CN111393719A - Bio-based degradable sheet and preparation method thereof - Google Patents
Bio-based degradable sheet and preparation method thereof Download PDFInfo
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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
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
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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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
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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
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention discloses a bio-based degradable sheet and a preparation method thereof, wherein the bio-based degradable sheet is prepared from the following raw materials in parts by weight: 40-60 parts of plant starch, 4-10 parts of inorganic compound, 10-35 parts of aliphatic polyester, 0.5-2 parts of coupling compound additive, 1-2 parts of thermoplastic additive, 0.1-0.3 part of nucleating agent and 0.5-1 part of functional additive. The bio-based degradable sheet disclosed by the invention can be effectively biodegraded by 69% in 60 days, is high in bio-based content and low in preparation cost; the coupling composite auxiliary agent, the nucleating agent and the functional auxiliary agent are added into the formula, so that the aliphatic polyester and the plant starch are well compatible, the stability of the formula is improved, the coupling composite auxiliary agent in the formula of the sheet can modify the plant starch, the nucleating agent can promote nucleation, and the heat resistance and the tensile strength of the inorganic compound can be remarkably improved by adding the modified calcium carbonate.
Description
Technical Field
The invention relates to the technical field of degradable sheets, in particular to a bio-based degradable sheet and a preparation method thereof.
Background
Starch is a renewable recyclable green material from natural plants, can be used as grain for human use, and is widely applied to the fields of chemical industry and new materials for preparing various composite materials. Due to the excellent biodegradability, starch is generally used as filling to prepare thermoplastic high-biochar-content bio-based composite materials, is widely applied to disposable products, and is more and more valued by people in the large environment that petrochemical resources are increasingly in shortage and white pollution is increasingly serious at present. Plant fiber is another biomass resource which widely exists in nature and is renewable, has larger length-diameter ratio and higher specific strength compared with starch, and is a very important raw material for preparing bio-based composite materials. The plant fiber with higher length-diameter ratio and specific strength can construct a three-dimensional structure in the composite material to form a supporting framework, and the supporting framework is connected with the continuous phase matrix to form a structural reinforcing material.
The addition of calcium carbonate, especially after surface treatment, can not only improve the tensile strength of the product, but also improve the heat resistance of the product. Calcium carbonate belongs to inorganic nonmetallic minerals, has a plurality of hydroxyl groups on the surface, is easy to absorb moisture, and the surface of calcium carbonate powder particles which are not subjected to surface treatment is hydrophilic and oleophobic and is strong in polarity, so that the calcium carbonate powder particles can not be chemically crosslinked with high molecular organic matters such as plastics, rubber and the like, are difficult to uniformly disperse in an organic medium, and are difficult to form good bonding on the interface. In addition, the ultrafine calcium carbonate has small particle size, extremely large specific surface area and higher specific surface energy, and is very easy to coagulate and agglomerate in the preparation and post-treatment processes to form secondary particles, so that the particle size is increased, and the functions of the ultrafine particles are lost in the application process, thereby influencing the actual application effect and failing to play the role of a functional filler.
Research shows that the double-layer compound coupling agent (compounded by silane coupling agent and titanate coupling agent) modified calcium carbonate can remarkably improve the tensile strength (37%) of the material, and the improvement amplitude of the material by using a single coupling agent is respectively 16.8% and 26.6%; in addition, the research reports that the compound of the aluminate coupling agent and the stearic acid is used as modified calcium carbonate are also many, and the calcium carbonate modified by the compound of the acid ester coupling agent and the stearic acid has good wettability.
The current bio-based degradable sheet is mainly made of polylactic acid P L A, polycaprolactone P L A, polyvinyl alcohol, polyhydroxyalkanoate and polybutylene succinate in polyester, but the price of the polyester is higher than the market price by 1-2 times and cannot be any for consumers and merchants, and the physical and mechanical properties and chemical properties of the material are greatly different from those of common plastics, particularly the heat resistance and tensile strength are not required, so that the requirements of the bio-based degradable material and the disposable bio-based degradable sheet are increasingly obvious and urgent.
Disclosure of Invention
The invention provides a bio-based degradable sheet and a preparation method thereof, wherein the sheet can be biodegraded, and has high bio-based content, good tensile strength and good heat resistance.
The invention adopts the following technical scheme for solving the technical problems:
a bio-based degradable sheet is prepared from the following raw materials in parts by weight: 40-60 parts of plant starch, 4-10 parts of inorganic compound, 10-35 parts of aliphatic polyester, 0.5-2 parts of coupling compound additive, 1-2 parts of thermoplastic additive, 0.1-0.3 part of nucleating agent and 0.5-1 part of functional additive.
As a most preferable scheme, the bio-based degradable sheet is prepared from the following raw materials in parts by weight: 50 parts of plant starch, 8 parts of inorganic compound, 25 parts of aliphatic polyester, 1.2 parts of coupling compound additive, 1.5 parts of thermoplastic additive, 0.2 part of nucleating agent and 0.8 part of functional additive.
Preferably, the plant starch is one or more of potato starch, corn starch, wheat starch, tapioca starch and taro starch.
As a most preferred scheme, the plant starch is potato starch, corn starch and wheat starch in a weight ratio of 1: 1:1 mixing.
Preferably, the inorganic compound is two or more of talcum powder, calcium carbonate, modified calcium carbonate and barium sulfate.
As a most preferred scheme, the inorganic compound is modified calcium carbonate and barium sulfate according to a weight ratio of 1: 0.4 mixing.
As a preferable scheme, the preparation method of the modified calcium carbonate comprises the following steps: s1, putting 40-60 parts of calcium carbonate and 8-12 parts of talcum powder into a mixer, and uniformly mixing to obtain a mixture for later use, wherein the rotating speed of the mixer is 600-800 r/min, and the mixing time is 4-8 min; s2, adding the mixture and the modifier into a mixer for modification and mixing uniformly, wherein the rotating speed of the mixer is 500-700 r/min, the mixing time is 8-12 min, and grinding to 800-1200 meshes to obtain the modified calcium carbonate.
As a preferable scheme, the modifier consists of 0.4-0.6 part of gamma-mercaptopropyl-trimethoxysilane, 0.6-1 part of KH-590 and 2-4 parts of citric acid.
In a preferred embodiment, the aliphatic polyester is one or two of polylactic acid and polybutylene glycol succinate.
In a most preferred embodiment, the aliphatic polyester is polytetramethylene glycol succinate.
Preferably, the coupling compound auxiliary agent is two or more of vinyltriethoxysilane, KH-570, KH-550, KH-560, KH-590, triisostearoyl isopropyl titanate, trioleoyl isopropyl titanate, dodecylbenzenesulfonyl, peanut oil, an aluminate coupling agent, an aluminum-titanium compound coupling agent and stearic acid.
As a most preferable scheme, the coupling compound auxiliary agent is KH-570 and stearic acid which are mixed according to the weight ratio of 1: 1.
Preferably, the thermoplastic auxiliary agent is one or more of 1, 4 butanediol, 2, 5 hexanediol, glycerol, ethylene glycol, propylene glycol, sorbitol, xylitol, maltitol, formamide and acetamide.
As a most preferred option, the thermoplastic adjuvant is glycerol.
As a preferable scheme, the nucleating agent is one or more of TMC-200, TMC-210, TMC-300, TMC-306, TMC-328, K L-4300, K L-4376 and K L4370B.
As a most preferred embodiment, the nucleating agent is TMC-210.
As a preferable scheme, the functional auxiliary agent consists of a lubricant and an antioxidant; the lubricant is one or more of fatty acid amide liquid paraffin, solid paraffin, microcrystalline paraffin, polyethylene wax, polytetrafluoroethylene wax and fatty acid; the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 622, antioxidant 215, antioxidant B561, antioxidant BHT, antioxidant T502, antioxidant DSTOP, and vitamin E.
As a most preferable scheme, the functional auxiliary agent is prepared from a lubricant and an antioxidant according to the weight ratio of 1: 0.8; the lubricant is microcrystalline paraffin; the antioxidant is antioxidant B215.
The invention also provides a preparation method of the bio-based degradable sheet, which comprises the following steps:
(1) drying the plant starch, weighing the raw materials according to the proportion, adding the plant starch and the composite inorganic substance into a high-speed mixer, and mixing uniformly;
(2) adding a coupling composite auxiliary agent into a high-speed mixer, wherein the rotating speed of the high-speed mixer is 1500-2000 r/min, the temperature is 120-130 ℃, and the mixing time is 10-20 min;
(3) adding aliphatic polyester, a thermoplastic additive, a composite nucleating agent and a functional additive into a high-speed mixer, wherein the rotating speed of the high-speed mixer is 1500-2000 r/min, the temperature is 120-130 ℃, and the mixing time is 5-10 min; after the mixing is finished, adding the materials into a cold mixer, and stopping mixing when the temperature is reduced to 50-70 ℃ to obtain a mixture;
(4) adding the mixture into a double-screw sheet machine to prepare a sheet, wherein the temperature of a screw area of the double-screw sheet machine is 150-180 ℃; the temperature of the die head area is 165-170 ℃; the temperature of the mirror surface roller zone is 45-75 ℃.
As a preferable scheme, the rotating speed of the high-speed mixer in the step (1) is 1000-1400 r/min, the temperature is 120-130 ℃, and the mixing time is 10-20 min.
The invention has the beneficial effects that: (1) the bio-based degradable sheet is prepared from plant starch, an inorganic compound, aliphatic polyester, a coupling compound auxiliary agent, a thermoplastic auxiliary agent, a nucleating agent and a functional auxiliary agent, can be effectively biodegraded, can be degraded by 69% in 60 days, and has high bio-based content and low preparation cost; (2) according to the invention, the coupling composite auxiliary agent, the nucleating agent and the functional auxiliary agent are added into the formula, so that the aliphatic polyester and the plant starch are well compatible, the stability of the formula is improved, the coupling composite auxiliary agent in the formula of the sheet can modify the plant starch, the nucleating agent can promote nucleation, the crystallization rate of the resin can be obviously improved, the molding cycle of the product is shortened, the production efficiency is improved, the physical and mechanical properties of the product are improved, and the thermal deformation temperature and the tensile strength of the product are improved; (3) according to the invention, inorganic substances are compounded and interact with each other, so that the inorganic substances can be well filled in the sheet material, fine gaps in the sheet material are reduced, the problem of powder removal can be solved, and the heat resistance and the tensile strength are obviously improved; (4) the inorganic compound can obviously improve the heat resistance and the tensile strength by adding the modified calcium carbonate, wherein the calcium carbonate is compounded with a small amount of talcum powder, and the double-layer compound coupling agent is added to obviously improve the heat resistance and the tensile strength.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, 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 a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive work based on the embodiments of the present invention, are within the scope of the present invention; the parts are all parts by weight.
Example 1
A bio-based degradable sheet is prepared from the following raw materials in parts by weight: 50 parts of plant starch, 8 parts of inorganic compound, 25 parts of aliphatic polyester, 1.2 parts of coupling compound additive, 1.5 parts of thermoplastic additive, 0.2 part of nucleating agent and 0.8 part of functional additive.
The plant starch is potato starch, corn starch and wheat starch in a weight ratio of 1: 1:1 mixing.
The inorganic compound is modified calcium carbonate and barium sulfate according to the weight ratio of 1: 0.4 mixing.
The inorganic compound is prepared by mixing modified calcium carbonate and barium sulfate, and the preparation method of the modified calcium carbonate comprises the following steps: s1, putting 50 parts of calcium carbonate and 10 parts of talcum powder into a mixer, and uniformly mixing to obtain a mixture for later use, wherein the rotating speed of the mixer is 700r/min, and the mixing time is 6 min; s2 compounding modifier with gamma-mercaptopropyl-trimethoxysilane 0.5 weight portions, KH-590 weight portions and citric acid 3 weight portions; and adding the mixture and the modifier into a mixer for modification and mixing uniformly, wherein the rotating speed of the mixer is 600r/min, the mixing time is 10min, and grinding to 1000 meshes to obtain the modified calcium carbonate.
The aliphatic polyester is polytetramethylene glycol butanediol ester.
The coupling composite additive is formed by mixing KH-570 and stearic acid according to the weight ratio of 1: 1.
The thermoplastic auxiliary agent is glycerol.
The nucleating agent is TMC-210.
The functional auxiliary agent is prepared from a lubricant and an antioxidant according to the weight ratio of 1: 0.8; the lubricant is microcrystalline paraffin; the antioxidant is antioxidant B215.
The preparation method of the bio-based degradable sheet comprises the following steps:
(1) drying plant starch, weighing raw materials according to a ratio, adding the plant starch and a composite inorganic substance into a high-speed mixer, uniformly mixing, wherein the rotating speed of the high-speed mixer is 1200r/min, the temperature is 125 ℃, and the mixing time is 15 min;
(2) adding the coupling composite auxiliary agent into a high-speed mixer, wherein the rotating speed of the high-speed mixer is 1800r/min, the temperature is 125 ℃, and the mixing time is 15 min;
(3) adding aliphatic polyester, a thermoplastic additive, a composite nucleating agent and a functional additive into a high-speed mixer, wherein the rotating speed of the high-speed mixer is 1800r/min, the temperature is 125 ℃, and the mixing time is 8 min; after the mixing is finished, adding the materials into a cold mixer, and stopping mixing when the temperature is reduced to 60 ℃ to obtain a mixture;
(4) adding the mixture into a double-screw sheet machine to prepare a sheet, wherein the temperature of a screw area of the double-screw sheet machine is 150-180 ℃; the temperature of the die head area is 165-170 ℃; the temperature of the mirror surface roller zone is 45-75 ℃.
Example 2
A bio-based degradable sheet is prepared from the following raw materials in parts by weight: 60 parts of plant starch, 10 parts of inorganic compound, 35 parts of aliphatic polyester, 2 parts of coupling compound additive, 2 parts of thermoplastic additive, 0.3 part of nucleating agent and 1 part of functional additive.
The plant starch is cassava starch and taro starch which are mixed according to the weight ratio of 1: 1.
The inorganic compound is talcum powder and modified calcium carbonate according to the weight ratio of 1: 2 and mixing.
The inorganic compound is prepared by mixing modified calcium carbonate and barium sulfate, and the preparation method of the modified calcium carbonate comprises the following steps: s1, putting 50 parts of calcium carbonate and 10 parts of talcum powder into a mixer, and uniformly mixing to obtain a mixture for later use, wherein the rotating speed of the mixer is 700r/min, and the mixing time is 6 min; s2 compounding modifier with gamma-mercaptopropyl-trimethoxysilane 0.5 weight portions, KH-590 weight portions and citric acid 3 weight portions; and adding the mixture and the modifier into a mixer for modification and mixing uniformly, wherein the rotating speed of the mixer is 600r/min, the mixing time is 10min, and grinding to 1000 meshes to obtain the modified calcium carbonate.
The aliphatic polyester is polylactic acid.
The coupling compound additive is formed by mixing KH-550 and peanut oil according to the weight ratio of 1: 1.
The thermoplastic auxiliary agent is maltitol.
The nucleating agent is TMC-200.
The functional auxiliary agent is prepared by mixing a lubricant and an antioxidant according to the weight ratio of 1: 1; the lubricant is polyethylene wax; the antioxidant is antioxidant BHT.
The preparation method of the bio-based degradable sheet comprises the following steps:
(1) drying plant starch, weighing raw materials according to a ratio, adding the plant starch and a composite inorganic substance into a high-speed mixer, uniformly mixing, wherein the rotating speed of the high-speed mixer is 1200r/min, the temperature is 125 ℃, and the mixing time is 15 min;
(2) adding the coupling composite auxiliary agent into a high-speed mixer, wherein the rotating speed of the high-speed mixer is 1800r/min, the temperature is 125 ℃, and the mixing time is 15 min;
(3) adding aliphatic polyester, a thermoplastic additive, a composite nucleating agent and a functional additive into a high-speed mixer, wherein the rotating speed of the high-speed mixer is 1800r/min, the temperature is 125 ℃, and the mixing time is 8 min; after the mixing is finished, adding the materials into a cold mixer, and stopping mixing when the temperature is reduced to 60 ℃ to obtain a mixture;
(4) adding the mixture into a double-screw sheet machine to prepare a sheet, wherein the temperature of a screw area of the double-screw sheet machine is 150-180 ℃; the temperature of the die head area is 165-170 ℃; the temperature of the mirror surface roller zone is 45-75 ℃.
Example 3
A bio-based degradable sheet is prepared from the following raw materials in parts by weight: 40 parts of plant starch, 4 parts of inorganic compound, 10 parts of aliphatic polyester, 0.5 part of coupling compound additive, 1 part of thermoplastic additive, 0.1 part of nucleating agent and 0.5 part of functional additive.
The plant starch is prepared by mixing corn starch and wheat starch according to the weight ratio of 1: 1.
The inorganic compound is formed by mixing talcum powder and barium sulfate according to the weight ratio of 1: 0.5.
The aliphatic polyester is polytetramethylene glycol butanediol ester.
The coupling composite additive is formed by mixing KH-560 and dodecyl benzene sulfonyl according to the weight ratio of 1: 0.8.
The thermoplastic auxiliary agent is formamide.
The nucleating agent is TMC-300.
The functional auxiliary agent is prepared by mixing a lubricant and an antioxidant according to the weight ratio of 1: 1; the lubricant is polytetrafluoroethylene wax; the antioxidant is antioxidant 1010.
The preparation method of the bio-based degradable sheet comprises the following steps:
(1) drying plant starch, weighing raw materials according to a ratio, adding the plant starch and a composite inorganic substance into a high-speed mixer, uniformly mixing, wherein the rotating speed of the high-speed mixer is 1200r/min, the temperature is 125 ℃, and the mixing time is 15 min;
(2) adding the coupling composite auxiliary agent into a high-speed mixer, wherein the rotating speed of the high-speed mixer is 1800r/min, the temperature is 125 ℃, and the mixing time is 15 min;
(3) adding aliphatic polyester, a thermoplastic additive, a composite nucleating agent and a functional additive into a high-speed mixer, wherein the rotating speed of the high-speed mixer is 1800r/min, the temperature is 125 ℃, and the mixing time is 8 min; after the mixing is finished, adding the materials into a cold mixer, and stopping mixing when the temperature is reduced to 60 ℃ to obtain a mixture;
(4) adding the mixture into a double-screw sheet machine to prepare a sheet, wherein the temperature of a screw area of the double-screw sheet machine is 150-180 ℃; the temperature of the die head area is 165-170 ℃; the temperature of the mirror surface roller zone is 45-75 ℃.
Example 4
Example 4 is different from example 1 in the composition of the inorganic composite, and is otherwise the same.
The inorganic compound is calcium carbonate and barium sulfate according to the weight ratio of 1: 0.4 mixing.
Comparative example 1
Comparative example 1 is different from example 1 in that comparative example 1 replaces the inorganic composite with calcium carbonate, and the others are the same.
Comparative example 2
Comparative example 2 is different from example 1 in that comparative example 2 describes a modified calcium carbonate modification method different from example 1, and the other is the same.
The preparation method of the modified calcium carbonate comprises the following steps: s1, putting 50 parts of calcium carbonate and 10 parts of talcum powder into a mixer, and uniformly mixing to obtain a mixture for later use, wherein the rotating speed of the mixer is 700r/min, and the mixing time is 6 min; s2, compounding 0.8 part of KH-590 and 3 parts of citric acid into a modifier; and adding the mixture and the modifier into a mixer for modification and mixing uniformly, wherein the rotating speed of the mixer is 600r/min, the mixing time is 10min, and grinding to 1000 meshes to obtain the modified calcium carbonate.
Comparative example 3
Comparative example 3 differs from example 1 in that the modified calcium carbonate modification process described in comparative example 3 differs from example 1, all other things being equal.
The inorganic compound is prepared by mixing modified calcium carbonate and barium sulfate, and the preparation method of the modified calcium carbonate comprises the following steps: s1, putting 50 parts of calcium carbonate and 10 parts of talcum powder into a mixer, and uniformly mixing to obtain a mixture for later use, wherein the rotating speed of the mixer is 700r/min, and the mixing time is 6 min; s2 compounding 0.5 part of gamma-mercaptopropyl-trimethoxysilane and 3 parts of citric acid into a modifier; and adding the mixture and the modifier into a mixer for modification and mixing uniformly, wherein the rotating speed of the mixer is 600r/min, the mixing time is 10min, and grinding to 1000 meshes to obtain the modified calcium carbonate.
Comparative example 4
Comparative example 4 is different from example 1 in that comparative example 3 describes a modified calcium carbonate modification method different from example 1, and the other is the same.
The inorganic compound is prepared by mixing modified calcium carbonate and barium sulfate, and the preparation method of the modified calcium carbonate comprises the following steps: s1, putting 50 parts of calcium carbonate and 10 parts of talcum powder into a mixer, and uniformly mixing to obtain a mixture for later use, wherein the rotating speed of the mixer is 700r/min, and the mixing time is 6 min; s2 compounding modifier with isopropyl trititanate 0.5 weight portions, KH560 weight portions and citric acid 3 weight portions; and adding the mixture and the modifier into a mixer for modification and mixing uniformly, wherein the rotating speed of the mixer is 600r/min, the mixing time is 10min, and grinding to 1000 meshes to obtain the modified calcium carbonate.
Comparative example 5
Comparative example 5 differs from example 1 in that the sheet formulation is different and the rest is the same.
A bio-based degradable sheet is prepared from the following raw materials in parts by weight: 50 parts of plant starch, 8 parts of inorganic compound, 25 parts of aliphatic polyester, 1.5 parts of thermoplastic auxiliary agent, 0.2 part of nucleating agent and 0.8 part of functional auxiliary agent.
Comparative example 6
Comparative example 6 differs from example 1 in that the sheet formulation is different and the rest is the same.
A bio-based degradable sheet is prepared from the following raw materials in parts by weight: 50 parts of plant starch, 8 parts of inorganic compound, 25 parts of aliphatic polyester, 1.2 parts of coupling compound additive, 1.5 parts of thermoplastic additive and 0.8 part of functional additive.
To further demonstrate the effect of the present invention, the following test methods were provided:
1. biodegradability test, the product is injected by a 300 g injection machine to obtain standard sample strips with the size of 100 mm × 10 mm × 1.0.0 mm, the standard sample strips are subjected to various performance tests by the following standard methods, the test results are shown in the following table 1, the weight of each standard sample strip at the moment is weighed and recorded, then the standard sample strips are respectively wrapped among gauzes and buried in flower garden soil 20 cm away from the ground, the standard sample strips are taken out after 60 days and cleaned, dried and weighed, and the weight is recorded, and the weight loss ratio (%) of the standard sample strips is calculated by the following method, namely the weight loss ratio (%) (the weight before the test-the weight after 60 days buried in the soil)/the weight before the test is × 100% respectively.
TABLE 1 biodegradability test
As can be seen from table 1, the resin according to the invention is capable of degrading 69.0% in 60 days.
2. The high temperature resistance is measured according to GB/T1634-.
TABLE 2 test results
As can be seen from table 2, the bio-based degradable sheet of the present invention has good heat resistance and tensile strength, wherein example 1 has the best tensile strength and heat resistance; as can be seen from comparison of examples 1 to 3, different proportions and raw material selection can affect tensile strength and heat resistance, wherein example 1 has the best proportion and the best raw material; comparing example 1 with example 4, it can be seen that the modified calcium carbonate of the present invention can significantly improve tensile strength and heat resistance; it can be seen from the comparison of example 1 with comparative example 1 that, when the inorganic composite of the present invention is substituted with the same substance, inorganic substance, the tensile strength and heat resistance are remarkably decreased; as can be seen from the comparison of example 1 and comparative examples 2 to 3, when the double-layer coupling agent in the modified calcium carbonate of the present invention is changed into a single coupling agent, the tensile strength and the heat resistance are significantly reduced; as can be seen from the comparison of example 1 and comparative example 4, the tensile strength and heat resistance of the modified calcium carbonate of the present invention are reduced after the double-layer compound coupling agent is replaced by other coupling agents; as can be seen from the comparison of example 1 and comparative examples 5-6, the tensile strength and heat resistance can be remarkably improved by adding the coupling composite assistant and the nucleating agent in the sheet formula.
In light of the foregoing description of preferred embodiments according to the invention, it is clear that many changes and modifications can be made by the person skilled in the art without departing from the scope of the invention. The technical scope of the present invention is not limited to the contents of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. The bio-based degradable sheet is characterized by being prepared from the following raw materials in parts by weight: 40-60 parts of plant starch, 4-10 parts of inorganic compound, 10-35 parts of aliphatic polyester, 0.5-2 parts of coupling compound additive, 1-2 parts of thermoplastic additive, 0.1-0.3 part of nucleating agent and 0.5-1 part of functional additive.
2. The bio-based degradable sheet according to claim 1, wherein the bio-based degradable sheet is prepared from the following raw materials in parts by weight: 50 parts of plant starch, 8 parts of inorganic compound, 25 parts of aliphatic polyester, 1.2 parts of coupling compound additive, 1.5 parts of thermoplastic additive, 0.2 part of nucleating agent and 0.8 part of functional additive.
3. The biodegradable sheet according to claim 1, wherein said plant starch is one or more of potato starch, corn starch, wheat starch, tapioca starch, and taro starch.
4. The biodegradable sheet according to claim 1, wherein said inorganic composite is two or more of talc, calcium carbonate, modified calcium carbonate, barium sulfate.
5. The biodegradable sheet according to claim 4, wherein said inorganic composite is modified calcium carbonate mixed with barium sulfate.
6. The bio-based degradable sheet according to claim 1, wherein the aliphatic polyester is one or two of polylactic acid and polybutylene glycol succinate; the coupling composite additive is two or more of vinyl triethoxysilane, KH-570, KH-550, KH-560, KH-590, triisostearoyl isopropyl titanate, trioleoyl isopropyl titanate, dodecylbenzenesulfonyl, peanut oil, an aluminate coupling agent, an aluminum-titanium composite coupling agent and stearic acid.
7. The bio-based degradable sheet according to claim 1, wherein the thermoplastic auxiliary agent is one or more of 1, 4 butanediol, 2, 5 hexanediol, glycerol, ethylene glycol, propylene glycol, sorbitol, xylitol, maltitol, formamide, acetamide; the above-mentioned
The nucleating agent is one or more of TMC-200, TMC-210, TMC-300, TMC-306, TMC-328, K L-4300, K L-4376 and K L4370B.
8. The bio-based degradable sheet according to claim 1, wherein the functional agent is composed of a lubricant, an antioxidant; the lubricant is one or more of fatty acid amide liquid paraffin, solid paraffin, microcrystalline paraffin, polyethylene wax, polytetrafluoroethylene wax and fatty acid; the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 622, antioxidant 215, antioxidant B561, antioxidant BHT, antioxidant T502, antioxidant DSTOP, and vitamin E.
9. The method for producing a biodegradable sheet according to any one of claims 1 to 8, comprising the steps of:
(1) drying the plant starch, weighing the raw materials according to the proportion, adding the plant starch and the composite inorganic substance into a high-speed mixer, and mixing uniformly;
(2) adding a coupling composite auxiliary agent into a high-speed mixer, wherein the rotating speed of the high-speed mixer is 1500-2000 r/min, the temperature is 120-130 ℃, and the mixing time is 10-20 min;
(3) adding aliphatic polyester, a thermoplastic additive, a composite nucleating agent and a functional additive into a high-speed mixer, wherein the rotating speed of the high-speed mixer is 1500-2000 r/min, the temperature is 120-130 ℃, and the mixing time is 5-10 min; after the mixing is finished, adding the materials into a cold mixer, and stopping mixing when the temperature is reduced to 50-70 ℃ to obtain a mixture;
(4) adding the mixture into a double-screw sheet machine to prepare a sheet, wherein the temperature of a screw area of the double-screw sheet machine is 150-180 ℃; the temperature of the die head area is 165-170 ℃; the temperature of the mirror surface roller zone is 45-75 ℃.
10. The method for preparing the bio-based degradable sheet material according to the claim 9, wherein the rotation speed of the high speed mixer in the step (1) is 1000-1400 r/min, the temperature is 120-130 ℃, and the mixing time is 10-20 min.
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| CN114539634A (en) * | 2022-02-08 | 2022-05-27 | 龙群科技(云南)有限公司 | Degradable environment-friendly plastic and preparation method thereof |
| CN115028977A (en) * | 2022-06-21 | 2022-09-09 | 惠州科碧尔生物新材料有限公司 | Blending modified sheet material prepared from natural biobased material and biodegradable raw material |
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| CN111393719B (en) | 2022-04-05 |
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