without adding rosin pentaerythritol ester, while the tensile strength of comparative example 2 is reduced from 34.3MPa to 28.1MPa and the elongation at break is reduced from 427% to 288% compared to example 1 without adding silane coupling agent modified starch, demonstrating that the use of rosin pentaerythritol ester and silane coupling agent modified starch can effectively improve the mechanical properties, especially toughness, of the degradable plastic bag.
Combining example 1 and comparative examples 3 to 4, and combining the data of table 6, it can be seen that the tensile strength of comparative example 3 was reduced from 34.3MPa to 25.3MPa, the elongation at break was reduced from 427% to 340% and the 90d biodegradation rate was reduced from 75.1% to 36.3% compared to example 1 without adding kaolin, while the tensile strength of comparative example 4 was reduced from 34.3MPa to 22.8MPa, the elongation at break was reduced from 427% to 340% compared to example 1 and the 90d biodegradation rate was reduced from 427% to 355% without adding coffee grounds, demonstrating that kaolin and coffee grounds can improve the mechanical properties of the degradable plastic bag while increasing the degradation rate and the degradation degree of the degradable plastic bag.
Combining examples 1-10 and the data in table 6, it can be seen that the optimal ratio of the degradable plastic bag material is the ratio of example 10.
By combining the data of examples 10-14 and table 6, it can be seen that the modification of starch and silane coupling agent at a weight ratio of 1:0.2 produces a silane coupling agent with a better effect on modifying degradable plastic bags.
As can be seen by combining examples 14 to 16 with the data in Table 6, the use of the glycerol ester of polymerized rosin having an acid value of not more than 10mgKOH/g enables the toughness of the degradable plastic bag to be further improved.
It can be seen from the data of examples 18 to 19 and table 6 that the use of coffee grounds and kaolin having a particle size of 0.01 to 0.1mm can reduce the possibility of polymer agglomeration in the degradable plastic bag and improve the mechanical properties of the degradable plastic bag.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The degradable plastic bag is characterized by being prepared from the following raw materials in parts by weight:
80-120 parts of polylactic acid
30-40 parts of rosin ester
15-35 parts of silane coupling agent modified starch
10-30 parts of kaolin
5-15 parts of coffee grounds.
2. The degradable plastic bag of claim 1, wherein: the acid value of the rosin ester is not higher than 10 mgKOH/g.
3. The degradable plastic bag of claim 1, wherein: the preparation method of the silane coupling agent modified starch comprises the following steps: and (3) carrying out ultrasonic oscillation on the dried starch, stirring and blending the starch and the silane coupling agent according to the weight ratio of 1 (0.1-0.3), heating to 70-90 ℃, carrying out heat preservation reaction for 1-2 h, drying and cooling to obtain the silane coupling agent modified starch.
4. The degradable plastic bag of claim 3, wherein: the weight ratio of the starch to the silane coupling agent is 1: 0.2.
5. The degradable plastic bag of claim 3, wherein: in the preparation step of the silane coupling agent modified starch, the ultrasonic frequency is 30-40 kHz, and the ultrasonic oscillation time is 10-20 min.
6. The degradable plastic bag of claim 1, wherein: and drying the coffee grounds, and then carrying out heat treatment at 230-300 ℃.
7. The degradable plastic bag of claim 6, wherein: the heat treatment temperature of the coffee grounds is 250 ℃.
8. The degradable plastic bag of claim 1, wherein: the particle size range of the coffee grounds is 0.01-0.1 mm.
9. The degradable plastic bag of claim 1, wherein: the particle size range of the kaolin is 0.01-0.1 mm.
10. The method for preparing a degradable plastic bag according to any one of claims 1 to 9, comprising the steps of: weighing polylactic acid, rosin ester, silane coupling agent modified starch, kaolin and coffee grounds according to the formula ratio, drying in vacuum, heating to 190-210 ℃, and stirring for reaction to obtain a mixed material; and extruding and cooling the mixture to form the degradable plastic bag.
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