CN114634689A - Completely biodegradable composite material and preparation method thereof - Google Patents

Completely biodegradable composite material and preparation method thereof Download PDF

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Publication number
CN114634689A
CN114634689A CN202011478680.XA CN202011478680A CN114634689A CN 114634689 A CN114634689 A CN 114634689A CN 202011478680 A CN202011478680 A CN 202011478680A CN 114634689 A CN114634689 A CN 114634689A
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starch
parts
resin composition
based resin
composite material
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邵晓涛
徐梦娇
孙丽
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02Starch; Degradation products thereof, e.g. dextrin
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04Homopolymers or copolymers of esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/02Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/06Biodegradable
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a completely biodegradable composite material, which comprises one or a mixture of more of polylactic acid, polybutylene succinate, polybutylene terephthalate-adipate, polybutylene succinate-co-terephthalate, polybutylene succinate-adipate-butylene glycol, polycaprolactone, polypropylene carbonate and polyhydroxyalkanoate series compounds, wherein a starch-based resin composition comprises 50-80 parts of starch, 30-50 parts of starch and acrylate graft copolymer and 10-30 parts of acrylate homopolymer, the biodegradable composite material prepared by the preparation method of a formula machine can improve the degradation speed and has better degradation performance, objects which are difficult to degrade such as packaging materials, convenient bags and the like can be completely degraded, and further white pollution to the environment is reduced, improve environmental quality, from long-term perspective, can carry out safe effectual popularization on a large scale, compare simultaneously in using chemical agent to degrade, its economic cost is lower.

Description

Completely biodegradable composite material and preparation method thereof
Technical Field
The invention relates to the technical field of biodegradation, in particular to a completely biodegradable composite material and a preparation method thereof.
Background
The application of the biodegradable material is very wide, and comprises medicine, agriculture, industrial packaging, family entertainment and the like. The biodegradable absorption polymer materials developed in recent years are materials that are hydrolyzed or enzymatically hydrolyzed into small molecules within a certain period of time after completing medical action, and then the small molecules participate in normal metabolic cycle, so that the small molecules are absorbed or excreted by human bodies. Biodegradable plastics have been used in the medical fields of vascular surgery, orthopedic surgery, in vivo drug delivery matrices, and absorbable sutures. The agricultural degradable material is finally converted into a material for improving soil texture, and mainly comprises agricultural film covering and controlled release of medicaments. The addition of degradable materials to plastic cards (e.g., credit cards, IP cards, etc.) also allows them to be rapidly degraded after disposal without environmental contamination.
At present, degradable paper materials or paper bags are used as packaging materials, convenient bags and the like in western developed countries such as the United states, the use of the materials greatly reduces white pollution to the environment and improves the environmental quality, however, some existing degradable materials cannot be completely degraded, the degradation speed is slow, and long time is needed for complete degradation.
Disclosure of Invention
The present invention aims at providing one kind of completely biodegradable composite material and its preparation process, and aims at solving the problems of the said background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a completely biodegradable composite material comprises one or a mixture of more of 10 parts of polylactic acid, 6 parts of polybutylene succinate, 3 parts of polybutylene terephthalate-adipate, 1 part of polybutylene succinate-co-terephthalate, 3 parts of polybutylene succinate-adipate, 12 parts of polycaprolactone, 2 parts of polypropylene carbonate and polyhydroxyalkanoate series compounds.
Preferably, the feed consists of the following raw materials in percentage by weight: 30-50 parts of starch-based resin composition containing starch and acrylate graft polymer, 20-30 parts of completely biodegradable resin and 2-4 parts of plasticizer, wherein the starch is one or more of common corn starch, modified corn starch, tapioca starch and wheat starch.
Preferably, the plasticizer is composed of polypropylene fibers, methyl cellulose, DM-200, PEO, a high-efficiency water reducing agent, calcium formate, a defoaming agent, brucite fibers, silica fume, waterproof powder, a surfactant, imported wear-resistant resin glue powder and the like, and the main materials of the plasticizer comprise common 425# portland cement, sulphoaluminate cement, graded quartz sand and national standard 160 g low-alkali grid cloth.
Preferably, the preparation method of the completely biodegradable composite material is characterized by comprising the following steps:
the method comprises the following steps: preparing enough starch, starch and acrylate graft copolymer and acrylate homopolymer for later use to prepare a starch-based resin composition of the starch and acrylate graft copolymer;
step two: firstly, adding polypropylene fiber, methyl cellulose, DM-200, PEO, a high-efficiency water reducing agent, calcium formate, a defoaming agent, brucite fiber, silica fume, waterproof powder, a surfactant and imported wear-resistant resin rubber powder into a high-speed stirring kettle, dehydrating for 20-30min at the temperature of 80-100 ℃, then adding a coupling agent, stirring for 10-20min, mixing uniformly, then extruding and forming the uniformly stirred mixture into granules through a double-screw extruder, and cooling after extruding into granules;
step three: placing the prepared starch-based resin composition in a dryer below 50 ℃ for dehydration for 20-30min, then adjusting the temperature to 80-100 ℃ and drying for 10-15min to keep the water content in the starch-based resin composition at about 10%;
step four: mixing 30-50 parts by weight of starch-based resin composition, 2-4 parts by weight of plasticizer and 20-30 parts by weight of completely biodegradable resin, uniformly stirring, extruding into granules, and cooling.
Preferably, the starch-based resin composition containing the starch and acrylate graft polymer in the first step is prepared from the following raw materials, by weight, 50-80 parts of starch, 30-50 parts of starch and acrylate graft copolymer and 10-30 parts of acrylate homopolymer.
Preferably, a filter screen is arranged at the bottom of the inner cavity of the reaction kettle in the second step, after stirring for 10-20min, the uniformly stirred mixture flows out of the filter screen, and the mixture which is not uniformly stirred is continuously left in the stirring kettle for stirring, so that the prepared starch-based resin composition has better quality, gas can be generated in the stirring kettle, and only a steam recovery pipe is arranged at the top of the stirring kettle and is connected with a waste gas recovery processing device.
Preferably, in the third step, when the starch-based resin composition is dehydrated, the extruded starch-based resin composition particles are laid in a loading tray to ensure that the starch-based resin composition is not stacked together, and then the loading tray is placed in a drying oven, and during the drying and dehydration, the content of the starch-based resin composition needs to be tested until the moisture in the starch-based resin composition is kept at about 10%.
Compared with the prior art, the invention has the beneficial effects that:
1. the completely biodegradable composite material consists of starch 50-80 weight portions, starch and acrylate grafted copolymer 30-50 weight portions, and acrylate homopolymer 10-30 weight portions, and through mixing in a stirring kettle, mixing in a stirrer for 10-20min, filtering in the bottom of the inner cavity of the reactor, and stirring for 10-20min to obtain homogeneous mixture flowing out from the filtering net while stirring.
2. The biodegradable composite material prepared by the preparation method of the formula machine can improve the degradation speed and has better degradation performance, and objects which are difficult to degrade, such as packaging materials, convenient bags and the like, can be completely degraded, so that the white pollution to the environment is reduced, the environment quality is improved, and the composite material can be safely and effectively popularized in a large range in a long term.
Drawings
FIG. 1 is a flow chart of the preparation of the completely biodegradable composite material of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, the present invention provides a technical solution: a completely biodegradable composite material comprises polylactic acid, including one or a mixture of more of 10 parts of polylactic acid, 6 parts of polybutylene succinate, 3 parts of polybutylene terephthalate-adipate, 1 part of polybutylene succinate-co-terephthalate, 3 parts of polybutylene succinate-adipate, 12 parts of polycaprolactone, 2 parts of polypropylene carbonate and polyhydroxyalkanoate series compounds.
Further, the completely biodegradable composite material is composed of the following raw materials in parts by weight: 30-50 parts of starch-based resin composition containing starch and acrylate graft polymer, 20-30 parts of completely biodegradable resin and 2-4 parts of plasticizer, wherein the starch is one or more of common corn starch, modified corn starch, tapioca starch and wheat starch.
Further, the plasticizer comprises polypropylene fiber, methyl cellulose, DM-200, PEO, a high-efficiency water reducing agent, calcium formate, a defoaming agent, brucite fiber, silica fume, waterproof powder, a surfactant, imported wear-resistant resin glue powder and the like, and the main materials of the plasticizer comprise common 425# portland cement, sulphoaluminate cement, graded quartz sand and national standard 160 g low-alkali grid cloth.
Further, the preparation method of the completely biodegradable composite material is characterized by comprising the following steps:
the method comprises the following steps: preparing enough starch, starch and acrylate graft copolymer and acrylate homopolymer for later use to prepare a starch-based resin composition of the starch and acrylate graft copolymer;
step two: firstly, adding polypropylene fiber, methyl cellulose, DM-200, PEO, a high-efficiency water reducing agent, calcium formate, a defoaming agent, brucite fiber, silica fume, waterproof powder, a surfactant and imported wear-resistant resin rubber powder into a high-speed stirring kettle, dehydrating for 20-30min at the temperature of 80-100 ℃, then adding a coupling agent, stirring for 10-20min, mixing uniformly, then extruding and forming the uniformly stirred mixture into granules through a double-screw extruder, and cooling after extruding into granules;
step three: placing the prepared starch-based resin composition in a dryer below 50 ℃ for dehydration for 20-30min, then adjusting the temperature to 80-100 ℃ and drying for 10-15min to keep the water content in the starch-based resin composition at about 10%;
step four: mixing 30-50 parts by weight of starch-based resin composition, 2-4 parts by weight of plasticizer and 20-30 parts by weight of completely biodegradable resin, uniformly stirring, extruding into granules, and cooling.
Further, the starch-based resin composition containing the starch and acrylate graft polymer in the step one comprises the following raw materials in parts by weight, 50-80 parts of starch, 30-50 parts of starch and acrylate graft copolymer and 10-30 parts of acrylate homopolymer.
Furthermore, a filter screen is arranged at the bottom of the inner cavity of the reaction kettle in the second step, after stirring for 10-20min, the uniformly stirred mixture flows out of the filter screen, and the mixture is continuously left in the stirring kettle to be stirred if the mixture is not uniformly stirred, so that the prepared starch-based resin composition has better quality, gas can be generated in the stirring kettle, and only a steam recovery pipe is arranged at the top of the stirring kettle and is connected with a waste gas recovery processing device.
Further, in the third step, when the starch-based resin composition is dehydrated, the extruded starch-based resin composition particles are flatly laid in a loading tray to ensure that the starch-based resin composition is not stacked together, and then the loading tray is placed in a drying oven, and during the drying and dehydration, the content of the starch-based resin composition needs to be tested until the moisture in the starch-based resin composition is kept at about 10%.
The working principle is as follows: preparing enough weight of starch, starch and acrylate graft copolymer and acrylate homopolymer for later use, preparing a starch-based resin composition of the starch and acrylate graft polymer, adding polypropylene fiber, methyl cellulose, DM-200, PEO, a high efficiency water reducing agent, calcium formate, a defoaming agent, brucite fiber, silica fume, waterproof powder, a surfactant and inlet wear-resistant resin rubber powder into a high-speed stirring kettle, dehydrating at the temperature of 80-100 ℃ for 20-30min, adding a coupling agent, stirring for 10-20min, mixing uniformly, extruding and forming the uniformly stirred mixture by a double-screw extruder, extruding and extruding into granules, cooling, arranging a filter screen at the bottom of an inner cavity of the reaction kettle, stirring for 10-20min, and allowing the uniformly stirred mixture to flow out of the filter screen, the starch-based resin composition which is not stirred uniformly is kept in the stirring kettle for stirring, so that the quality of the prepared starch-based resin composition is better, and gas is generated in the process of the stirring kettle, only a steam recovery pipe is arranged at the top of the stirring kettle and is connected with a waste gas recovery processing device, so that the waste gas is prevented from being directly discharged to cause harm to the environment and human bodies, step three, the prepared starch-based resin composition is placed in a dryer below 50 ℃ for dehydration for 20-30min, and fourthly, adjusting the temperature to 80-100 ℃, drying for 10-15min to keep the water content inside the starch-based resin composition to be about 10%, mixing and stirring 30-50 parts by weight of the starch-based resin composition, 2-4 parts by weight of plasticizer and 20-30 parts by weight of completely biodegradable resin uniformly, extruding into granules, and cooling.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (7)

1. A completely biodegradable composite material is characterized by comprising one or a mixture of more of 10 parts of polylactic acid, 6 parts of polybutylene succinate, 3 parts of polybutylene terephthalate-adipate, 1 part of polybutylene succinate-co-terephthalate, 3 parts of polybutylene succinate-adipate, 12 parts of polycaprolactone, 2 parts of polypropylene carbonate and a polyhydroxyalkanoic acid series compound.
2. The completely biodegradable composite material is characterized by comprising the following raw materials in percentage by weight: 30-50 parts of starch-based resin composition containing starch and acrylate graft polymer, 20-30 parts of completely biodegradable resin and 2-4 parts of plasticizer, wherein the starch is one or more of common corn starch, modified corn starch, tapioca starch and wheat starch.
3. A completely biodegradable composite material according to claim 2, characterized in that: the plasticizer comprises polypropylene fibers, methyl cellulose, DM-200, PEO, a high-efficiency water reducing agent, calcium formate, a defoaming agent, brucite fibers, silica fume, waterproof powder, a surfactant, imported wear-resistant resin glue powder and the like, and the main materials of the plasticizer comprise ordinary 425# silicate cement, sulphoaluminate cement, graded quartz sand and national standard 160 g low-alkali mesh cloth.
4. A preparation method of a completely biodegradable composite material is characterized by comprising the following steps:
the method comprises the following steps: preparing enough starch, starch and acrylate graft copolymer and acrylate homopolymer for later use to prepare a starch-based resin composition of the starch and acrylate graft copolymer;
step two: firstly, adding polypropylene fiber, methyl cellulose, DM-200, PEO, a high-efficiency water reducing agent, calcium formate, a defoaming agent, brucite fiber, silica fume, waterproof powder, a surfactant and imported wear-resistant resin rubber powder into a high-speed stirring kettle, dehydrating for 20-30min at the temperature of 80-100 ℃, then adding a coupling agent, stirring for 10-20min, mixing uniformly, then extruding and forming the uniformly stirred mixture into granules through a double-screw extruder, and cooling after extruding into granules;
step three: placing the prepared starch-based resin composition in a dryer below 50 ℃ for dehydration for 20-30min, then adjusting the temperature to 80-100 ℃ and drying for 10-15min to keep the water content in the starch-based resin composition at about 10%;
step four: mixing 30-50 parts by weight of starch-based resin composition, 2-4 parts by weight of plasticizer and 20-30 parts by weight of completely biodegradable resin, uniformly stirring, extruding into granules, and cooling.
5. The method for preparing a completely biodegradable composite material as claimed in claim 4, wherein the starch-based resin composition containing starch and acrylate graft polymer in the first step is prepared from the raw materials of, by weight, 50-80 parts of starch, 30-50 parts of starch and acrylate graft copolymer, and 10-30 parts of acrylate homopolymer.
6. The method for preparing a completely biodegradable composite material as claimed in claim 5, wherein in the second step, a filter screen is disposed at the bottom of the inner cavity of the reaction kettle, after 10-20min of stirring, the uniformly stirred mixture flows out of the filter screen, and the mixture is continuously stirred in the stirring kettle without being uniformly stirred, so that the prepared starch-based resin composition has better quality, and gas is generated in the stirring kettle, and only a steam recovery pipe is disposed at the top of the stirring kettle and connected to a waste gas recovery processing device.
7. The method for preparing a fully biodegradable composite material as claimed in claim 6, wherein in the third step, the extruded starch-based resin composition particles are spread on a carrier plate during the dehydration of the starch-based resin composition, so as to ensure that the starch-based resin composition is not piled up, and then the carrier plate is placed in a drying oven, and during the drying and dehydration, the content of the starch-based resin composition is tested until the moisture content in the starch-based resin composition is kept at about 10%.
CN202011478680.XA 2020-12-15 2020-12-15 Completely biodegradable composite material and preparation method thereof Pending CN114634689A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115059456A (en) * 2022-07-26 2022-09-16 河南省科学院同位素研究所有限责任公司 Degradable radioactive isotope tracer and preparation method thereof
CN116515174A (en) * 2023-04-13 2023-08-01 西达(无锡)生物科技有限公司 Starch-based degradable composite material and preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115059456A (en) * 2022-07-26 2022-09-16 河南省科学院同位素研究所有限责任公司 Degradable radioactive isotope tracer and preparation method thereof
CN115059456B (en) * 2022-07-26 2024-02-13 河南省科学院同位素研究所有限责任公司 Degradable radioisotope tracer and preparation method thereof
CN116515174A (en) * 2023-04-13 2023-08-01 西达(无锡)生物科技有限公司 Starch-based degradable composite material and preparation method and application thereof
CN116515174B (en) * 2023-04-13 2024-05-24 西达(无锡)生物科技有限公司 Starch-based degradable composite material and preparation method and application thereof

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