A kind of preparation method of biodegradable PLA-fibrous composite
Technical field
The present invention relates to a kind of preparation method of biodegradable PLA-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 random in large quantities
It is discarded in natural environment, pollution is caused to environment, therefore Biodegradable material and its packing articles are increasingly becoming currently
The focus of research and development.If providing that a kind of 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 at 60%.Up to now, scale or the biodegradable plastic kind of pilot scale
Class has PLA (PLA), PHA (PHA, including PHB, PHBV, P (3HB, 4HB) and PHBH etc.), poly-succinic fourth
It is diester (PBS), terephthalic acid (TPA) adipic acid butanediol copolymer (PBAT), poly-succinic-adipic acid-fourth diester (PBSA), poly-
Propylene carbonate (PPC), polycaprolactone (PCL) etc..
Wherein, PLA (PLA) is a kind of synthesis macromolecule with excellent biocompatibility and biodegradable
Material.This linear thermoplastic's biodegradable aliphatic polyesters of PLA are to be extracted in some plants such as corn, wheat, cassava
Starch be initial raw material, decomposed by enzyme and obtain glucose, then become lactic acid after lactobacillus-fermented, then by chemistry
Synthesis obtains high-purity PLA.Ester bond facile hydrolysis in PLA, can the effect degraded through microorganism in vivo or in soil
Lactic acid is generated, metabolic end-product is water and carbon dioxide, so will not produce toxic side effect to human body, use is very safe.
Therefore PLA is applied to many aspects such as medical science, pharmacy, is such as used as surgical sewing thread, drug controlled release system
System etc..
CN104693427A discloses a kind of PLA biodegradation material and its preparation method and application.Its step is:1)
Water removal:The method being dehydrated using still refluxed evaporator or using azeotropic solvent removes the moisture in lactic raw material;2) precondensation:
Using the higher lactic raw material of purity, in the presence of a catalyst, precondensation is carried out;3) condensation polymerization;In the presence of a catalyst,
The lactic acid polymer obtained using preshrunk polymerizing technology carries out reduced vacuum polycondensation as raw material.CN104559101A discloses a kind of high-strength
High-ductility fully-degradable polylactic acid composite and preparation method thereof, 52.0~60.4MPa of its tensile strength, elongation 57~210%,
4.2~8.3KJ/m of notch impact strength2;It is prepared from using melt-blending process.Preparing raw material is by mass fraction:PLA
70~90 parts of resin;10-30 parts of polycarbonate elastomer body;1 part of antioxidant;Graphene oxide is polylactic resin and makrolon
The 0.1~1% of elastomer gross mass;Each raw material is put into baking oven, at a temperature of 60~80 DEG C, dried 4~6 hours, it is rear to add
Mixed in high speed mixer to uniform, then mixed uniformly material is added in screw extruder, in being extruded at 160~180 DEG C
Produce.
If using complete PLA as master package material, the problem of cost is too high can be caused, it is therefore desirable to provide
It is a kind of based on polylactic acid degradable, while having the composite degradation packaging material of lower cost.As tobacco leaf production big country,
The t of the annual yield of tobacco 450 of China~5,000,000, goes out of use wherein there are about the leftover bits and pieces such as nearly 25% tobacco leaf, offal, it is impossible to be used in
Production of cigarettes, such as Yunnan there are about 30%~35% as the big province of tobacco, in annual yield of flue-cured tobacco and belong to that Cigarette processing can not be carried out
It is low or wait outer level tobacco leaf, fail rationally to be utilized.
The content of the invention
The purpose of the present invention is:PLA-fiber composite that a kind of good mechanical property, cost are low, degradation speed is fast is provided
Material, wherein employing waste and old tobacco leaf as fiber-filled material.
Technical scheme is as follows:
A kind of preparation method of biodegradable PLA-fibrous composite, comprises the following steps:
1st step, by weight, fine powder is ground into by 10~20 parts of offal, 30~40 parts of offal, add to water 300~
In 400 parts, β -5~10 parts of malt carbohydrate inversion enzyme, 2~4 parts of aminopeptidase, 1,5-AF 4~8 are added
Part, enzyme digestion reaction is carried out at 45~50 DEG C, enzymolysis liquid is obtained;
2nd step, is heated to 70~80 DEG C to the enzymolysis liquid obtained by the 1st step and extracts and the enzyme that goes out, leaching liquor is sent into milipore filter
Filtered, obtain that liquid is concentrated by ultrafiltration, will be concentrated by ultrafiltration after liquid spray drying, the tobacco leaf fiber after being handled;
3rd step, by weight, weighs 30~50 parts of konjaku powder, is dissolved in 300~400 parts of distilled water, stirs
Into colloidal sol;Add inorganic base aqueous solution to stir, it is 9~13 to make sol pH;Reacted at 65~80 DEG C of heating, after terminating
Cooling and standings, are then washed with distilled water immersion, and gel is placed in freezing tank and freezed, then room temperature is melted, and obtain big after freezing
Hole glucomannan hydrogel of konnjaku;
4th step, by weight, after 1~2 part of crushing of string, 5~20 parts mix with inorganic acid solution, heating
Be hydrolyzed reaction at 75~95 DEG C, after reaction terminates, filter out residue, residue is cleaned neutral to pH with water, then by residue,
0.2~0.4 part of polyethylene glycol, 5~8 parts of water are well mixed, and are warming up to 80~90 DEG C and are reacted, obtain white slurries, spray
Modified microcrystalline cellulose is obtained after drying;
5th step, by weight, takes 10~20 parts of tobacco leaf fiber after 60~90 parts of PLA, processing, macropore konjaku Portugal
Sweet 10~20 parts of glycan hydrogel, 4~10 parts of modified microcrystalline cellulose, 15~20 parts of filler, 1~3 part of plasticizer, crosslinking agent 1
~3 parts, 1~3 part of nucleator, 1~3 part of coupling agent, 1~3 part of bulking agent, 1~3 part of lubricant, 1~3 part of surfactant mix
After closing uniformly, it is put into extruder, the screw rod rotary speed control of extruder is in 40~50 rpm, and extrusion temperature is controlled 170
~195 DEG C, then granulated.
The granular size of fine powder is in the mesh of 200 mesh~400 in 1st step.
In the 2nd described step, the retention component of milipore filter is the pressure limit of ultrafiltration between 200000~400000da
It is 0.1~0.5Mpa, the temperature of ultra-filtration process is 20~40 DEG C.
In the 3rd described step, the mixing of one or two kinds of of the inorganic base in sodium hydroxide or potassium hydroxide.
In the 4th described step, one or several kinds of the string in cotton fiber, wood-fibred, bamboo fibre, flaxen fiber
Mixture;Inorganic acid solution is hydrochloric acid, sulfuric acid or phosphoric acid solution, and acid concentration is 0.1~1.0mol/L.
Described PLA is transparent extrusion grade or injection grade, and fusing point is 145~170 DEG C, and melt index is 2~30g/
10min。
Described nucleator in amide-type organic nucleating agent, hydrazides class organic nucleating agent, terres rares nucleator one
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
One or more in TMOS, isopropyl two (methylacryloyl) isostearoyl base titanate esters are mixed in any proportion
Thing.
The lubricant is selected from stearic acid or atoleine.
Described plasticizer can be the one or several kinds in ethylene glycol, propane diols, sorbierite or glycerine.
Described crosslinking agent can be one kind 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 kind in alkene copolymer.
Surfactant can use lauryl sodium sulfate, diethanolamine of fat acyl, AEO sulfuric acid
One or more of mixtures in ammonium, sodium sulfate of polyethenoxy ether of fatty alcohol.
One or several kinds of the filler in calcium carbonate, titanium oxide or magnesium carbonate.
Beneficial effect
The PLA degradable material that the present invention is prepared, employs waste and old tobacco leaf as fiber-filled material, with machine
The advantage that tool performance is good, cost is low, degradation speed is fast.
Embodiment
Embodiment 1
1st step, by weight, the mesh fine powder of 200 mesh~400 is ground into by 10 parts of offal, 30 parts of offal, added to water
In 300 parts, β -5 parts of malt carbohydrate inversion enzyme, 2 parts of aminopeptidase, 4 parts of 1,5-AF are added, at 45 DEG C
Lower carry out enzyme digestion reaction, obtains enzymolysis liquid;
2nd step, is heated to 70 DEG C to the enzymolysis liquid obtained by the 1st step and extracts and the enzyme that goes out, and leaching liquor feeding milipore filter is carried out
Filtering, the retention component of milipore filter is that, in 200000da, the pressure limit of ultrafiltration is 0.1Mpa, and the temperature of ultra-filtration process is 20
DEG C, obtain that liquid is concentrated by ultrafiltration, will be concentrated by ultrafiltration after liquid spray drying, the tobacco leaf fiber after being handled;
3rd step, by weight, weighs 30 parts of konjaku powder, is dissolved in 300 parts of distilled water, is stirred into colloidal sol;Again
Add sodium hydrate aqueous solution to stir, it is 9 to make sol pH;Reacted at 65 DEG C of heating, terminate rear cooling and standings, Ran Houyong
Distilled water immersion is washed, and gel is placed in freezing tank and freezed, then room temperature is melted, and macropore konjak portuguese gansu polyose syrup is obtained after freezing
Gel;
4th step, by weight, after 1 part of crushing of bamboo fibre, 5 parts mix with 0.1mol/L hydrochloric acid solutions, heat 75 DEG C
Under be hydrolyzed reaction, after reaction terminates, filter out residue, residue cleaned neutral to pH with water, then by residue, polyethylene glycol
0.2 part, 5 parts of water be well mixed, be warming up to 80 DEG C and reacted, obtain obtaining modification of microcrystalline fibre after white slurries, spray drying
Dimension element;
5th step, by weight, taking PLA, (described PLA is transparent extrusion grade or injection grade, and fusing point is 145
DEG C, melt index is 2g/10min) 60 parts, 10 parts of tobacco leaf fiber after processing, 10 parts of macropore glucomannan hydrogel of konnjaku,
4 parts of modified microcrystalline cellulose, 15 parts of filler-calcium carbonate, 1 part of Plasticizers Propylene glycol, 1 part of crosslinking agent paraformaldehyde, hydrazides class are organic
1 part of nucleator, γ -1 part of glycidyl ether oxygen propyl trimethoxy silicane coupling agent, 1 part of bulking agent ethylene ethyl acrylate, profit
After 1 part of lubrication prescription stearic acid, 1 part of Surfactant SDS are well mixed, it is put into extruder, the screw rod of extruder
Rotary speed control is in 40rpm, and extrusion temperature is controlled at 170 DEG C, then is granulated.
Embodiment 2
1st step, by weight, the mesh fine powder of 200 mesh~400 is ground into by 20 parts of offal, 40 parts of offal, added to water
In 400 parts, β -10 parts of malt carbohydrate inversion enzyme, 4 parts of aminopeptidase, 8 parts of 1,5-AF are added, at 50 DEG C
Lower carry out enzyme digestion reaction, obtains enzymolysis liquid;
2nd step, is heated to 80 DEG C to the enzymolysis liquid obtained by the 1st step and extracts and the enzyme that goes out, and leaching liquor feeding milipore filter is carried out
Filtering, the retention component of milipore filter is 400000da, and the pressure limit of ultrafiltration is 0.5Mpa, and the temperature of ultra-filtration process is 40 DEG C,
Obtain that liquid is concentrated by ultrafiltration, will be concentrated by ultrafiltration after liquid spray drying, the tobacco leaf fiber after being handled;
3rd step, by weight, weighs 50 parts of konjaku powder, is dissolved in 400 parts of distilled water, is stirred into colloidal sol;Again
Add sodium hydrate aqueous solution to stir, it is 13 to make sol pH;Reacted at 80 DEG C of heating, terminate rear cooling and standings, then
Washed with distilled water immersion, gel is placed in freezing tank and freezed, then room temperature is melted, and macropore konjaku glucomannan is obtained after freezing
Hydrogel;
4th step, by weight, after 2 parts of crushing of bamboo fibre, 20 parts mix with 1.0mol/L hydrochloric acid solutions, heating 95
It is hydrolyzed reaction at DEG C, after reaction terminates, filters out residue, residue is cleaned neutral to pH with water, then by residue, poly- second two
0.4 part of alcohol, 8 parts of water are well mixed, and are warming up to 90 DEG C and are reacted, modification of microcrystalline is obtained after obtaining white slurries, spray drying
Cellulose;
5th step, by weight, taking PLA, (described PLA is transparent extrusion grade or injection grade, and fusing point is 170
DEG C, melt index is 30g/10min) 90 parts, 20 parts of tobacco leaf fiber after processing, macropore glucomannan hydrogel of konnjaku 20
Part, 10 parts of modified microcrystalline cellulose, 20 parts of filler-calcium carbonate, 3 parts of Plasticizers Propylene glycol, 3 parts of crosslinking agent paraformaldehyde, hydrazides class
3 parts of organic nucleating agent, γ -3 parts of glycidyl ether oxygen propyl trimethoxy silicane coupling agent, bulking agent ethylene ethyl acrylate 3
After part, 3 parts of lubricant stearic acid, 3 parts of Surfactant SDS are well mixed, it is put into extruder, extruder
The control of screw rod rotary speed in 50 rpm, extrusion temperature is controlled at 195 DEG C, then is granulated.
Embodiment 3
1st step, by weight, the mesh fine powder of 200 mesh~400 is ground into by 15 parts of offal, 35 parts of offal, added to water
In 350 parts, β -7 parts of malt carbohydrate inversion enzyme, 3 parts of aminopeptidase, 5 parts of 1,5-AF are added, at 48 DEG C
Lower carry out enzyme digestion reaction, obtains enzymolysis liquid;
2nd step, is heated to 75 DEG C to the enzymolysis liquid obtained by the 1st step and extracts and the enzyme that goes out, and leaching liquor feeding milipore filter is carried out
Filtering, the retention component of milipore filter is 300000da, and the pressure limit of ultrafiltration is 0.3Mpa, and the temperature of ultra-filtration process is 30 DEG C,
Obtain that liquid is concentrated by ultrafiltration, will be concentrated by ultrafiltration after liquid spray drying, the tobacco leaf fiber after being handled;
3rd step, by weight, weighs 40 parts of konjaku powder, is dissolved in 350 parts of distilled water, is stirred into colloidal sol;Again
Add sodium hydrate aqueous solution to stir, it is 11 to make sol pH;Reacted at 70 DEG C of heating, terminate rear cooling and standings, then
Washed with distilled water immersion, gel is placed in freezing tank and freezed, then room temperature is melted, and macropore konjaku glucomannan is obtained after freezing
Hydrogel;
4th step, by weight, after 2 parts of crushing of bamboo fibre, 8 parts mix with 0.5mol/L hydrochloric acid solutions, heat 80 DEG C
Under be hydrolyzed reaction, after reaction terminates, filter out residue, residue cleaned neutral to pH with water, then by residue, polyethylene glycol
0.3 part, 7 parts of water be well mixed, be warming up to 85 DEG C and reacted, obtain obtaining modification of microcrystalline fibre after white slurries, spray drying
Dimension element;
5th step, by weight, taking PLA, (described PLA is transparent extrusion grade or injection grade, and fusing point is 160
DEG C, melt index is 10g/10min) 80 parts, 15 parts of tobacco leaf fiber after processing, 15 parts of macropore glucomannan hydrogel of konnjaku,
5 parts of modified microcrystalline cellulose, 18 parts of filler-calcium carbonate, 2 parts of Plasticizers Propylene glycol, 2 parts of crosslinking agent paraformaldehyde, hydrazides class are organic
2 parts of nucleator, γ -2 parts of glycidyl ether oxygen propyl trimethoxy silicane coupling agent, 2 parts of bulking agent ethylene ethyl acrylate, profit
After 2 parts of lubrication prescription stearic acid, 2 parts of Surfactant SDS are well mixed, it is put into extruder, the screw rod of extruder
Rotary speed control is in 45rpm, and extrusion temperature is controlled at 185 DEG C, then is granulated.
Reference examples 1
Difference with embodiment 3 is:Macropore glucomannan hydrogel of konnjaku is not added in composite.
1st step, by weight, the mesh fine powder of 200 mesh~400 is ground into by 15 parts of offal, 35 parts of offal, added to water
In 350 parts, β -7 parts of malt carbohydrate inversion enzyme, 3 parts of aminopeptidase, 5 parts of 1,5-AF are added, at 48 DEG C
Lower carry out enzyme digestion reaction, obtains enzymolysis liquid;
2nd step, is heated to 75 DEG C to the enzymolysis liquid obtained by the 1st step and extracts and the enzyme that goes out, and leaching liquor feeding milipore filter is carried out
Filtering, the retention component of milipore filter is 300000da, and the pressure limit of ultrafiltration is 0.3Mpa, and the temperature of ultra-filtration process is 30 DEG C,
Obtain that liquid is concentrated by ultrafiltration, will be concentrated by ultrafiltration after liquid spray drying, the tobacco leaf fiber after being handled;
3rd step, by weight, after 2 parts of crushing of bamboo fibre, 8 parts mix with 0.5mol/L hydrochloric acid solutions, heat 80 DEG C
Under be hydrolyzed reaction, after reaction terminates, filter out residue, residue cleaned neutral to pH with water, then by residue, polyethylene glycol
0.3 part, 7 parts of water be well mixed, be warming up to 85 DEG C and reacted, obtain obtaining modification of microcrystalline fibre after white slurries, spray drying
Dimension element;
4th step, by weight, taking PLA, (described PLA is transparent extrusion grade or injection grade, and fusing point is 160
DEG C, melt index is 10g/10min) 80 parts, 15 parts of tobacco leaf fiber after processing, 5 parts of modified microcrystalline cellulose, filler carbonic acid
18 parts of calcium, 2 parts of Plasticizers Propylene glycol, 2 parts of crosslinking agent paraformaldehyde, 2 parts of hydrazides class organic nucleating agent, γ-glycidyl ether oxygen
2 parts of propyl trimethoxy silicane coupling agent, 2 parts of bulking agent ethylene ethyl acrylate, 2 parts of lubricant stearic acid, surfactant
After 2 parts of lauryl sodium sulfate is well mixed, it is put into extruder, the screw rod rotary speed control of extruder is in 45rpm, extrusion
Temperature control is at 185 DEG C, then is granulated.
Reference examples 2
Difference with embodiment 3 is:Leaching liquor is without ultrafiltration membrane treatment.
1st step, by weight, the mesh fine powder of 200 mesh~400 is ground into by 15 parts of offal, 35 parts of offal, added to water
In 350 parts, β -7 parts of malt carbohydrate inversion enzyme, 3 parts of aminopeptidase, 5 parts of 1,5-AF are added, at 48 DEG C
Lower carry out enzyme digestion reaction, obtains enzymolysis liquid;
2nd step, is heated to 75 DEG C to the enzymolysis liquid obtained by the 1st step and extracts and the enzyme that goes out, after leaching liquor is spray-dried, obtain
Tobacco leaf fiber after to processing;
3rd step, by weight, weighs 40 parts of konjaku powder, is dissolved in 350 parts of distilled water, is stirred into colloidal sol;Again
Add sodium hydrate aqueous solution to stir, it is 11 to make sol pH;Reacted at 70 DEG C of heating, terminate rear cooling and standings, then
Washed with distilled water immersion, gel is placed in freezing tank and freezed, then room temperature is melted, and macropore konjaku glucomannan is obtained after freezing
Hydrogel;
4th step, by weight, after 2 parts of crushing of bamboo fibre, 8 parts mix with 0.5mol/L hydrochloric acid solutions, heat 80 DEG C
Under be hydrolyzed reaction, after reaction terminates, filter out residue, residue cleaned neutral to pH with water, then by residue, polyethylene glycol
0.3 part, 7 parts of water be well mixed, be warming up to 85 DEG C and reacted, obtain obtaining modification of microcrystalline fibre after white slurries, spray drying
Dimension element;
5th step, by weight, taking PLA, (described PLA is transparent extrusion grade or injection grade, and fusing point is 160
DEG C, melt index is 10g/10min) 80 parts, 15 parts of tobacco leaf fiber after processing, 15 parts of macropore glucomannan hydrogel of konnjaku,
5 parts of modified microcrystalline cellulose, 18 parts of filler-calcium carbonate, 2 parts of Plasticizers Propylene glycol, 2 parts of crosslinking agent paraformaldehyde, hydrazides class are organic
2 parts of nucleator, γ -2 parts of glycidyl ether oxygen propyl trimethoxy silicane coupling agent, 2 parts of bulking agent ethylene ethyl acrylate, profit
After 2 parts of lubrication prescription stearic acid, 2 parts of Surfactant SDS are well mixed, it is put into extruder, the screw rod of extruder
Rotary speed control is in 45rpm, and extrusion temperature is controlled at 185 DEG C, then is granulated.
The composite injection molding that embodiment 1~3 and reference examples 1~2 are obtained is standard tensile batten and impact sample
Bar, wherein, 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 carry 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 is prepared has good mechanical performance, wherein embodiment 3
For reference examples 2, ultrafiltration membrane treatment is passed through by leaching liquor, some impurity in leaching liquor can be got rid of, and then
Improve the mechanical performance of material.
The composite that above example 1~3 and reference examples 1~2 are obtained by single screw extrusion machine die extrusion, and
Melt is entered into curtain coating head, head temperature is 130~190 DEG C, control the rate of feeding of single screw extrusion machine, screw speed and
It is cast head membrana oralis gap, and the gross thickness for making thin-film material is 0.060mm.
The Absolute oral degradation rate and Relative biological resolution ratio of thin-film material are surveyed by GB/T 19277.1-2011 methods
Examination, oxygen and carbon dioxide transmitance are tested according to GB/T 1038-2000 methods, and water vapour permeability is by GB/
T 1037-1988 methods are tested, as a result as shown in table 2.
As can be seen from the above table, the composite that the present invention is prepared has good decomposability, the wherein phase of embodiment 3
For reference examples 1, by adding macropore glucomannan hydrogel of konnjaku, and then decomposability is improved.