CN110218424A - Straw powder/PLA/PBAT biomass full degradable plastics and preparation method - Google Patents
Straw powder/PLA/PBAT biomass full degradable plastics and preparation method Download PDFInfo
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- CN110218424A CN110218424A CN201910485627.3A CN201910485627A CN110218424A CN 110218424 A CN110218424 A CN 110218424A CN 201910485627 A CN201910485627 A CN 201910485627A CN 110218424 A CN110218424 A CN 110218424A
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a kind of straw powder/PLA/PBAT biomass full degradable plastics and preparation methods, straw powder/PLA/PBAT biomass full degradable plastics comprise the following components in parts by weight component: 15-30 parts of straw powder, PLA35-50 parts, PBAT35-50 parts, 2-4 parts of plasticizer, 1-3 parts of coupling agent, 1-3 parts of chain extender, 1-3 parts of lubricant, 1-3 parts of heat stabilizer, 0.1-0.3 parts of antioxidant.Straw powder provided by the invention/PLA/PBAT biomass full degradable plastics is mixed to get the better material of comprehensive performance by PLA, PBAT and straw powder, and the addition of straw powder reduces cost of manufacture, provides more selections for the application and development of degradative plastics.
Description
Technical field
The present invention relates to technical field of polymer materials, complete more particularly, to a kind of straw powder/PLA/PBAT biomass
Degradative plastics and preparation method.
Background technique
Environmental protection is increasingly concerned as a global problem.And plastics as one every field all
The material being widely used, yield is very big, and most plastics are difficult to decompose in the natural environment because of its stable structure,
The a large amount of waste plastic of long-term accumulated causes serious pollution to environment, so people study degradation plastic
And exploitation.
Complete degradable plastic refers to, can be degraded, decompose under enzyme or chemical breakdown effect by microorganism or its secretion
At H2O, CO2, CH4 or the material of the polymer of some small-molecular-weights, the last only remaining product nontoxic to environment.And biology drop
Material is solved mostly using renewable resource as raw material, such as rice husk, corn, starch etc..Therefore biological plastics is wide in environmental protection
General concern.
Polybutylene terephthalate-adipic acid butanediol copolyester PBAT is a kind of biodegradable fragrant adoption
Ester, intensity is lower and elongation at break is very high, is the fabulous elastomeric material of the fabulous elastomeric material toughness of flexibility.But
Its price is 2-3 times of common plastics, and thermal stability and mechanical performance existing defects, limits its application.
Polylactic acid (PLA) is the fermented manufactured lactic acid by being raw material containing biological materials such as sugar, starch, celluloses,
The biodegradation material that polylactic acid high molecular material is made is closed by lactic acid.It is with good biocompatibility, the transparency and machine
Tool intensity but elongation at break is very low, brittleness is very big, limits its application.It is with the comprehensive performance that the mode of blending improves material
A kind of common method, but PBAT and PLA are two kinds of incompatible systems, so needing to improve the compatibility of PBAT and PLA.
Biomass refers in any reproducible or recyclable organic substance, animals and plants, microorganism and by their institutes
The organic matter of generation is all to belong to biomass, such as rice husk, rice husk, shell etc..China is a large agricultural country, is about generated every year
1200000000 tons of agriculture and forestry organic waste material, have a large amount of waste not to rationally utilize, so the exploitation of biomass-based material can
To promote the reasonable employment of agriculture and forestry organic waste material.But cellulose, hemicellulose and lignin due to biomass etc. is containing a large amount of
Polarity alcoholic extract hydroxyl group and phenolic hydroxyl group functional group, make it have very strong chemical polarity, incompatible with hydrophobic plastic basis material.
Summary of the invention
On the one hand, the present invention provides a kind of straw powder/PLA/PBAT biomass full degradable plastics, which is characterized in that packet
Include the component of following parts by weight:
Wherein, the mesh number of the straw powder is 600-800 mesh, and successively to pass through basic hydrolysis, sulfuric acid molten for the straw powder
Swollen and ultrasonication processing step, comprising:
The sodium hydroxide solution that mass fraction is 6% will be added in the straw powder of the 600-800 mesh to be hydrolyzed, hydrolyze
170-180 DEG C of temperature, 15-25min is hydrolyzed, neutrality is washed with distilled water to after hydrolysis, obtains hydrolyzing straw powder after dry；
It is the dense of 70-74% that the hydrolyzing straw powder is added while stirring to mass fraction under conditions of 38 DEG C again
Sulfuric acid carries out swelling treatment, is filtered and is washed to neutrality again after processing, and swelling straw powder is obtained；
Finally the swelling straw powder deionized water is dispersed, is ultrasonically treated 40min, ultrasonic power 1000-1100w,
Ice-water bath is used in ultrasonic procedure, is carried out high speed centrifugation processing after ultrasonic treatment, is gone supernatant to obtain white precipitate, the white precipitate
For the pretreated straw powder in the straw powder/PLA/PBAT biomass full degradable plastics；
The heat stabilizer is epoxidized soybean oil, and the epoxidized soybean oil is using genetically engineered soybean oil as made from raw material
Epoxidized soybean oil.
Optionally, the production method of the epoxidized soybean oil the following steps are included: be added soybean oil, load in a kettle
Type heteropolyacid salt catalyst and formic acid are heated to 70-80 DEG C, are under stiring equably added in hydrogen peroxide in 40min
In reaction kettle, logical cold water is cooling when temperature increases, and insulation reaction 10-11h filters after reaction, filters carried heteropoly acid
Salt catalyst, static layering, oil are mutually neutralized with the saturated sodium-chloride water solution of 2-3% sodium hydroxide to pH value 8.5, then with pure
Neutrality is washed in water purification, and not chloride ion-containing position, after static 30min, separates lower water layer, the crude product after washing is put into
In distillation still, vacuum distillation dehydration obtains epoxidized soybean oil.
Optionally, the carried heteropoly acid salt catalyst heteropolyacid anions are the heteropolymolybdate of structure with Keggin,
Hetero atom is P or As, and counter cation is H or Cs, the carrier of load be dealuminzation USY molecular sieve, MCM-41 molecular sieve or from
Sub-exchange resin.
Optionally, the coupling agent is silane coupling agent KH560, and the chain extender is BASF chain extender ADR, the profit
Lubrication prescription is stearic acid；The plasticizer is acetyl tri-n-butyl citrate ATBC；The antioxidant is BASF antioxidant
1010。
On the other hand, above-mentioned straw powder/PLA/PBAT biomass full degradable plastics side is prepared the present invention provides a kind of
Method, comprising steps of
Straw powder is pre-processed, the mesh number of the straw powder is 600-800 mesh, and the straw powder successively passes through alkali
Property hydrolysis, sulfuric acid swelling and ultrasonication processing step, comprising:
The sodium hydroxide solution that mass fraction is 6% will be added in the straw powder of the 600-800 mesh to be hydrolyzed, hydrolyze
170-180 DEG C of temperature, 15-25min is hydrolyzed, neutrality is washed with distilled water to after hydrolysis, obtains hydrolyzing straw powder after dry；
It is the dense of 70-74% that the hydrolyzing straw powder is added while stirring to mass fraction under conditions of 38 DEG C again
Sulfuric acid carries out swelling treatment, is filtered and is washed to neutrality again after processing, and swelling straw powder is obtained；
Finally the swelling straw powder deionized water is dispersed, is ultrasonically treated 40min, ultrasonic power 1000-1100w,
Ice-water bath is used in ultrasonic procedure, is carried out high speed centrifugation processing after ultrasonic treatment, is gone supernatant to obtain white precipitate, the white precipitate
For the pretreated straw powder in the straw powder/PLA/PBAT biomass full degradable plastics；
The pretreated straw powder is dried, a part of coupling agent and ethyl alcohol are made into the solution that volume ratio is 1:5,
Microwave drying is then used through high mixer mixed at high speed 10-15min, frequency 50Hz with the pretreated straw powder of the drying again
Equipment is dried, and 80-90 DEG C of drying temperature；
Again by the coupling agent of surplus and ethyl alcohol be made into volume ratio be the solution of 1:5, the PLA, PBAT of raw material part, plasticizer,
High-speed mixer and mixing is added in chain extender, lubricant, heat stabilizer and antioxidant, is mixed to get with the pretreated straw powder
Mixture；
The mixture is used into double screw extruder extruding pelletization.
Optionally, by the mixture use double screw extruder extruding pelletization, comprising: extrusion temperature at 140-160 DEG C,
Engine speed is 130rad/min, and feeding frequency is 1-2Hz, pelletizing unit frequency 10-12Hz.
Compared with prior art, straw powder provided by the invention/PLA/PBAT biomass full degradable plastics and preparation method,
At least realize it is following the utility model has the advantages that
Straw powder provided by the invention/PLA/PBAT biomass full degradable plastics passes through the mixed of PLA, PBAT and straw powder
Conjunction obtains the better material of comprehensive performance, and the addition of straw powder reduces cost of manufacture, provides for the application and development of degradative plastics
More selections；
Using straw powder, PLA, PBAT as major ingredient in the present invention, plasticizer, coupling agent, chain extender, lubricant, heat is surely
Determine agent, antioxidant has high tensile strength, elongation at break height, heat steady as biomass-based complete degradable plastic made from auxiliary material
Qualitative good complete degradable plastic；
Epoxidized soybean oil in the present invention is made using genetically engineered soybean oil as raw material, and genetically engineered soybean oil belongs to renewable
The energy, flash-point is high, smoke point is high, and epoxidized soybean oil obtained is compared with the epoxidized soybean oil thermal stability that Non-transgenic soybean oil obtains
It is high；
Straw powder mesh number in the present invention is 600-800 mesh, and by basic hydrolysis, sulfuric acid swelling and ultrasonication
Processing step, so straw powder obtained/PLA/PBAT biomass full degradable plastic tensile intensity significantly improves；
First by a part of coupling agent and second in straw powder of the invention/PLA/PBAT biomass full degradable plastics preparation method
After the mixed liquor mixed at high speed that alcohol is made into, then mixed solution, raw material part that the coupling agent of surplus and ethyl alcohol are made into PLA,
High-speed mixer and mixing is added in PBAT, plasticizer, chain extender, lubricant, heat stabilizer and antioxidant, due to first with a part
Coupling agent is coupled cellulose, the lignin in pretreated straw powder, then adds and be again made into the coupling agent of surplus with ethyl alcohol
Mixed solution, raw material part PLA, PBAT, plasticizer, chain extender, lubricant, heat stabilizer and antioxidant, by straw powder
It is coupled with PLA and PBAT, obtained biomass-based complete degradable plastic tensile strength significantly improves, and elongation at break also compares
It is high.
Certainly, implementing any of the products of the present invention specific needs while must not reach all the above technical effect.
By referring to the drawings to the detailed description of exemplary embodiment of the present invention, other feature of the invention and its
Advantage will become apparent.
Detailed description of the invention
It is combined in the description and the attached drawing for constituting part of specification shows the embodiment of the present invention, and even
With its explanation together principle for explaining the present invention.
Fig. 1 is straw powder in embodiment 1/PLA/PBAT biomass full degradable plastics preparation method flow chart.
Specific embodiment
Carry out the various exemplary embodiments of detailed description of the present invention now with reference to attached drawing.It should also be noted that unless in addition having
Body explanation, the unlimited system of component and the positioned opposite of step, numerical expression and the numerical value otherwise illustrated in these embodiments is originally
The range of invention.
Be to the description only actually of at least one exemplary embodiment below it is illustrative, never as to the present invention
And its application or any restrictions used.
Technology, method and apparatus known to person of ordinary skill in the relevant may be not discussed in detail, but suitable
In the case of, the technology, method and apparatus should be considered as part of specification.
It is shown here and discuss all examples in, any occurrence should be construed as merely illustratively, without
It is as limitation.Therefore, other examples of exemplary embodiment can have different values.
It should also be noted that similar label and letter indicate similar terms in following attached drawing, therefore, once a certain Xiang Yi
It is defined in a attached drawing, then in subsequent attached drawing does not need that it is further discussed.
Embodiment 1:
Present embodiments provide a kind of straw powder/PLA/PBAT biomass full degradable plastics, the group including following parts by weight
Point:
The coupling agent is silane coupling agent KH560, and the chain extender is BASF chain extender ADR, and the lubricant is
Stearic acid；The plasticizer is acetyl tri-n-butyl citrate ATBC；The antioxidant is BASF antioxidant 1010.
Using straw powder, PLA, PBAT as major ingredient in the present invention, plasticizer, coupling agent, chain extender, lubricant, heat is surely
Determine agent, antioxidant has high tensile strength, elongation at break height, heat steady as biomass-based complete degradable plastic made from auxiliary material
Qualitative good complete degradable plastic.
The mesh number of the straw powder is 800 mesh, and the straw powder successively passes through basic hydrolysis, sulfuric acid swelling and ultrasound
The processing step of broken wall, comprising:
The sodium hydroxide solution that mass fraction is 6% will be added in the straw powder of 800 mesh to be hydrolyzed, hydrolysis temperature
180 DEG C, 25min is hydrolyzed, neutrality is washed with distilled water to after hydrolysis, obtains hydrolyzing straw powder after dry；
The hydrolyzing straw powder is added while stirring to the dense sulphur that mass fraction is 74% under conditions of 38 DEG C again
Acid carries out swelling treatment, is filtered and is washed to neutrality again after processing, and swelling straw powder is obtained；
Finally the swelling straw powder deionized water is dispersed, is ultrasonically treated 40min, ultrasonic power 1100w, ultrasonic mistake
Cheng Zhongyong ice-water bath carries out high speed centrifugation processing after ultrasonic treatment, goes supernatant to obtain white precipitate, which is described
Pretreated straw powder in straw powder/PLA/PBAT biomass full degradable plastics.
Straw powder mesh number in the present invention is 600-800 mesh, and by basic hydrolysis, sulfuric acid swelling and ultrasonication
Processing step, so straw powder obtained/PLA/PBAT biomass full degradable plastic tensile intensity significantly improves.
The heat stabilizer is epoxidized soybean oil, and the epoxidized soybean oil is using genetically engineered soybean oil as made from raw material
Epoxidized soybean oil.
Epoxidized soybean oil in the present invention is made using genetically engineered soybean oil as raw material, and genetically engineered soybean oil belongs to renewable
The energy, flash-point is high, smoke point is high, and epoxidized soybean oil obtained is compared with the epoxidized soybean oil thermal stability that Non-transgenic soybean oil obtains
It is high
The production method of the epoxidized soybean oil is the following steps are included: addition soybean oil, support type are miscellaneous more in a kettle
Phosphate catalyst and formic acid are heated to 80 DEG C, under stiring equably add hydrogen peroxide in 40min in a kettle,
Logical cold water is cooling when temperature increases, and insulation reaction 11h is filtered after reaction, filters carried heteropoly acid salt catalyst, static
The saturated sodium-chloride water solution of layering, oil 3% sodium hydroxide of phase is neutralized to pH value 8.5, then with pure washing to neutrality, and
And not chloride ion-containing position, after static 30min, lower water layer is separated, the crude product after washing is put into distillation still, decompression is steamed
Dehydration is evaporated, epoxidized soybean oil is obtained.
The carried heteropoly acid salt catalyst heteropolyacid anions are the heteropolymolybdate of structure with Keggin, and hetero atom is
P or As, counter cation are H or Cs, and the carrier of load is dealuminzation USY molecular sieve, MCM-41 molecular sieve or amberlite
Rouge.
The present invention uses carried heteropoly acid salt catalyst excellent catalytic effect, and high yield rate, the reaction time is shorter.
The present embodiment additionally provides a kind of side of above-mentioned straw powder/PLA/PBAT biomass full degradable plastics of production, including
Following steps:
Step S101: pre-processing 30 parts of straw powder of raw material part, and the mesh number of the straw powder is 800 mesh, and institute
State the processing step that straw powder successively passes through basic hydrolysis, sulfuric acid swelling and ultrasonication, comprising:
The sodium hydroxide solution that mass fraction is 6% will be added in the straw powder of 800 mesh to be hydrolyzed, hydrolysis temperature
180 DEG C, 25min is hydrolyzed, neutrality is washed with distilled water to after hydrolysis, obtains hydrolyzing straw powder after dry；
The hydrolyzing straw powder is added while stirring to the dense sulphur that mass fraction is 74% under conditions of 38 DEG C again
Acid carries out swelling treatment, is filtered and is washed to neutrality again after processing, and swelling straw powder is obtained；
Finally the swelling straw powder deionized water is dispersed, is ultrasonically treated 40min, ultrasonic power 1100w, ultrasonic mistake
Cheng Zhongyong ice-water bath carries out high speed centrifugation processing after ultrasonic treatment, goes supernatant to obtain white precipitate, which is described
Pretreated straw powder in straw powder/PLA/PBAT biomass full degradable plastics；
Step S102: drying the pretreated straw powder, and it is 1 that 0.6 part of coupling agent and ethyl alcohol, which are made into volume ratio:
5 solution, then microwave is then used through high mixer mixed at high speed 15min, frequency 50Hz with the pretreated straw powder of the drying
Drying equipment is dried, and 80-90 DEG C of drying temperature；
Step S103: it is the solution of 1:5, raw material part that 2.4 parts of coupling agent of surplus and ethyl alcohol, which are made into volume ratio, again
High-speed mixer and mixing is added in PLA, PBAT, plasticizer, chain extender, lubricant, heat stabilizer and antioxidant, with the pre- place
Reason straw powder is mixed to get mixture；
Step S104: the mixture is used into double screw extruder extruding pelletization.
Wherein engine speed is 130rad/min in step S104, and feeding frequency is 2Hz, pelletizing unit frequency 12Hz, is squeezed out
Temperature is set as 150 DEG C, 150 DEG C, 150 DEG C, 155 DEG C, 160 DEG C, 160 DEG C, 155 DEG C, 150 DEG C, 150 DEG C, 150 DEG C.
First by a part of coupling agent and second in straw powder of the invention/PLA/PBAT biomass full degradable plastics preparation method
After the mixed liquor mixed at high speed that alcohol is made into, then mixed solution, raw material part that the coupling agent of surplus and ethyl alcohol are made into PLA,
High-speed mixer and mixing is added in PBAT, plasticizer, chain extender, lubricant, heat stabilizer and antioxidant, due to first with a part
Coupling agent is coupled cellulose, the lignin in pretreated straw powder, then adds and be again made into the coupling agent of surplus with ethyl alcohol
Mixed solution, raw material part PLA, PBAT, plasticizer, chain extender, lubricant, heat stabilizer and antioxidant, by straw powder
It is coupled with PLA and PBAT, obtained biomass-based complete degradable plastic tensile strength significantly improves, and elongation at break also compares
It is high.
The straw powder that the present embodiment obtains/PLA/PBAT biomass full degradable plastics are through detecting, tensile strength 28MPa,
Elongation at break is 285%, and half a year compost degradation rate reaches 99%.
Embodiment 2:
Present embodiments provide a kind of straw powder/PLA/PBAT biomass full degradable plastics, the group including following parts by weight
Point:
Wherein, the coupling agent is silane coupling agent KH560, and the chain extender is BASF chain extender ADR, the lubrication
Agent is stearic acid；The plasticizer is acetyl tri-n-butyl citrate ATBC；The antioxidant is BASF antioxidant
1010。
The mesh number of the straw powder is 700 mesh, and the straw powder successively passes through basic hydrolysis, sulfuric acid swelling and ultrasound
The processing step of broken wall, comprising:
The sodium hydroxide solution that mass fraction is 6% will be added in the straw powder of 700 mesh to be hydrolyzed, hydrolysis temperature
175 DEG C, 20min is hydrolyzed, neutrality is washed with distilled water to after hydrolysis, obtains hydrolyzing straw powder after dry；
The hydrolyzing straw powder is added while stirring to the dense sulphur that mass fraction is 72% under conditions of 38 DEG C again
Acid carries out swelling treatment, is filtered and is washed to neutrality again after processing, and swelling straw powder is obtained；
Finally the swelling straw powder deionized water is dispersed, is ultrasonically treated 40min, ultrasonic power 1050w, ultrasonic mistake
Cheng Zhongyong ice-water bath carries out high speed centrifugation processing after ultrasonic treatment, goes supernatant to obtain white precipitate, which is described
Pretreated straw powder in straw powder/PLA/PBAT biomass full degradable plastics；
The heat stabilizer is epoxidized soybean oil, and the epoxidized soybean oil is using genetically engineered soybean oil as made from raw material
Epoxidized soybean oil.
The production method of the epoxidized soybean oil is the following steps are included: addition soybean oil, support type are miscellaneous more in a kettle
Phosphate catalyst and formic acid are heated to 75 DEG C, under stiring equably add hydrogen peroxide in 40min in a kettle,
Logical cold water is cooling when temperature increases, and insulation reaction 11h is filtered after reaction, filters carried heteropoly acid salt catalyst, static
The saturated sodium-chloride water solution of layering, oil 3% sodium hydroxide of phase is neutralized to pH value 8.5, then with pure washing to neutrality, and
And not chloride ion-containing position, after static 30min, lower water layer is separated, the crude product after washing is put into distillation still, decompression is steamed
Dehydration is evaporated, epoxidized soybean oil is obtained.
The carried heteropoly acid salt catalyst heteropolyacid anions are the heteropolymolybdate of structure with Keggin, and hetero atom is
P or As, counter cation are H or Cs, and the carrier of load is dealuminzation USY molecular sieve, MCM-41 molecular sieve or amberlite
Rouge.
The present embodiment additionally provides a kind of side of above-mentioned straw powder/PLA/PBAT biomass full degradable plastics of production, including
Following steps:
Step S201: pre-processing straw powder, and the mesh number of the straw powder is 700 mesh, and the straw powder is successively
By the processing step of basic hydrolysis, sulfuric acid swelling and ultrasonication, comprising:
The sodium hydroxide solution that mass fraction is 6% will be added in the straw powder of 700 mesh to be hydrolyzed, hydrolysis temperature
175 DEG C, 20min is hydrolyzed, neutrality is washed with distilled water to after hydrolysis, obtains hydrolyzing straw powder after dry；
The hydrolyzing straw powder is added while stirring to the dense sulphur that mass fraction is 72% under conditions of 38 DEG C again
Acid carries out swelling treatment, is filtered and is washed to neutrality again after processing, and swelling straw powder is obtained；
Finally the swelling straw powder deionized water is dispersed, is ultrasonically treated 40min, ultrasonic power 1050w, ultrasonic mistake
Cheng Zhongyong ice-water bath carries out high speed centrifugation processing after ultrasonic treatment, goes supernatant to obtain white precipitate, which is described
Pretreated straw powder in straw powder/PLA/PBAT biomass full degradable plastics；
Step S202: drying the pretreated straw powder, and it is 1 that 0.5 part of coupling agent and ethyl alcohol, which are made into volume ratio:
5 solution, then microwave is then used through high mixer mixed at high speed 13min, frequency 50Hz with the pretreated straw powder of the drying
Drying equipment is dried, and 80-90 DEG C of drying temperature；
Step S203: again by 1.5 parts of coupling agent and ethyl alcohol be made into volume ratio be the solution of 1:5, raw material part PLA,
High-speed mixer and mixing is added in PBAT, plasticizer, chain extender, lubricant, heat stabilizer and antioxidant, with pretreated straw powder
It is mixed to get mixture；
Step S204: the mixture is used into double screw extruder extruding pelletization.
Wherein engine speed is 130rad/min in step S104, and feeding frequency is 1.5Hz, pelletizing unit frequency 11Hz, is squeezed
Temperature is set out are as follows: 150 DEG C, 150 DEG C, 150 DEG C, 155 DEG C, 160 DEG C, 160 DEG C, 155 DEG C, 150 DEG C, 150 DEG C, 150 DEG C.
The straw powder that the present embodiment obtains/PLA/PBAT biomass full degradable plastics are through detecting, tensile strength 19MPa,
Elongation at break is 264%, and half a year compost degradation rate reaches 98%.
Embodiment 3:
Present embodiments provide a kind of straw powder/PLA/PBAT biomass full degradable plastics, the group including following parts by weight
Point:
Wherein, the coupling agent is silane coupling agent KH560, and the chain extender is BASF chain extender ADR, the lubrication
Agent is stearic acid；The plasticizer is acetyl tri-n-butyl citrate ATBC；The antioxidant is BASF antioxidant
1010。
The mesh number of the straw powder is 600 mesh, and the straw powder successively passes through basic hydrolysis, sulfuric acid swelling and ultrasound
The processing step of broken wall, comprising:
The sodium hydroxide solution that mass fraction is 6% will be added in the straw powder of 600 mesh to be hydrolyzed, hydrolysis temperature
170 DEG C, 15min is hydrolyzed, neutrality is washed with distilled water to after hydrolysis, obtains hydrolyzing straw powder after dry；
The hydrolyzing straw powder is added while stirring to the dense sulphur that mass fraction is 70% under conditions of 38 DEG C again
Acid carries out swelling treatment, is filtered and is washed to neutrality again after processing, and swelling straw powder is obtained；
Finally the swelling straw powder deionized water is dispersed, is ultrasonically treated 40min, ultrasonic power 1000w, ultrasonic mistake
Cheng Zhongyong ice-water bath carries out high speed centrifugation processing after ultrasonic treatment, goes supernatant to obtain white precipitate, which is described
Pretreated straw powder in straw powder/PLA/PBAT biomass full degradable plastics；
The heat stabilizer is epoxidized soybean oil, and the epoxidized soybean oil is using genetically engineered soybean oil as made from raw material
Epoxidized soybean oil.
The production method of the epoxidized soybean oil is the following steps are included: addition soybean oil, support type are miscellaneous more in a kettle
Phosphate catalyst and formic acid are heated to 70 DEG C, under stiring equably add hydrogen peroxide in 40min in a kettle,
Logical cold water is cooling when temperature increases, and insulation reaction 10h is filtered after reaction, filters carried heteropoly acid salt catalyst, static
The saturated sodium-chloride water solution of layering, oil 2% sodium hydroxide of phase is neutralized to pH value 8.5, then with pure washing to neutrality, and
And not chloride ion-containing position, after static 30min, lower water layer is separated, the crude product after washing is put into distillation still, decompression is steamed
Dehydration is evaporated, epoxidized soybean oil is obtained.
The carried heteropoly acid salt catalyst heteropolyacid anions are the heteropolymolybdate of structure with Keggin, and hetero atom is
P or As, counter cation are H or Cs, and the carrier of load is dealuminzation USY molecular sieve, MCM-41 molecular sieve or amberlite
Rouge.
The present embodiment additionally provides a kind of side of above-mentioned straw powder/PLA/PBAT biomass full degradable plastics of production, including
Following steps:
Step S301: pre-processing straw powder, and the mesh number of the straw powder is 600 mesh, and the straw powder is successively
By the processing step of basic hydrolysis, sulfuric acid swelling and ultrasonication, comprising:
The sodium hydroxide solution that mass fraction is 6% will be added in the straw powder of 600 mesh to be hydrolyzed, hydrolysis temperature
170 DEG C, 15-25min is hydrolyzed, neutrality is washed with distilled water to after hydrolysis, obtains hydrolyzing straw powder after dry；
The hydrolyzing straw powder is added while stirring to the dense sulphur that mass fraction is 70% under conditions of 38 DEG C again
Acid carries out swelling treatment, is filtered and is washed to neutrality again after processing, and swelling straw powder is obtained；
Finally the swelling straw powder deionized water is dispersed, is ultrasonically treated 40min, ultrasonic power 1000w, ultrasonic mistake
Cheng Zhongyong ice-water bath carries out high speed centrifugation processing after ultrasonic treatment, goes supernatant to obtain white precipitate, which is described
Pretreated straw powder in straw powder/PLA/PBAT biomass full degradable plastics；
Step S302: drying the pretreated straw powder, and 0.3 part of coupling agent, which is made into volume ratio with ethyl alcohol, is
The solution of 1:5, then with the pretreated straw powder of the drying through high mixer mixed at high speed 10min, frequency 50Hz, then with micro-
Wave drying equipment is dried, and 80-90 DEG C of drying temperature；
Step S303: it is the solution of 1:5, the PLA, PBAT of raw material part, increasing that 0.7 coupling agent and ethyl alcohol, which are made into volume ratio, again
It moulds agent, chain extender, lubricant, heat stabilizer and antioxidant and high-speed mixer and mixing is added, mixed with the pretreated straw powder
Obtain mixture；
Step S304: the mixture is used into double screw extruder extruding pelletization.
Wherein engine speed is 130rad/min in step S104, and feeding frequency is 1Hz, pelletizing unit frequency 10Hz, is squeezed out
Temperature setting are as follows: 150 DEG C, 150 DEG C, 150 DEG C, 155 DEG C, 160 DEG C, 160 DEG C, 155 DEG C, 150 DEG C, 150 DEG C, 150 DEG C.
The straw powder that the present embodiment obtains/PLA/PBAT biomass full degradable plastics are through detecting, tensile strength 18MPa,
Elongation at break is 275%, and half a year compost degradation rate reaches 98%.
Embodiment 4:
Present embodiments provide a kind of straw powder/PLA/PBAT biomass full degradable plastics, the group including following parts by weight
Point:
Wherein, the coupling agent is silane coupling agent KH560, and the chain extender is BASF chain extender ADR, the lubrication
Agent is stearic acid；The plasticizer is acetyl tri-n-butyl citrate ATBC；The antioxidant is BASF antioxidant
1010。
The mesh number of the straw powder is 700 mesh, and the straw powder successively passes through basic hydrolysis, sulfuric acid swelling and ultrasound
The processing step of broken wall, comprising:
The sodium hydroxide solution that mass fraction is 6% will be added in the straw powder of 700 mesh to be hydrolyzed, hydrolysis temperature
175 DEG C, 20min is hydrolyzed, neutrality is washed with distilled water to after hydrolysis, obtains hydrolyzing straw powder after dry；
The hydrolyzing straw powder is added while stirring to the dense sulphur that mass fraction is 72% under conditions of 38 DEG C again
Acid carries out swelling treatment, is filtered and is washed to neutrality again after processing, and swelling straw powder is obtained；
Finally the swelling straw powder deionized water is dispersed, is ultrasonically treated 40min, ultrasonic power 1050w, ultrasonic mistake
Cheng Zhongyong ice-water bath carries out high speed centrifugation processing after ultrasonic treatment, goes supernatant to obtain white precipitate, which is described
Pretreated straw powder in straw powder/PLA/PBAT biomass full degradable plastics；
The heat stabilizer is epoxidized soybean oil, and the epoxidized soybean oil is using genetically engineered soybean oil as made from raw material
Epoxidized soybean oil.
The production method of the epoxidized soybean oil is the following steps are included: addition soybean oil, support type are miscellaneous more in a kettle
Phosphate catalyst and formic acid are heated to 75 DEG C, under stiring equably add hydrogen peroxide in 40min in a kettle,
Logical cold water is cooling when temperature increases, and insulation reaction 11h is filtered after reaction, filters carried heteropoly acid salt catalyst, static
The saturated sodium-chloride water solution of layering, oil 3% sodium hydroxide of phase is neutralized to pH value 8.5, then with pure washing to neutrality, and
And not chloride ion-containing position, after static 30min, lower water layer is separated, the crude product after washing is put into distillation still, decompression is steamed
Dehydration is evaporated, epoxidized soybean oil is obtained.
The carried heteropoly acid salt catalyst heteropolyacid anions are the heteropolymolybdate of structure with Keggin, and hetero atom is
P or As, counter cation are H or Cs, and the carrier of load is dealuminzation USY molecular sieve, MCM-41 molecular sieve or amberlite
Rouge.
The present embodiment additionally provides a kind of side of above-mentioned straw powder/PLA/PBAT biomass full degradable plastics of production, including
Following steps:
Step S401: pre-processing straw powder, and the mesh number of the straw powder is 700 mesh, and the straw powder is successively
By the processing step of basic hydrolysis, sulfuric acid swelling and ultrasonication, comprising:
The sodium hydroxide solution that mass fraction is 6% will be added in the straw powder of 700 mesh to be hydrolyzed, hydrolysis temperature
175 DEG C, 20min is hydrolyzed, neutrality is washed with distilled water to after hydrolysis, obtains hydrolyzing straw powder after dry；
The hydrolyzing straw powder is added while stirring to the dense sulphur that mass fraction is 72% under conditions of 38 DEG C again
Acid carries out swelling treatment, is filtered and is washed to neutrality again after processing, and swelling straw powder is obtained；
Finally the swelling straw powder deionized water is dispersed, is ultrasonically treated 40min, ultrasonic power 1050w, ultrasonic mistake
Cheng Zhongyong ice-water bath carries out high speed centrifugation processing after ultrasonic treatment, goes supernatant to obtain white precipitate, which is described
Pretreated straw powder in straw powder/PLA/PBAT biomass full degradable plastics；
Step S402: drying the pretreated straw powder, and 0.7 part of coupling agent, which is made into volume ratio with ethyl alcohol, is
The solution of 1:5, then with the pretreated straw powder of the drying through high mixer mixed at high speed 14min, frequency 50Hz, then with micro-
Wave drying equipment is dried, and 80-90 DEG C of drying temperature；
Step S403: again by 1.5 parts of coupling agent and ethyl alcohol be made into volume ratio be the solution of 1:5, raw material part PLA,
High-speed mixer and mixing is added in PBAT, plasticizer, chain extender, lubricant, heat stabilizer and antioxidant, with pretreated straw powder
It is mixed to get mixture；
Step S404: the mixture is used into double screw extruder extruding pelletization.
Wherein engine speed is 130rad/min in step S104, and feeding frequency is 1.5Hz, pelletizing unit frequency 11Hz, is squeezed
Temperature is set out are as follows: 150 DEG C, 150 DEG C, 150 DEG C, 155 DEG C, 160 DEG C, 160 DEG C, 155 DEG C, 150 DEG C, 150 DEG C, 150 DEG C.
The straw powder that the present embodiment obtains/PLA/PBAT biomass full degradable plastics are through detecting, tensile strength 27MPa,
Elongation at break is 294%, and half a year compost degradation rate reaches 99%.
Through the foregoing embodiment it is found that straw powder provided by the invention/PLA/PBAT biomass full degradable plastics and preparation
Method, at least realize it is following the utility model has the advantages that
Straw powder provided by the invention/PLA/PBAT biomass full degradable plastics passes through the mixed of PLA, PBAT and straw powder
Conjunction obtains the better material of comprehensive performance, and the addition of straw powder reduces cost of manufacture, provides for the application and development of degradative plastics
More selections；
Using straw powder, PLA, PBAT as major ingredient in the present invention, plasticizer, coupling agent, chain extender, lubricant, heat is surely
Determine agent, antioxidant has high tensile strength, elongation at break height, heat steady as biomass-based complete degradable plastic made from auxiliary material
Qualitative good complete degradable plastic；
Epoxidized soybean oil in the present invention is made using genetically engineered soybean oil as raw material, and genetically engineered soybean oil belongs to renewable
The energy, flash-point is high, smoke point is high, and epoxidized soybean oil obtained is compared with the epoxidized soybean oil thermal stability that Non-transgenic soybean oil obtains
It is high；
Straw powder mesh number in the present invention is 600-800 mesh, and by basic hydrolysis, sulfuric acid swelling and ultrasonication
Processing step, so straw powder obtained/PLA/PBAT biomass full degradable plastic tensile intensity significantly improves；
First by a part of coupling agent and second in straw powder of the invention/PLA/PBAT biomass full degradable plastics preparation method
After the mixed liquor mixed at high speed that alcohol is made into, then mixed solution, raw material part that the coupling agent of surplus and ethyl alcohol are made into PLA,
High-speed mixer and mixing is added in PBAT, plasticizer, chain extender, lubricant, heat stabilizer and antioxidant, due to first with a part
Coupling agent is coupled cellulose, the lignin in pretreated straw powder, then adds and be again made into the coupling agent of surplus with ethyl alcohol
Mixed solution, raw material part PLA, PBAT, plasticizer, chain extender, lubricant, heat stabilizer and antioxidant, by straw powder
It is coupled with PLA and PBAT, obtained biomass-based complete degradable plastic tensile strength significantly improves, and elongation at break also compares
It is high.
Although some specific embodiments of the invention are described in detail by example, the skill of this field
Art personnel it should be understood that example above merely to being illustrated, the range being not intended to be limiting of the invention.The skill of this field
Art personnel are it should be understood that can without departing from the scope and spirit of the present invention modify to above embodiments.This hair
Bright range is defined by the following claims.
Claims (6)
1. a kind of straw powder/PLA/PBAT biomass full degradable plastics, which is characterized in that comprise the following components in parts by weight:
Wherein, the mesh number of the straw powder be 600-800 mesh, and the straw powder successively pass through basic hydrolysis, sulfuric acid swelling and
The processing step of ultrasonication, comprising:
The sodium hydroxide solution that mass fraction is 6% will be added in the straw powder of the 600-800 mesh to be hydrolyzed, hydrolysis temperature
170-180 DEG C, 15-25min is hydrolyzed, neutrality is washed with distilled water to after hydrolysis, obtains hydrolyzing straw powder after dry；
The hydrolyzing straw powder is added while stirring to the concentrated sulfuric acid that mass fraction is 70-74% under conditions of 38 DEG C again
Swelling treatment is carried out, is filtered and is washed to neutrality again after processing, swelling straw powder is obtained；
Finally the swelling straw powder deionized water is dispersed, is ultrasonically treated 40min, ultrasonic power 1000-1100w, ultrasound
Ice-water bath is used in the process, is carried out high speed centrifugation processing after ultrasonic treatment, is gone supernatant to obtain white precipitate, which is institute
State the pretreated straw powder in straw powder/PLA/PBAT biomass full degradable plastics；
The heat stabilizer is epoxidized soybean oil, and the epoxidized soybean oil is using genetically engineered soybean oil as epoxy made from raw material
Soybean oil.
2. straw powder according to claim 1/PLA/PBAT biomass full degradable plastics, which is characterized in that the epoxy
The production method of soybean oil the following steps are included: soybean oil, carried heteropoly acid salt catalyst and formic acid are added in a kettle,
It is heated to 70-80 DEG C, is under stiring equably added hydrogen peroxide in a kettle in 40min, temperature increases Shi Tongleng
Water is cooling, and insulation reaction 10-11h is filtered after reaction, filters carried heteropoly acid salt catalyst, static layering, and oil is mutually used
The saturated sodium-chloride water solution of 2-3% sodium hydroxide is neutralized to pH value 8.5, then with pure washing to neutrality, and is free of chlorine
Ion position after static 30min, separates lower water layer, the crude product after washing is put into distillation still, vacuum distillation dehydration,
Obtain epoxidized soybean oil.
3. straw powder according to claim 2/PLA/PBAT biomass full degradable plastics, which is characterized in that the load
Type heteropolyacid salt catalyst heteropolyacid anions are the heteropolymolybdate of structure with Keggin, and hetero atom is P or As, counter cation
For H or Cs, the carrier of load is dealuminzation USY molecular sieve, MCM-41 molecular sieve or ion exchange resin.
4. straw powder according to claim 1/PLA/PBAT biomass full degradable plastics, which is characterized in that the coupling
Agent is silane coupling agent KH560, and the chain extender is BASF chain extender ADR, and the lubricant is stearic acid；The plasticizer
For acetyl tri-n-butyl citrate ATBC；The antioxidant is BASF antioxidant 1010.
5. a kind of prepare any straw powder/PLA/PBAT biomass full degradable plastics method of claim 1-4, spy
Sign is, comprising steps of
Straw powder is pre-processed, the mesh number of the straw powder is 600-800 mesh, and the straw powder successively passes through alkaline water
Solution, the processing step of sulfuric acid swelling and ultrasonication, comprising:
The sodium hydroxide solution that mass fraction is 6% will be added in the straw powder of the 600-800 mesh to be hydrolyzed, hydrolysis temperature
170-180 DEG C, 15-25min is hydrolyzed, neutrality is washed with distilled water to after hydrolysis, obtains hydrolyzing straw powder after dry；
The hydrolyzing straw powder is added while stirring to the concentrated sulfuric acid that mass fraction is 70-74% under conditions of 38 DEG C again
Swelling treatment is carried out, is filtered and is washed to neutrality again after processing, swelling straw powder is obtained；
Finally the swelling straw powder deionized water is dispersed, is ultrasonically treated 40min, ultrasonic power 1000-1100w, ultrasound
Ice-water bath is used in the process, is carried out high speed centrifugation processing after ultrasonic treatment, is gone supernatant to obtain white precipitate, which is institute
State the pretreated straw powder in straw powder/PLA/PBAT biomass full degradable plastics；
The pretreated straw powder is dried, a part of coupling agent and ethyl alcohol are made into volume ratio as the solution of 1:5, then with
Then the pretreated straw powder of the drying uses microwave dryer through high mixer mixed at high speed 10-15min, frequency 50Hz
It is dried, 80-90 DEG C of drying temperature；
It is the solution of 1:5, the PLA, PBAT of raw material part, plasticizer, chain extension that the coupling agent of surplus and ethyl alcohol, which are made into volume ratio, again
High-speed mixer and mixing is added in agent, lubricant, heat stabilizer and antioxidant, is mixed to get and mixes with the pretreated straw powder
Object；
The mixture is used into double screw extruder extruding pelletization.
6. according to the method described in claim 5, it is characterized in that, the mixture is made using double screw extruder extrusion
Grain, comprising: for extrusion temperature at 140-160 DEG C, engine speed 130rad/min, feeding frequency is 1-2Hz, pelletizing unit frequency
10-12Hz。
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112341766A (en) * | 2020-10-30 | 2021-02-09 | 辽宁幸福人科技有限公司 | Fully-degradable bio-based composite material product and preparation method thereof |
| CN112920567A (en) * | 2021-03-05 | 2021-06-08 | 柳州塑友科技有限公司 | Wheat straw filled modified PLA fully-degradable plastic and preparation method thereof |
| CN113150521A (en) * | 2021-05-08 | 2021-07-23 | 汕头市春叶新材料环保有限公司 | High-toughness biodegradable composite material, and preparation device and method thereof |
| CN113234305A (en) * | 2021-05-14 | 2021-08-10 | 河北凯力华维包装科技有限公司 | Degradable composite material and preparation method and application thereof |
| CN113831748A (en) * | 2021-09-26 | 2021-12-24 | 南京五瑞生物降解新材料研究院有限公司 | Biomass fully-degradable material and preparation process thereof |
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| CN114605359A (en) * | 2022-03-09 | 2022-06-10 | 苏州禾广吉智能装备有限公司 | Method for preparing FDCA (fully drawn yarn) and total bio-based filler by using non-grain biomass raw material |
| CN114933815A (en) * | 2022-05-17 | 2022-08-23 | 江苏中科睿赛污染控制工程有限公司 | Straw composite material master batch and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006213830A (en) * | 2005-02-04 | 2006-08-17 | Achilles Corp | Fumigation sheet having high gas barrier property against pine weevil |
| CN105001603A (en) * | 2014-11-25 | 2015-10-28 | 江苏天仁生物材料有限公司 | Fully biodegradable material with polylactic acid/polyterephthalic dibutyl adipate used as base materials and preparation method thereof |
| CN106336531A (en) * | 2016-09-12 | 2017-01-18 | 葛袁园 | Modified corn straw granule enhanced PBAT [poly(butyleneadipate-co-terephthalate)] starch composite material and preparation method thereof |
| CN108410145A (en) * | 2018-03-23 | 2018-08-17 | 河南省科学院同位素研究所有限责任公司 | The method for preparing stalk fibre/PBAT composite materials based on radiation modification |
| CN111574754A (en) * | 2020-06-13 | 2020-08-25 | 嘉善天惠服饰有限公司 | Basic formula of full-biodegradable button |
-
2019
- 2019-06-05 CN CN201910485627.3A patent/CN110218424A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006213830A (en) * | 2005-02-04 | 2006-08-17 | Achilles Corp | Fumigation sheet having high gas barrier property against pine weevil |
| CN105001603A (en) * | 2014-11-25 | 2015-10-28 | 江苏天仁生物材料有限公司 | Fully biodegradable material with polylactic acid/polyterephthalic dibutyl adipate used as base materials and preparation method thereof |
| CN106336531A (en) * | 2016-09-12 | 2017-01-18 | 葛袁园 | Modified corn straw granule enhanced PBAT [poly(butyleneadipate-co-terephthalate)] starch composite material and preparation method thereof |
| CN108410145A (en) * | 2018-03-23 | 2018-08-17 | 河南省科学院同位素研究所有限责任公司 | The method for preparing stalk fibre/PBAT composite materials based on radiation modification |
| CN111574754A (en) * | 2020-06-13 | 2020-08-25 | 嘉善天惠服饰有限公司 | Basic formula of full-biodegradable button |
Non-Patent Citations (3)
| Title |
|---|
| 姜俊青: "固体催化大豆油化学改性的研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 徐鼐: "《通用级聚乳酸的改性与加工成型》", 30 January 2016, 中国科学技术大学出版社 * |
| 韩丹妮: "稻壳预处理及稻壳中木聚糖的提取工艺研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (11)
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|---|---|---|---|---|
| CN112341766A (en) * | 2020-10-30 | 2021-02-09 | 辽宁幸福人科技有限公司 | Fully-degradable bio-based composite material product and preparation method thereof |
| CN112341766B (en) * | 2020-10-30 | 2023-08-25 | 辽宁幸福人科技有限公司 | Fully-degradable bio-based composite material product and preparation method thereof |
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| CN113150521B (en) * | 2021-05-08 | 2022-01-25 | 江西昕禾生态科技有限公司 | High-toughness biodegradable composite material, and preparation device and method thereof |
| CN113234305A (en) * | 2021-05-14 | 2021-08-10 | 河北凯力华维包装科技有限公司 | Degradable composite material and preparation method and application thereof |
| CN113831748A (en) * | 2021-09-26 | 2021-12-24 | 南京五瑞生物降解新材料研究院有限公司 | Biomass fully-degradable material and preparation process thereof |
| CN114479379A (en) * | 2022-02-14 | 2022-05-13 | 营口东盛实业有限公司 | Composite Chinese herbal medicine-based antibacterial fully-degradable plastic material and preparation method thereof |
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