CN113462132A - Biodegradable composite material, preparation method thereof and biodegradable breathable film - Google Patents

Biodegradable composite material, preparation method thereof and biodegradable breathable film Download PDF

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CN113462132A
CN113462132A CN202110763938.9A CN202110763938A CN113462132A CN 113462132 A CN113462132 A CN 113462132A CN 202110763938 A CN202110763938 A CN 202110763938A CN 113462132 A CN113462132 A CN 113462132A
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parts
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biodegradable
composite material
biodegradable composite
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王雷
吴摞
刘玉城
李荣群
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Hefei Yuanrong New Material Co ltd
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Hefei Yuanrong New Material Co ltd
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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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C08J2329/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2429/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Abstract

The invention discloses a biodegradable composite material, a preparation method thereof and a biodegradable breathable film, wherein the biodegradable composite material is prepared from 25-30 parts of polybutylene succinate, 20-30 parts of polyvinyl alcohol, 20-30 parts of calcium carbonate, 2-4 parts of glycerol, 1-2 parts of sorbitol, 3-6 parts of diethylene glycol, 5-10 parts of polylactic acid, 0.1-0.3 part of antioxidant, 1-2 parts of lubricant and 0.1-0.3 part of chain extender by weight. The biodegradable composite material has high stability and plasticity, can be stably molded in the subsequent blow molding film forming process, and has no defects of holes, patterns, bubbles and the like.

Description

Biodegradable composite material, preparation method thereof and biodegradable breathable film
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a biodegradable composite material and a preparation method thereof, and a biodegradable breathable film prepared from the biodegradable composite material.
Background
At present, the breathable film mainly takes LLDPE, PU and other matrix resins as main materials, is filled and modified by ultrafine calcium carbonate, and is widely applied to the fields of medical protective clothing, baby diapers, adult diapers, sanitary napkins, warmers and packaging. The traditional modified plastic cannot be biodegraded, only a small part of the traditional modified plastic can be recycled, a large amount of plastic waste is accumulated year by year to seriously damage the ecological balance, and the traditional modified plastic has serious adverse effect on the living environment of people. Therefore, the development and application of biodegradable modified plastics are urgent, and especially, the pollution of plastic garbage to the ecological environment can be greatly improved by adopting biodegradable materials for disposable consumables such as disposable tableware, disposable packaging films, agricultural films, shopping bags and the like.
At present, biodegradable plastics are mainly used for disposable tableware (such as cups, straws and lunch boxes), shopping bags, packaging films and the like, and the research on biodegradable breathable films is less. The biodegradable breathable film is mainly applied to the packaging field, agricultural mulching films and the like at present, has biodegradability and good air permeability, can increase air permeability and simultaneously isolate moisture and microorganisms in the packaging field such as sanitary material packaging and food packaging, and is favorable for prolonging the shelf life. The biodegradable breathable film is applied to the field of agricultural films, can be dynamically exchanged with external air, and can dynamically balance oxygen and carbon dioxide in a closed space inside the film, so that the biodegradable breathable film has a certain heat preservation effect, and simultaneously has sufficient humidity and oxygen, and is beneficial to the rapid growth of crops. The biodegradable breathable film can be completely biodegraded, and the damage of the traditional plastic film to the environment is greatly improved.
The existing biodegradable materials commonly used for the biodegradable breathable film comprise PBAT, PLA, PBS, starch and the like, and calcium carbonate is added for blending modification, and because the processing performance of the biodegradable material is poorer than that of the traditional materials such as PE and PP, the defects that the blown film of the decomposed and modified material is easy to yellow, break holes, generate dark lines, bubbles and the like are easy to occur. And the toughness of the material is reduced after a large amount of calcium carbonate is filled, and meanwhile, a large amount of shear heat is generated in the processing process, so that the material decomposition is further increased, the defects are more serious, and even the film blowing molding cannot be performed.
Disclosure of Invention
In view of the above, the present invention needs to provide a biodegradable composite material, a preparation method thereof and a biodegradable breathable film, which significantly improves the stability and plasticity of the biodegradable composite material through a special plasticizing modification and chain extender technology, thereby ensuring stable molding in the subsequent blow molding process and avoiding the generation of defects such as holes, patterns, bubbles, etc.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly provides a biodegradable composite material, which is prepared from 25-30 parts of polybutylene succinate (PBS), 20-30 parts of polyvinyl alcohol (PVA), 20-30 parts of calcium carbonate, 2-4 parts of glycerol, 1-2 parts of sorbitol, 3-6 parts of diethylene glycol, 5-10 parts of polylactic acid (PLA), 0.1-0.3 part of antioxidant, 1-2 parts of lubricant and 0.1-0.3 part of chain extender by weight.
According to the invention, glycerol, sorbitol and diethylene glycol are used for plasticizing and modifying PVA, and then the PVA is introduced into PBS, so that on one hand, the thermoplastic processing performance is improved, on the other hand, the biodegradation speed is improved, and the biodegradation efficiency is obviously improved. In addition, the proper amount of PLA is introduced into the system, so that the film strength and hardness after subsequent blow molding film forming are improved, the film blowing stability of the material is improved, the decomposition of the material is greatly reduced by adding the PLA, and the dispersion of calcium carbonate is improved. Furthermore, by introducing a chain extender and a lubricant system, the melt strength of the material is effectively ensured, the thermal decomposition of the material is reduced, the dispersion of calcium carbonate is promoted, the material can be stably molded in the blow molding film forming process, and the defects of holes, patterns, bubbles and the like are avoided.
Further, the biodegradable composite of the present invention is primarily intended for blown film, and thus, in one or more embodiments of the present invention, the polybutylene succinate is selected from blown grades.
Further, the degree of polymerization of the polyvinyl alcohol is not less than 1700, and the degree of alcoholysis is in the range of 88% -90%, and preferably, in one or more embodiments of the present invention, the degree of polymerization is 1700, and the degree of alcoholysis is 88%.
Further, the calcium carbonate is selected from fine calcium carbonate, and the D50 of the fine calcium carbonate is 1.5-2 μm.
Preferably, in one or more embodiments of the present invention, the glycerol has a purity of 99% or more; the sorbitol is industrial powder sorbitol.
Further, the polylactic acid is blow molding grade, and the melt index of the polylactic acid is 3-5g/10min under the test condition of 190 ℃ and 2.16 kg.
Further, the lubricant is a compound mixture of OPE wax, stearate and erucamide, and the proportion of the lubricant is not particularly limited, and can be adjusted according to needs, and in one or more embodiments of the invention, the proportion of the lubricant is 4: 2: 1-6: 2: 1, in one or more embodiments of the invention, the OPE wax, stearate, erucamide are present in a mass ratio of 4: 2: 1, the compounding mode is not specially limited, and the conventional blending in the field is adopted.
Further, the chain extender is selected from copolymers containing epoxy groups, and specific examples that may be mentioned include, but are not limited to, ADR4468 from BASF.
The invention also provides a preparation method of the biodegradable composite material, which comprises the following steps:
fully and uniformly mixing polyvinyl alcohol, glycerol, sorbitol and diethylene glycol according to a ratio to form a fluffy premix for later use; it is understood that the mixing manner is not particularly limited, and the mixing is uniform and the fluffy state is formed, and in one or more embodiments of the present invention, the specific mixing parameters are as follows: mixing at 60-80 deg.C and 1000r/min at high speed for 25-35 min.
Drying the poly (butylene succinate) and the polylactic acid until the water content is within 300ppm, wherein the drying time can be adjusted according to the requirement; in one or more embodiments of the invention, PBS and PLA are dried at 100 ℃ for 4-6 h.
Fully mixing the dried polybutylene succinate, the polylactic acid, the premix, the lubricant, the antioxidant and the chain extender according to the proportion, feeding by main feeding, feeding calcium carbonate by two sections by side feeding, melting, mixing, dispersing, extruding and granulating by a double-screw extruder to prepare the biodegradable composite material. It is understood that the mixing manner of the raw materials is not particularly limited as long as the raw materials are uniformly mixed, and in one or more embodiments of the present invention, the raw materials are added into a high speed mixer and mixed for 5 to 8 min.
Further, the length-diameter ratio of the double-screw extruder is not less than 48: 1, the working temperature is 160-.
The invention further provides a biodegradable breathable film which is prepared by blow molding of the biodegradable composite material.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, glycerol, sorbitol and diethylene glycol are used for plasticizing and modifying PVA, and then the PVA is introduced into PBS, so that on one hand, the thermoplastic processing performance is improved, on the other hand, the biodegradation speed is improved, and the biodegradation efficiency is obviously improved. In addition, the proper amount of PLA is introduced into the system, so that the film strength and hardness after subsequent blow molding film forming are improved, the film blowing stability of the material is improved, the decomposition of the material is greatly reduced by adding the PLA, and the dispersion of calcium carbonate is improved. Furthermore, by introducing a chain extender and a lubricant system, the melt strength of the material is effectively ensured, the thermal decomposition of the material is reduced, the dispersion of calcium carbonate is promoted, the material can be stably molded in the blow molding film forming process, and the defects of holes, patterns, bubbles and the like are avoided.
The screw extrusion process adopts a specific screw combination and process, and can reduce the decomposition of materials, so that calcium carbonate can be better dispersed in a system, and the stability of subsequent blow molding film forming is obviously improved.
The biodegradable composite breathable film prepared from the degradable biological composite material has high degradation efficiency, greatly improves the damage of the traditional plastic to the environment, and has the defects of good breathability, high film strength, no holes, patterns, bubbles and the like.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In the following examples and comparative examples, the specific information of each raw material is:
PBS is commercially available blow molding grade;
the polymerization degree of PVA is 1700, the alcoholysis degree is 88 percent, and the mark is PVA-1788;
PLA is high viscosity blow molding grade, the melt index is 3-5g/10min (190 ℃, 2.16kg), and the mark is PLA-XR 175;
the lubricant is the mixture of the OPE wax, stearate and erucamide according to a mass ratio of 4: 2: 1 a compound;
the antioxidant is Basff 1010;
the chain extender is basf ADR 4468.
In the following examples and comparative examples, unless otherwise specified, "parts" means parts by weight.
Example 1
Pretreatment of PVA
Adding 25 parts of PVA, 4 parts of glycerol, 2 parts of sorbitol and 6 parts of diethylene glycol into a high-speed mixer, and mixing at a high speed of 60-80 ℃ for 30min to form a fluffy premix for later use.
Drying treatment of PBS and PLA
Drying the PBS and PLA raw materials in a dehumidifying dryer for 4-6h at 100 ℃ to ensure that the water content is within 300 ppm.
Preparation of degradable biological composite material
Mixing 25 parts of dried PBS, 10 parts of PLA, premix, 2 parts of lubricant, 0.3 part of antioxidant and 0.3 part of chain extender in a high-speed mixer for 5-8min, and adding the mixture with the length-diameter ratio of 48: 1, simultaneously feeding 20 parts of activated calcium carbonate into the double-screw extruder in two sections, melting, mixing, dispersing, extruding and granulating to obtain the degradable biological composite material, wherein the processing temperature of the double-screw extruder is 160 ℃ in the first zone, 180 ℃ in the second zone, 190 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 190 ℃ in the sixth zone, 190 ℃ in the seventh zone, 180 ℃ in the eighth zone, 180 ℃ in the ninth zone, 180 ℃ in the tenth zone, 180 ℃ in the eleventh zone, the head temperature is 200 ℃, and the screw rotation speed is controlled at 500r/min of 450 materials.
Example 2
Pretreatment of PVA
The difference from example 1 is that: 23 parts of PVA, 2 parts of glycerol, 2 parts of sorbitol and 6 parts of diethylene glycol are added.
Drying treatment of PBS and PLA
The same as in example 1.
Preparation of degradable biological composite material
Mixing 30 parts of dried PBS, 5 parts of PLA, premix, 2 parts of lubricant, 0.1 part of antioxidant and 0.1 part of chain extender in a high-speed mixer for 5-8min, and adding the mixture with the length-diameter ratio of 48: 1, simultaneously feeding 30 parts of activated calcium carbonate into the double-screw extruder in two sections, and carrying out melting, mixing, dispersing, extruding and granulating to obtain the degradable biological composite material, wherein the processing temperature of the double-screw extruder is 160 ℃ in the first zone, 180 ℃ in the second zone, 190 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 190 ℃ in the sixth zone, 190 ℃ in the seventh zone, 180 ℃ in the eighth zone, 180 ℃ in the ninth zone, 180 ℃ in the tenth zone, 180 ℃ in the eleventh zone, the head temperature is 200 ℃, and the screw rotation speed is controlled at 500r/min of 450 materials.
Example 3
Pretreatment of PVA
The difference from example 1 is that: 20 parts of PVA, 4 parts of glycerol, 2 parts of sorbitol and 3 parts of diethylene glycol are added.
Drying treatment of PBS and PLA
The same as in example 1.
Preparation of degradable biological composite material
Mixing 30 parts of dried PBS, 8 parts of PLA, premix, 2 parts of lubricant, 0.3 part of antioxidant and 0.3 part of chain extender in a high-speed mixer for 5-8min, and adding the mixture with the length-diameter ratio of 48: 1, simultaneously feeding 30 parts of activated calcium carbonate into the double-screw extruder in two sections, and carrying out melting, mixing, dispersing, extruding and granulating to obtain the degradable biological composite material, wherein the processing temperature of the double-screw extruder is 160 ℃ in the first zone, 180 ℃ in the second zone, 190 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 190 ℃ in the sixth zone, 190 ℃ in the seventh zone, 180 ℃ in the eighth zone, 180 ℃ in the ninth zone, 180 ℃ in the tenth zone, 180 ℃ in the eleventh zone, the head temperature is 200 ℃, and the screw rotation speed is controlled at 500r/min of 450 materials.
Example 4
Pretreatment of PVA
The difference from example 1 is that: 28 parts of PVA, 3 parts of glycerol, 1.5 parts of sorbitol and 4 parts of diethylene glycol are added.
Drying treatment of PBS and PLA
The same as in example 1.
Preparation of degradable biological composite material
Mixing 25 parts of dried PBS, 10 parts of PLA, premix, 1.5 parts of lubricant, 0.25 part of antioxidant and 0.2 part of chain extender in a high-speed mixer for 5-8min, and adding the mixture with the length-diameter ratio of 48: the method comprises the following steps of 1, simultaneously feeding 27 parts of activated calcium carbonate into a double-screw extruder in two sections, melting, mixing, dispersing, extruding and granulating to obtain the degradable biological composite material, wherein the processing temperature of the double-screw extruder is 160 ℃ in the first zone, 180 ℃ in the second zone, 190 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 190 ℃ in the sixth zone, 190 ℃ in the seventh zone, 180 ℃ in the eighth zone, 180 ℃ in the ninth zone, 180 ℃ in the tenth zone, 180 ℃ in the eleventh zone, the head temperature is 200 ℃, and the screw rotation speed is controlled at 500r/min of 450 materials.
Example 5
Pretreatment of PVA
30 parts of PVA, 4 parts of glycerol, 2 parts of sorbitol and 6 parts of diethylene glycol are added into a high-speed mixer and mixed for 30min at a high speed of 60-80 ℃ to form a fluffy premix for later use.
Drying treatment of PBS and PLA
Same as example 1
Preparation of degradable biological composite material
Mixing 26 parts of dried PBS, 8 parts of PLA, a premix, 2 parts of a lubricant (a compound of OPE wax, stearate and erucamide in a mass ratio of 5: 2: 1), 0.3 part of an antioxidant and 0.3 part of a chain extender in a high-speed mixer for 5-8min, and then adding the mixture into a mixer with a length-diameter ratio of 48: 1, simultaneously feeding 20 parts of activated calcium carbonate into the double-screw extruder in two sections, melting, mixing, dispersing, extruding and granulating to obtain the degradable biological composite material, wherein the processing temperature of the double-screw extruder is 160 ℃ in the first zone, 180 ℃ in the second zone, 190 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 190 ℃ in the sixth zone, 190 ℃ in the seventh zone, 180 ℃ in the eighth zone, 180 ℃ in the ninth zone, 180 ℃ in the tenth zone, 180 ℃ in the eleventh zone, the head temperature is 200 ℃, and the screw rotation speed is controlled at 500r/min of 450 materials.
Example 6
The embodiment of example 5 was used, with the following differences: in this embodiment, the lubricant is OPE wax, stearate, erucamide with a mass ratio of 6: 2: 1, compounding.
Comparative example 1
Drying treatment of PBS and PLA
The same as in example 1.
Preparation of degradable biological composite material
Mixing 90 parts of dried PBS, 10 parts of PLA, 2 parts of lubricant, 0.2 part of antioxidant and 0.15 part of chain extender in a high-speed mixer for 5-8min, and adding the mixture with the length-diameter ratio of 48: the method comprises the following steps of 1, simultaneously feeding 27 parts of activated calcium carbonate into a double-screw extruder in two sections, melting, mixing, dispersing, extruding and granulating to obtain the degradable biological composite material, wherein the processing temperature of the double-screw extruder is 160 ℃ in the first zone, 180 ℃ in the second zone, 190 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 190 ℃ in the sixth zone, 190 ℃ in the seventh zone, 180 ℃ in the eighth zone, 180 ℃ in the ninth zone, 180 ℃ in the tenth zone, 180 ℃ in the eleventh zone, the head temperature is 200 ℃, and the screw rotation speed is controlled at 500r/min of 450 materials.
Comparative example 2
Drying treatment of PBS and PLA
The same as in example 1.
Preparation of degradable biological composite material
Mixing 53 parts of dried PBS, 5 parts of PLA, 2 parts of lubricant, 0.1 part of antioxidant and 0.1 part of chain extender in a high-speed mixer for 5-8min, and adding the mixture with the length-diameter ratio of 48: 1, simultaneously feeding 30 parts of activated calcium carbonate into the double-screw extruder in two sections, and carrying out melting, mixing, dispersing, extruding and granulating to obtain the degradable biological composite material, wherein the processing temperature of the double-screw extruder is 160 ℃ in the first zone, 180 ℃ in the second zone, 190 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 190 ℃ in the sixth zone, 190 ℃ in the seventh zone, 180 ℃ in the eighth zone, 180 ℃ in the ninth zone, 180 ℃ in the tenth zone, 180 ℃ in the eleventh zone, the head temperature is 200 ℃, and the screw rotation speed is controlled at 500r/min of 450 materials.
Comparative example 3
Drying treatment of PBS and PLA
The same as in example 1.
Preparation of degradable biological composite material
Mixing 30 parts of dried PBS, 23 parts of PVA, 5 parts of PLA, 2 parts of lubricant, 0.1 part of antioxidant and 0.1 part of chain extender in a high-speed mixer for 5-8min, and adding the mixture into a mixer with the length-diameter ratio of 48: 1, simultaneously feeding 30 parts of activated calcium carbonate into the double-screw extruder in two sections, and carrying out melting, mixing, dispersing, extruding and granulating to obtain the degradable biological composite material, wherein the processing temperature of the double-screw extruder is 160 ℃ in the first zone, 180 ℃ in the second zone, 190 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 190 ℃ in the sixth zone, 190 ℃ in the seventh zone, 180 ℃ in the eighth zone, 180 ℃ in the ninth zone, 180 ℃ in the tenth zone, 180 ℃ in the eleventh zone, the head temperature is 200 ℃, and the screw rotation speed is controlled at 500r/min of 450 materials.
Comparative example 4
Pretreatment of PVA
The difference from example 1 is that: 23 parts of PVA, 2 parts of glycerol, 2 parts of sorbitol and 6 parts of diethylene glycol are added.
Drying treatment of PBS and PLA
The same as in example 1.
Preparation of degradable biological composite material
Mixing 30 parts of dried PBS, 5 parts of PLA, premix, 2 parts of lubricant, 0.1 part of antioxidant and 0.1 part of chain extender in a high-speed mixer for 5-8min, and adding the mixture with the length-diameter ratio of 48: 1, simultaneously feeding 30 parts of activated calcium carbonate into the double-screw extruder in two sections, and carrying out melting, mixing, dispersing, extruding and granulating to obtain the degradable biological composite material, wherein the processing temperature of the double-screw extruder is 160 ℃ in the first zone, 180 ℃ in the second zone, 190 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 190 ℃ in the sixth zone, 190 ℃ in the seventh zone, 180 ℃ in the eighth zone, 180 ℃ in the ninth zone, 180 ℃ in the tenth zone, 180 ℃ in the eleventh zone, the head temperature is 200 ℃, and the screw rotation speed is controlled at 500r/min of 450 materials.
Comparative example 5
Pretreatment of PVA
The difference from example 1 is that: 23 parts of PVA, 2 parts of glycerol, 2 parts of sorbitol and 6 parts of diethylene glycol are added.
Drying treatment of PBS
The same as in example 1.
Preparation of degradable biological composite material
Mixing 35 parts of dried PBS, 2 parts of premix, 2 parts of lubricant, 0.1 part of antioxidant and 0.1 part of chain extender in a high-speed mixer for 5-8min, and adding the mixture into a mixer with the length-diameter ratio of 48: 1, simultaneously feeding 30 parts of activated calcium carbonate into the double-screw extruder in two sections, and carrying out melting, mixing, dispersing, extruding and granulating to obtain the degradable biological composite material, wherein the processing temperature of the double-screw extruder is 160 ℃ in the first zone, 180 ℃ in the second zone, 190 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 190 ℃ in the sixth zone, 190 ℃ in the seventh zone, 180 ℃ in the eighth zone, 180 ℃ in the ninth zone, 180 ℃ in the tenth zone, 180 ℃ in the eleventh zone, the head temperature is 200 ℃, and the screw rotation speed is controlled at 500r/min of 450 materials.
Comparative example 6
Pretreatment of PVA
The difference from example 1 is that: 23 parts of PVA, 2 parts of glycerol, 2 parts of sorbitol and 6 parts of diethylene glycol are added.
Drying treatment of PBS and PLA
The same as in example 1.
Preparation of degradable biological composite material
Mixing 30 parts of dried PBS, 5 parts of PLA, a premix, 2 parts of a lubricant and 0.1 part of an antioxidant in a high-speed mixer for 5-8min, and adding the mixture into a mixer with a length-diameter ratio of 48: 1, simultaneously feeding 30 parts of activated calcium carbonate into the double-screw extruder in two sections, and carrying out melting, mixing, dispersing, extruding and granulating to obtain the degradable biological composite material, wherein the processing temperature of the double-screw extruder is 160 ℃ in the first zone, 180 ℃ in the second zone, 190 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 190 ℃ in the sixth zone, 190 ℃ in the seventh zone, 180 ℃ in the eighth zone, 180 ℃ in the ninth zone, 180 ℃ in the tenth zone, 180 ℃ in the eleventh zone, the head temperature is 200 ℃, and the screw rotation speed is controlled at 500r/min of 450 materials.
Comparative example 7
Pretreatment of PVA
The difference from example 1 is that: 23 parts of PVA, 2 parts of glycerol, 2 parts of sorbitol and 6 parts of diethylene glycol are added.
Drying treatment of PBS and PLA
The same as in example 1.
Preparation of degradable biological composite material
Mixing 30 parts of dried PBS, 5 parts of PLA, a premix, 2 parts of lubricant EBS, 0.1 part of antioxidant and 0.1 part of chain extender in a high-speed mixer for 5-8min, and adding the mixture into a mixer with the length-diameter ratio of 48: 1, simultaneously feeding 30 parts of activated calcium carbonate into the double-screw extruder in two sections, and carrying out melting, mixing, dispersing, extruding and granulating to obtain the degradable biological composite material, wherein the processing temperature of the double-screw extruder is 160 ℃ in the first zone, 180 ℃ in the second zone, 190 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 190 ℃ in the sixth zone, 190 ℃ in the seventh zone, 180 ℃ in the eighth zone, 180 ℃ in the ninth zone, 180 ℃ in the tenth zone, 180 ℃ in the eleventh zone, the head temperature is 200 ℃, and the screw rotation speed is controlled at 500r/min of 450 materials.
Comparative example 8
This comparative example uses the same embodiment as example 1 except that: the raw materials are mixed in a common low-speed mixer (50-100r/min) for 3 minutes, and the ratio of length to diameter is 40: 1, extruding and granulating in a double-screw extruder to prepare the biodegradable composite material. Wherein the processing temperature of the extruder is 160 ℃ in the first zone, 200 ℃ in the second zone, 200 ℃ in the third zone, 210 ℃ in the fourth zone, 210 ℃ in the fifth zone, 200 ℃ in the sixth zone, 200 ℃ in the seventh zone, 200 ℃ in the eighth zone, 200 ℃ in the ninth zone, 190 ℃ in the tenth zone, 190 ℃ in the eleventh zone, the head temperature is 220 ℃, and the rotating speed of the screw is controlled at 500 r/min.
Test example
(1) And (3) testing the biodegradation performance:
according to GB/T19277, a compost degradation test is carried out on the material, a sample material and compost inoculum are mixed and then are put into a composting container, a sufficient composting experiment is carried out under the conditions of certain oxygen, temperature (58 +/-2 ℃) and humidity (50% -55%), the ratio of the release amount of carbon dioxide after the material is degraded for 3 months to a theoretical value is determined in the experiment, the biodegradation rate is calculated, and finally the percentage is shown in Table 1:
(2) and (3) testing the air permeability of the material:
the air permeability of a material is expressed by testing the moisture transmission of the material, with higher moisture transmission indicating better air permeability of the material. Preparing the material by blowing film to 30g/m2Reference is made to GB/T12704.1-2009.
(3) Testing the strength of the film: the tensile strength of the film was tested in N according to the GB/T1040-2018 film test standards.
The results are shown in Table 1.
TABLE 1 test results of examples and comparative examples
Figure BDA0003150107340000101
As can be seen from the experimental data of examples 1-4 and comparative examples, the biodegradable breathable film composite material not only has better biodegradation rate, but also has better ventilation efficiency, the degradation rate of the compost experimental material after 3 months is more than 80%, and the biodegradation rate of the biodegradable experimental material is improved by more than 50% compared with that of a PBS material. The moisture permeability of the material is improved to 1700 g/(m) from 02D) has better air permeability. The addition of PVA can promote the biodegradation efficiency, the PVA plasticizing treatment and the addition of the chain extender are more favorable for improving the strength of the film, the PVA plasticizing treatment can improve the processing performance of the film, the film is favorable for being compatible with other materials, and the chain extender can effectively avoid the thermal degradation in the material processing process, so that the material strength is increased. Meanwhile, a proper lubricating system is favorable for the dispersion of powder, and the air permeability and the tensile strength of the film can be increased.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The biodegradable composite material is characterized by being prepared from 25-30 parts of polybutylene succinate, 20-30 parts of polyvinyl alcohol, 20-30 parts of calcium carbonate, 2-4 parts of glycerol, 1-2 parts of sorbitol, 3-6 parts of diethylene glycol, 5-10 parts of polylactic acid, 0.1-0.3 part of antioxidant, 1-2 parts of lubricant and 0.1-0.3 part of chain extender in parts by weight.
2. The biodegradable composite according to claim 1, characterized in that said polybutylene succinate is selected from the group consisting of blow-molding grades;
the polymerization degree of the polyvinyl alcohol is more than or equal to 1700, and the alcoholysis degree is 88-99%.
3. Biodegradable composite material according to claim 1, characterized in that said calcium carbonate is selected from fine calcium carbonate having a D50 comprised between 1.5 and 2 μm.
4. The biodegradable composite according to claim 1, characterized in that said glycerol has a purity of more than 99%; the sorbitol is industrial powder sorbitol.
5. The biodegradable composite according to claim 1 characterized in that said polylactic acid is of blow-molding grade having a melt index of 3 to 5g/10min at 190 ℃ under 2.16kg test conditions.
6. The biodegradable composite of claim 1 wherein the lubricant is a combination of OPE wax, stearate, and erucamide.
7. Biodegradable composite according to claim 1, characterized in that said chain extender is selected from copolymers containing epoxy groups.
8. A method for preparing a biodegradable composite material according to any one of claims 1 to 7, characterized in that it comprises the following steps:
fully and uniformly mixing polyvinyl alcohol, glycerol, sorbitol and diethylene glycol according to a ratio to form a fluffy premix for later use;
drying the poly (butylene succinate) and the polylactic acid until the water content is within 300 ppm;
fully mixing the dried polybutylene succinate, the polylactic acid, the premix, the lubricant, the antioxidant and the chain extender according to the proportion, feeding by main feeding, feeding calcium carbonate by two sections by side feeding, melting, mixing, dispersing, extruding and granulating by a double-screw extruder to prepare the biodegradable composite material.
9. The method of claim 8, wherein the twin screw extruder has a length to diameter ratio of not less than 48: 1, the working temperature is 160-.
10. Biodegradable breathable film, characterized in that it is obtained by blow-moulding a biodegradable composite according to any one of claims 1 to 7.
CN202110763938.9A 2021-07-06 2021-07-06 Biodegradable composite material, preparation method thereof and biodegradable breathable film Pending CN113462132A (en)

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WO2023141597A1 (en) * 2022-01-21 2023-07-27 Okeanos Group, Llc Layer including calcium carbonate

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CN103044716A (en) * 2013-01-04 2013-04-17 四川长虹电器股份有限公司 Biodegradable material and preparation method thereof
CN109294190A (en) * 2018-09-26 2019-02-01 瑞德纳米科技（广州）有限公司 A kind of Degradable high polymer film and preparation method thereof
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WO1998039382A1 (en) * 1997-03-07 1998-09-11 Solplax Limited Improved biodegradable plastics material and a method for its manufacture
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