CN105968756A - Preparation method of biodegradable polylactic acid-fiberous composite - Google Patents
Preparation method of biodegradable polylactic acid-fiberous composite Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to a preparation method of a biodegradable polylactic acid-fiberous composite, and belongs to the technical field of composite materials. The method comprises the steps that tobacco stems and tobacco waste ware subjected to the hydrolase effect to obtain an enzymatic hydrolysate, the enzymatic hydrolysate is heated, digested and subjected to enzyme deactivation, the enzymatic hydrolysate is fed into an ultra-filtration membrane to be filtered, and after spray drying is performed on an ultra-filtration condensation solution, treated tobacco fiber is obtained; the plant fiber and an inorganic acid solution are mixed, a hydrolysis reaction is performed, after the reaction is ended, residues, polyethylene glycol and water are mixed to be subjected to a reaction, and modified microcrystalline cellulose is obtained; polylactic acid, treated tobacco fiber, macropore konjak glucomannan hydrogel, modified microcrystalline cellulose, filler, a plasticizer, a cross-linking agent, a nucleating agent, a coupling agent, a compatibilizer, a lubricant and a surface active agent are mixed to be uniform and placed into an extruder for extrusion, and granulation is performed to obtain the biodegradable polylactic acid-fiberous composite. According to the polylactic acid degradable material, waste tobacco is used as the fiber filling material, and the biodegradable polylactic acid-fiberous composite has the advantages of being good in mechanical performance and high in degradation speed.
Description
Technical field
The present invention relates to the preparation method of a kind of biodegradable polylactic acid-fibrous composite, belong to composite
Technical field.
Background technology
Conventional plastic packaging use after, due to be not recycled or because be not easily recycled and by the most random
Being discarded in natural environment, environment is caused pollution, therefore Biodegradable material and packing articles thereof are increasingly becoming currently
The focus of research and development.If regulation one homogenous material is tested according to GB/T 19277.1 in China's standard GB/T/T 20197,
Its biological decomposition rate is Biodegradable material when 60%.Up to now, the biodegradable plastic kind of scale or pilot scale
Class has polylactic acid (PLA), PHA (PHA, including PHB, PHBV, P (3HB, 4HB) and PHBH etc.), poly-succinic fourth
Diester (PBS), p-phthalic acid adipic acid butanediol copolymer (PBAT), poly-succinic-adipic acid-fourth diester (PBSA), poly-
Propylene carbonate (PPC), polycaprolactone (PCL) etc..
Wherein, polylactic acid (PLA) is a kind of synthesis macromolecule with excellent biocompatibility and biodegradable
Material.PLA this linear thermoplastic biodegradable aliphatic polyester is to extract in some plants such as Semen Maydis, Semen Tritici aestivi, Maninot esculenta crantz.
Starch be initial raw material, decompose through enzyme and obtain glucose, then after lactic acid bacteria fermentation, become lactic acid, be then passed through chemistry
Synthesis obtains high-purity polylactic acid.Ester bond facile hydrolysis in polylactic acid, can degrade in vivo or in soil in effect through microorganism
Generating lactic acid, metabolic end-product is water and carbon dioxide, so human body will not be produced toxic and side effects, uses the safest.
Therefore polylactic acid is applied to many aspects such as medical science, pharmacy, as surgical sewing thread, drug controlled release system
System etc..
Open a kind of polylactic acid biodegradation material of CN104693427A and its preparation method and application.The steps include: 1)
Except water: use dephlegmator refluxed evaporator or use the method for azeotropic solvent dehydration to remove the moisture in lactic raw material；2) precondensation:
Use the lactic raw material that purity is higher, in the presence of a catalyst, carry out precondensation；3) condensation polymerization;In the presence of a catalyst,
Reduced vacuum polycondensation is carried out for raw material with the lactic acid polymer that precondensation technique obtains.CN104559101A discloses a kind of high-strength
High-ductility fully-degradable polylactic acid composite and preparation method thereof, its hot strength 52.0～60.4MPa, percentage elongation 57～210%,
Notch impact strength 4.2～8.3KJ/m2；Employing melt-blending process is prepared from.Preparing raw material by mass fraction is: polylactic acid
Resin 70～90 parts；Polycarbonate elastomer body 10-30 part；1 part of antioxidant；Graphene oxide is polylactic resin and Merlon
The 0.1～1% of elastomer gross mass；Each raw material is put in baking oven, at a temperature of 60～80 DEG C, is dried 4～6 hours, adds afterwards
Mixing is to uniformly in high speed mixer, then is added by mixed uniformly material in screw extruder, extrudes at 160～180 DEG C
Obtain.
If use completely polylactic acid as master package material, the problem that high cost can be caused, it is therefore desirable to provide
A kind of based on polylactic acid degradable, there are the composite degradation packaging material of lower cost simultaneously.As tobacco leaf production big country,
The annual yield of tobacco of China 450～5,000,000 t, the leftover bits and pieces such as Nicotiana tabacum L., offal of wherein there are about nearly 25% goes out of use, it is impossible to be used for
Production of cigarettes, if Yunnan is as the big province of Nicotiana tabacum L., there are about 30%～35% and belongs to and cannot be carried out Cigarette processing in annual yield of flue-cured tobacco
Low grade or etc. outer level Nicotiana tabacum L., fail to obtain Appropriate application.
Summary of the invention
It is an object of the invention to: polylactic acid-fiber composite that a kind of good mechanical property, low cost, degradation speed are fast is provided
Material, wherein have employed waste and old Nicotiana tabacum L. as fiber-filled material.
Technical scheme is as follows:
The preparation method of a kind of biodegradable polylactic acid-fibrous composite, comprises the steps:
1st step, by weight, is ground into fine powder, addition to water 300～400 parts by cabo 10～20 parts, offal 30～40 parts
In, add β-Fructus Hordei Germinatus carbon hydrate hydrolytic enzyme 5～10 parts, amino peptidase 2～4 parts, 1,5-AF 4～8 parts,
Carry out enzyme digestion reaction at 45～50 DEG C, obtain enzymolysis solution；
2nd step, is heated to 70～80 DEG C of extractions enzyme denaturing to the enzymolysis solution of the 1st step gained, lixiviating solution is sent into ultrafilter membrane and carries out
Filter, obtain liquid is concentrated by ultrafiltration, after liquid spray drying will be concentrated by ultrafiltration, the tobacco leaf fiber after being processed；
3rd step, by weight, weighs konjaku powder 30～50 parts, is dissolved in distilled water 300～400 parts, is stirred into molten
Glue；Adding inorganic base aqueous solution to stir, making sol pH is 9～13；Heat up and react at 65～80 DEG C, cool down after terminating
Stand, then wash with distilled water immersion, gel is placed in freezing tank freezing, then room temperature is melted, after lyophilizing, obtain macropore evil spirit
Taro glucomannan hydrogel；
4th step, by weight, after Plant fiber 1～2 parts being pulverized, mix with inorganic acid solution 5～20 parts, heat 75～
Be hydrolyzed at 95 DEG C reaction, after reaction terminates, filters out residue, cleans residue use water to pH neutral, then by residue, poly-second
Glycol 0.2～0.4 part, water 5～8 parts of mix homogeneously, be warming up to 80～90 DEG C and react, and obtains white serosity, is spray-dried
After obtain modified microcrystalline cellulose；
5th step, by weight, take polylactic acid 60～90 parts, process after tobacco leaf fiber 10～20 parts, macropore konjak portuguese gansu polyose
Sucrose solution gel 10～20 parts, modified microcrystalline cellulose 4～10 parts, filler 15～20 parts, plasticizer 1～3 parts, cross-linking agent 1～3
Part, nucleator 1～3 parts, coupling agent 1～3 parts, bulking agent 1～3 parts, lubricant 1～3 parts, surfactant 1～3 parts of mixing are all
After even, putting in extruder, the screw rod rotary speed of extruder controls at 40～50 rpm, and extrusion temperature controls 170～195
DEG C, then carry out pelletize.
In 1st step, the granular size of fine powder is at 200 mesh～400 mesh.
In the 2nd described step, the component that retains of ultrafilter membrane is between 200000～400000da, the pressure limit of ultrafiltration
Being 0.1～0.5Mpa, the temperature of ultra-filtration process is 20～40 DEG C.
In the 3rd described step, the mixing of inorganic base one or two kinds of in sodium hydroxide or potassium hydroxide.
In the 4th described step, Plant fiber is selected from one or several in cotton fiber, the wood fiber, bamboo fibre, flaxen fiber
Mixture；Inorganic acid solution is hydrochloric acid, sulphuric acid or phosphoric acid solution, and acid concentration is 0.1～1.0mol/L.
Described polylactic acid is transparent extrusion grade or injection grade, and fusing point is 145～170 DEG C, and melt index is 2～30g/
10min。
Described nucleator is selected from amide-type organic nucleating agent, hydrazides class organic nucleating agent, terres rares nucleator
Kind.
Described coupling agent is selected from N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-(methacryloxypropyl)
Propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, r-chloropropyl trimethoxyl silane, ethyl front three
TMOS, one or more in isopropyl two (methylacryloyl) isostearoyl base titanate esters mix in any proportion
Thing.
Described lubricant is selected from stearic acid or liquid paraffin.
Described plasticizer can be one or several in ethylene glycol, propylene glycol, sorbitol or glycerol.
Described cross-linking agent can be the one in formaldehyde, paraformaldehyde, acetaldehyde, Metaldehyde or epoxychloropropane or
Person is several.
Described bulking agent is ethylene acrylic acid co polymer, ethylene ethyl acrylate, maleic anhydride grafted ethene acetic acid second
One in alkene copolymer.
Surfactant can use sodium lauryl sulphate, diethanolamine of fat acyl, fatty alcohol-polyoxyethylene ether sulphuric acid
One or more mixture in ammonium, polyoxyethylenated alcohol sodium sulfate.
Filler is selected from one or several in calcium carbonate, titanium oxide or magnesium carbonate.
Beneficial effect
The polylactic acid degradable material that the present invention prepares, have employed waste and old Nicotiana tabacum L. as fiber-filled material, has mechanicalness
The advantage that energy is good, low cost, degradation speed are fast.
Detailed description of the invention
Embodiment 1
1st step, by weight, is ground into 200 mesh～400 mesh fine powders by cabo 10 parts, offal 30 parts, adds to 300 parts of water
In, add β-Fructus Hordei Germinatus carbon hydrate hydrolytic enzyme 5 parts, amino peptidase 2 parts, 1,5-AF 4 parts, carry out at 45 DEG C
Enzyme digestion reaction, obtains enzymolysis solution；
2nd step, is heated to 70 DEG C of extractions enzyme denaturing to the enzymolysis solution of the 1st step gained, lixiviating solution is sent into ultrafilter membrane and filters,
The component that retains of ultrafilter membrane is at 200000da, and the pressure limit of ultrafiltration is 0.1Mpa, and the temperature of ultra-filtration process is 20 DEG C, obtains
Liquid is concentrated by ultrafiltration, after liquid spray drying will be concentrated by ultrafiltration, the tobacco leaf fiber after being processed；
3rd step, by weight, weighs konjaku powder 30 parts, is dissolved in distilled water 300 parts, is stirred into colloidal sol；Add
Sodium hydrate aqueous solution stirs, and making sol pH is 9；Heating up and react at 65 DEG C, after terminating, cooling stands, then with distillation
Water soaking washs, and gel is placed in freezing tank freezing, then room temperature is melted, and obtains macropore Rhizoma amorphophalli glucomannan water-setting after lyophilizing
Glue；
4th step, by weight, after being pulverized by bamboo fibre 1 part, mixes with 0.1mol/L hydrochloric acid solution 5 parts, enters at heating 75 DEG C
Row hydrolysis, after reaction terminates, filters out residue, cleans residue use water to pH neutral, then by residue, Polyethylene Glycol 0.2
Part, 5 parts of mix homogeneously of water, be warming up to 80 DEG C and react, and obtains white serosity, obtains modification of microcrystalline fiber after spray drying
Element；
5th step, by weight, (described polylactic acid is transparent extrusion grade or injection grade, and fusing point is 145 DEG C, molten to take polylactic acid
Melting index is 2g/10min) 60 parts, process after tobacco leaf fiber 10 parts, macropore glucomannan hydrogel of konnjaku 10 parts, modified micro-
Crystalline cellulose 4 parts, filler-calcium carbonate 15 parts, Plasticizers Propylene glycol 1 part, cross-linking agent paraformaldehyde 1 part, hydrazides class organic nucleating agent
1 part, γ-glycidyl ether oxygen propyl trimethoxy silicane coupling agent 1 part, bulking agent ethylene ethyl acrylate 1 part, lubricant hard
After fat acid 1 part, 1 part of mix homogeneously of Surfactant SDS, putting in extruder, the screw rod of extruder rotates speed
Degree controls at 40rpm, and extrusion temperature controls at 170 DEG C, then carries out pelletize.
Embodiment 2
1st step, by weight, is ground into 200 mesh～400 mesh fine powders by cabo 20 parts, offal 40 parts, adds to 400 parts of water
In, add β-Fructus Hordei Germinatus carbon hydrate hydrolase 10 part, amino peptidase 4 parts, 1,5-AF 8 parts, enter at 50 DEG C
Row enzyme digestion reaction, obtains enzymolysis solution；
2nd step, is heated to 80 DEG C of extractions enzyme denaturing to the enzymolysis solution of the 1st step gained, lixiviating solution is sent into ultrafilter membrane and filters,
The component that retains of ultrafilter membrane is 400000da, and the pressure limit of ultrafiltration is 0.5Mpa, and the temperature of ultra-filtration process is 40 DEG C, is surpassed
Filter concentration liquid, after liquid spray drying will be concentrated by ultrafiltration, the tobacco leaf fiber after being processed；
3rd step, by weight, weighs konjaku powder 50 parts, is dissolved in distilled water 400 parts, is stirred into colloidal sol；Add
Sodium hydrate aqueous solution stirs, and making sol pH is 13；Heating up and react at 80 DEG C, after terminating, cooling stands, then with steaming
Distilled water washing by soaking, is placed in freezing tank freezing by gel, then room temperature is melted, and obtains macropore Rhizoma amorphophalli glucomannan water-setting after lyophilizing
Glue；
4th step, by weight, after being pulverized by bamboo fibre 2 parts, mixes with 1.0mol/L hydrochloric acid solution 20 parts, at heating 95 DEG C
Be hydrolyzed reaction, after reaction terminates, filters out residue, cleans residue use water to pH neutral, then by residue, Polyethylene Glycol
0.4 part, 8 parts of mix homogeneously of water, be warming up to 90 DEG C and react, and obtains white serosity, obtains modification of microcrystalline fine after spray drying
Dimension element；
5th step, by weight, (described polylactic acid is transparent extrusion grade or injection grade, and fusing point is 170 DEG C, molten to take polylactic acid
Melting index is 30g/10min) 90 parts, process after tobacco leaf fiber 20 parts, macropore glucomannan hydrogel of konnjaku 20 parts, modified
Microcrystalline Cellulose 10 parts, filler-calcium carbonate 20 parts, Plasticizers Propylene glycol 3 parts, cross-linking agent paraformaldehyde 3 parts, the organic one-tenth of hydrazides class
Core agent 3 parts, γ-glycidyl ether oxygen propyl trimethoxy silicane coupling agent 3 parts, bulking agent ethylene ethyl acrylate 3 parts, lubrication
After agent stearic acid 3 parts, 3 parts of mix homogeneously of Surfactant SDS, put in extruder, the screw rod rotation of extruder
Rotary speed controls at 50 rpm, and extrusion temperature controls at 195 DEG C, then carries out pelletize.
Embodiment 3
1st step, by weight, is ground into 200 mesh～400 mesh fine powders by cabo 15 parts, offal 35 parts, adds to 350 parts of water
In, add β-Fructus Hordei Germinatus carbon hydrate hydrolytic enzyme 7 parts, amino peptidase 3 parts, 1,5-AF 5 parts, carry out at 48 DEG C
Enzyme digestion reaction, obtains enzymolysis solution；
2nd step, is heated to 75 DEG C of extractions enzyme denaturing to the enzymolysis solution of the 1st step gained, lixiviating solution is sent into ultrafilter membrane and filters,
The component that retains of ultrafilter membrane is 300000da, and the pressure limit of ultrafiltration is 0.3Mpa, and the temperature of ultra-filtration process is 30 DEG C, is surpassed
Filter concentration liquid, after liquid spray drying will be concentrated by ultrafiltration, the tobacco leaf fiber after being processed；
3rd step, by weight, weighs konjaku powder 40 parts, is dissolved in distilled water 350 parts, is stirred into colloidal sol；Add
Sodium hydrate aqueous solution stirs, and making sol pH is 11；Heating up and react at 70 DEG C, after terminating, cooling stands, then with steaming
Distilled water washing by soaking, is placed in freezing tank freezing by gel, then room temperature is melted, and obtains macropore Rhizoma amorphophalli glucomannan water-setting after lyophilizing
Glue；
4th step, by weight, after being pulverized by bamboo fibre 2 parts, mixes with 0.5mol/L hydrochloric acid solution 8 parts, enters at heating 80 DEG C
Row hydrolysis, after reaction terminates, filters out residue, cleans residue use water to pH neutral, then by residue, Polyethylene Glycol 0.3
Part, 7 parts of mix homogeneously of water, be warming up to 85 DEG C and react, and obtains white serosity, obtains modification of microcrystalline fiber after spray drying
Element；
5th step, by weight, (described polylactic acid is transparent extrusion grade or injection grade, and fusing point is 160 DEG C, molten to take polylactic acid
Melting index is 10g/10min) 80 parts, process after tobacco leaf fiber 15 parts, macropore glucomannan hydrogel of konnjaku 15 parts, modified
Microcrystalline Cellulose 5 parts, filler-calcium carbonate 18 parts, Plasticizers Propylene glycol 2 parts, cross-linking agent paraformaldehyde 2 parts, the organic nucleation of hydrazides class
Agent 2 parts, γ-glycidyl ether oxygen propyl trimethoxy silicane coupling agent 2 parts, bulking agent ethylene ethyl acrylate 2 parts, lubricant
After stearic acid 2 parts, 2 parts of mix homogeneously of Surfactant SDS, putting in extruder, the screw rod of extruder rotates
Speed controlling is at 45rpm, and extrusion temperature controls at 185 DEG C, then carries out pelletize.
Reference examples 1
Difference with embodiment 3 is: do not add macropore glucomannan hydrogel of konnjaku in composite.
1st step, by weight, is ground into 200 mesh～400 mesh fine powders by cabo 15 parts, offal 35 parts, adds to water
In 350 parts, add β-Fructus Hordei Germinatus carbon hydrate hydrolytic enzyme 7 parts, amino peptidase 3 parts, 1,5-AF 5 parts, at 48 DEG C
Under carry out enzyme digestion reaction, obtain enzymolysis solution；
2nd step, is heated to 75 DEG C of extractions enzyme denaturing to the enzymolysis solution of the 1st step gained, lixiviating solution is sent into ultrafilter membrane and filters,
The component that retains of ultrafilter membrane is 300000da, and the pressure limit of ultrafiltration is 0.3Mpa, and the temperature of ultra-filtration process is 30 DEG C, is surpassed
Filter concentration liquid, after liquid spray drying will be concentrated by ultrafiltration, the tobacco leaf fiber after being processed；
3rd step, by weight, after being pulverized by bamboo fibre 2 parts, mixes with 0.5mol/L hydrochloric acid solution 8 parts, enters at heating 80 DEG C
Row hydrolysis, after reaction terminates, filters out residue, cleans residue use water to pH neutral, then by residue, Polyethylene Glycol 0.3
Part, 7 parts of mix homogeneously of water, be warming up to 85 DEG C and react, and obtains white serosity, obtains modification of microcrystalline fiber after spray drying
Element；
4th step, by weight, (described polylactic acid is transparent extrusion grade or injection grade, and fusing point is 160 DEG C, molten to take polylactic acid
Melting index is 10g/10min) 80 parts, process after tobacco leaf fiber 15 parts, modified microcrystalline cellulose 5 parts, filler-calcium carbonate 18
Part, Plasticizers Propylene glycol 2 parts, cross-linking agent paraformaldehyde 2 parts, hydrazides class organic nucleating agent 2 parts, γ-glycidyl ether oxygen propyl
Trimethoxysilane coupling agent 2 parts, bulking agent ethylene ethyl acrylate 2 parts, lubricant stearic acid 2 parts, surfactant 12
After 2 parts of mix homogeneously of alkyl sodium sulfate, putting in extruder, the screw rod rotary speed of extruder controls at 45rpm, extrusion temperature
Control at 185 DEG C, then carry out pelletize.
Reference examples 2
Difference with embodiment 3 is: lixiviating solution is without ultrafiltration membrane treatment.
1st step, by weight, is ground into 200 mesh～400 mesh fine powders by cabo 15 parts, offal 35 parts, adds to water
In 350 parts, add β-Fructus Hordei Germinatus carbon hydrate hydrolytic enzyme 7 parts, amino peptidase 3 parts, 1,5-AF 5 parts, at 48 DEG C
Under carry out enzyme digestion reaction, obtain enzymolysis solution；
2nd step, is heated to 75 DEG C of extractions enzyme denaturing to the enzymolysis solution of the 1st step gained, after being spray-dried by lixiviating solution, obtains everywhere
Tobacco leaf fiber after reason；
3rd step, by weight, weighs konjaku powder 40 parts, is dissolved in distilled water 350 parts, is stirred into colloidal sol；Add
Sodium hydrate aqueous solution stirs, and making sol pH is 11；Heating up and react at 70 DEG C, after terminating, cooling stands, then with steaming
Distilled water washing by soaking, is placed in freezing tank freezing by gel, then room temperature is melted, and obtains macropore Rhizoma amorphophalli glucomannan water-setting after lyophilizing
Glue；
4th step, by weight, after being pulverized by bamboo fibre 2 parts, mixes with 0.5mol/L hydrochloric acid solution 8 parts, enters at heating 80 DEG C
Row hydrolysis, after reaction terminates, filters out residue, cleans residue use water to pH neutral, then by residue, Polyethylene Glycol 0.3
Part, 7 parts of mix homogeneously of water, be warming up to 85 DEG C and react, and obtains white serosity, obtains modification of microcrystalline fiber after spray drying
Element；
5th step, by weight, (described polylactic acid is transparent extrusion grade or injection grade, and fusing point is 160 DEG C, molten to take polylactic acid
Melting index is 10g/10min) 80 parts, process after tobacco leaf fiber 15 parts, macropore glucomannan hydrogel of konnjaku 15 parts, modified
Microcrystalline Cellulose 5 parts, filler-calcium carbonate 18 parts, Plasticizers Propylene glycol 2 parts, cross-linking agent paraformaldehyde 2 parts, the organic nucleation of hydrazides class
Agent 2 parts, γ-glycidyl ether oxygen propyl trimethoxy silicane coupling agent 2 parts, bulking agent ethylene ethyl acrylate 2 parts, lubricant
After stearic acid 2 parts, 2 parts of mix homogeneously of Surfactant SDS, putting in extruder, the screw rod of extruder rotates
Speed controlling is at 45rpm, and extrusion temperature controls at 185 DEG C, then carries out pelletize.
By embodiment 1～3 and the composite injection mo(u)lding that obtains of reference examples 1～2 be standard tensile batten and impact batten, its
In, injection temperature is 175～185 DEG C, and injection pressure is 70～90MPa, and dwell pressure is 45MPa.According to GB/T 1040.2-
2006, GB/T 9341-2008 and GB/T 1843-2008 carries out tensile property, bending property and notch impact strength test, its
Test result is as shown in table 1.
As can be seen from the above table, the composite that the present invention prepares has good mechanical performance, wherein embodiment 3
For reference examples 2, by lixiviating solution through ultrafiltration membrane treatment, some impurity in lixiviating solution can be got rid of, and then
Improve the mechanical performance of material.
By above example 1～3 and the composite that obtains of reference examples 1～2 by single screw extrusion machine die extrusion, and
By melt enter curtain coating head, head temperature is 130～190 DEG C, control the rate of feeding of single screw extrusion machine, screw speed and
Its casting machine draught animals film gap, the gross thickness making thin-film material is 0.060mm.
Absolute oral degradation rate and the Relative biological resolution ratio of thin-film material are surveyed by GB/T 19277.1-2011 method
Testing according to GB/T 1038-2000 method of examination, oxygen and carbon dioxide transmitance, water vapour permeability presses GB/
T 1037-1988 method is tested, and result is as shown in table 2.
As can be seen from the above table, the composite that the present invention prepares has a good decomposability, wherein embodiment 3 relative to
For reference examples 1, by adding macropore glucomannan hydrogel of konnjaku, and then improve decomposability.
Claims (10)
1. the preparation method of biodegradable polylactic acid-fibrous composite, it is characterised in that comprise the steps:
1st step, by weight, is ground into fine powder, addition to water 300～400 parts by cabo 10～20 parts, offal 30～40 parts
In, add β-Fructus Hordei Germinatus carbon hydrate hydrolytic enzyme 5～10 parts, amino peptidase 2～4 parts, 1,5-AF 4～8 parts, excellent
It is selected at 45～50 DEG C and carries out enzyme digestion reaction, obtain enzymolysis solution；
2nd step, is heated to 70～80 DEG C of extractions enzyme denaturing to the enzymolysis solution of the 1st step gained, lixiviating solution is sent into ultrafilter membrane and carries out
Filter, obtain liquid is concentrated by ultrafiltration, after liquid spray drying will be concentrated by ultrafiltration, the tobacco leaf fiber after being processed；
3rd step, by weight, weighs konjaku powder 30～50 parts, is dissolved in distilled water 300～400 parts, is stirred into molten
Glue；Adding inorganic base aqueous solution to stir, making sol pH is 9～13；Heat up and react at 65～80 DEG C, cool down after terminating
Stand, then wash with distilled water immersion, gel is placed in freezing tank freezing, then room temperature is melted, after lyophilizing, obtain macropore evil spirit
Taro glucomannan hydrogel；
4th step, by weight, after Plant fiber 1～2 parts being pulverized, mix with inorganic acid solution 5～20 parts, heat 75～
Be hydrolyzed at 95 DEG C reaction, after reaction terminates, filters out residue, cleans residue use water to pH neutral, then by residue, poly-second
Glycol 0.2～0.4 part, water 5～8 parts of mix homogeneously, be warming up to 80～90 DEG C and react, and obtains white serosity, is spray-dried
After obtain modified microcrystalline cellulose；
5th step, by weight, take polylactic acid 60～90 parts, process after tobacco leaf fiber 10～20 parts, macropore konjak portuguese gansu polyose
Sucrose solution gel 10～20 parts, modified microcrystalline cellulose 4～10 parts, filler 15～20 parts, plasticizer 1～3 parts, cross-linking agent 1～3
Part, nucleator 1～3 parts, coupling agent 1～3 parts, bulking agent 1～3 parts, lubricant 1～3 parts, surfactant 1～3 parts of mixing are all
After even, putting in extruder, the screw rod rotary speed of extruder controls at 40～50 rpm, and extrusion temperature controls 170～195
DEG C, then carry out pelletize.
The preparation method of biodegradable polylactic acid-fibrous composite the most according to claim 1, its feature exists
In: in the 1st step, the granular size of fine powder is at 200 mesh～400 mesh.
The preparation method of biodegradable polylactic acid-fibrous composite the most according to claim 1, its feature exists
In: in the 2nd described step, the component that retains of ultrafilter membrane is between 200000～400000da, and the pressure limit of ultrafiltration is 0.1
～0.5Mpa, the temperature of ultra-filtration process is 20～40 DEG C.
The preparation method of biodegradable polylactic acid-fibrous composite the most according to claim 1, its feature exists
In: in the 3rd described step, the mixing of inorganic base one or two kinds of in sodium hydroxide or potassium hydroxide.
The preparation method of biodegradable polylactic acid-fibrous composite the most according to claim 1, its feature exists
In: in the 4th described step, Plant fiber's one or several mixing in cotton fiber, the wood fiber, bamboo fibre, flaxen fiber
Thing；Inorganic acid solution is hydrochloric acid, sulphuric acid or phosphoric acid solution, and acid concentration is 0.1～1.0mol/L.
The preparation method of biodegradable polylactic acid-fibrous composite the most according to claim 1, its feature exists
In: described polylactic acid is transparent extrusion grade or injection grade, and fusing point is 145～170 DEG C, and melt index is 2～30g/10min.
The preparation method of biodegradable polylactic acid-fibrous composite the most according to claim 1, its feature exists
In: described nucleator one in amide-type organic nucleating agent, hydrazides class organic nucleating agent, terres rares nucleator；Institute
The coupling agent stated is selected from N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-(methacryloxypropyl) propyl group trimethoxy
Base silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, r-chloropropyl trimethoxyl silane, ethyl trimethoxy silane,
One or more in isopropyl two (methylacryloyl) isostearoyl base titanate esters mixture in any proportion；Described profit
Lubrication prescription is selected from stearic acid or liquid paraffin.
The preparation method of biodegradable polylactic acid-fibrous composite the most according to claim 1, its feature exists
In: described plasticizer can be one or several in ethylene glycol, propylene glycol, sorbitol or glycerol；Described crosslinking
Agent can be one or several in formaldehyde, paraformaldehyde, acetaldehyde, Metaldehyde or epoxychloropropane；Described increase-volume
Agent is the one in ethylene acrylic acid co polymer, ethylene ethyl acrylate, ethylene-vinylacetate grafting maleic anhydride copolymer.
The preparation method of biodegradable polylactic acid-fibrous composite the most according to claim 1, its feature exists
In: surfactant can use sodium lauryl sulphate, diethanolamine of fat acyl, AESA, fat
One or more mixture in fat polyoxyethylenated alcohol sodium sulfate.
The preparation method of biodegradable polylactic acid-fibrous composite the most according to claim 1, its feature exists
In: filler is selected from one or several in calcium carbonate, titanium oxide or magnesium carbonate.
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| CN109957256A (en) * | 2019-03-13 | 2019-07-02 | 安庆市泽烨新材料技术推广服务有限公司 | A kind of processing method of degradable resin |
| KR20190136989A (en) * | 2018-05-31 | 2019-12-10 | 쉐 조우 | heat-not-burn tobacco |
| CN111674045A (en) * | 2020-05-27 | 2020-09-18 | 安徽元琛环保科技股份有限公司 | Preparation method of PLA-based composite material for 3D printing and prepared material |
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| CN107540877A (en) * | 2017-09-30 | 2018-01-05 | 江苏瑞腾涂装科技有限公司 | A kind of degradable packaging bag |
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