CN107141816A - A kind of high-barrier biodegradation material and preparation method thereof and application - Google Patents
A kind of high-barrier biodegradation material and preparation method thereof and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The present invention relates to a kind of high-barrier biodegradation material and preparation method thereof and application.The raw material of high-barrier biodegradation material includes following components by weight：During each component material polymerization reaction, different molecular and functional group's interphase interaction and formed with spatial network molecular structure and very fine and close material, reduce the motion frequency of high polymer material segment under glassy state, free volume occurs between reduction macromolecular chain frequency or reduce free volume, the passage for being even switched off being available for water vapour molecule to spread is reduced, so as to improve vapor water barriers performance.Meanwhile, above-mentioned material is a kind of environment-friendly new bio-based materials.
Description
Technical field
The present invention relates to environment-friendly new bio-based materials field, more particularly to a kind of high-barrier biodegradation material
And preparation method thereof and application.
Background technology
Separated packaging material is the material for having function of shielding to gas-liquid penetrant, can prevent oxygen, water vapour, liquid and
The infiltration of fragrance, protects that content is not spoiled, never degenerate, and extends circulation cycle and the shelf life of commodity.Therefore, barrier package
Material is widely used in the packaging of the products such as food, medicine, chemicals, particularly frozen food, meat products, fatty foods, tea
The packaging of the commodity such as leaf, spices, cosmetics and agricultural chemicals.
Now, the separated packaging material of in the market mainly have aluminium foil, metallized film, ethylene-vinyl alcohol copolymer (EVOH),
The conventional obstructive material such as polyvinylidene chloride (PVDC) and PEN (PEN) and plating silica or plating oxidation
The novel barrier material such as aluminium film.
However, traditional separated packaging material can all bring more or less ring during processing and manufacturing and post processing
Border problem.For example, not degradable containing metal level (such as aluminium foil) in packaging material, the aluminium foil in composite packaging material is domestic and incompetent at present
Power is separated, as a result cause paper constructed of aluminium and plastic-aluminum structure composite discarded object both can not recycling, again
It can not burn, the harm to environmental protection is very big.Meanwhile, aluminium foil or plating aluminum packaging materials are opaque, it is impossible to be used in microwave is heated, aluminium foil
Folding resistance is poor, cost is high, intensity difference of aluminizing (aluminium lamination meets the easy Automatic-falling of water).And polyvinylidene chloride (PVDC) has following lack
Point：First, heat endurance is poor, and membrance casting condition is harsh, even across the PVDC plastics of plasticising, stabilized formulations processing, it is also necessary to make
With the extraordinary extrusion equipment with special alloy screw rod, barrel and die head, under strict process regulation, could smoothly it give birth to
The multi-layer co-extruded film of output barrier layer containing PVDC, the environmentally friendly bad adaptability of film of the barrier layer containing PVDC, because PVDC heat is steady
Qualitative difference, the film scrap and reclaimed materials of the barrier layer containing PVDC, still can not granulate regeneration by heat fusing at present；Its
It is secondary, the harmful substance of vinyl chloride etc can be produced during PVDC burning disposals, or even produce strong carcinogen bioxin.And for second
Alkene-ethenol copolymer (EVOH), when ambient humidity is more than 50%RH, its barrier property is drastically deteriorated.
Above-mentioned petroleum-based barrier material is using fossil resources as raw material, while being caused harm to environment, being unfavorable for should
With.And the equipment investment for plating the novel barrier material such as silica and alumina-plated film is extremely expensive, process technology is very difficult,
Therefore product cost is high.
Therefore, the sustainable requirement of the increasingly exhausted and human survival and development with fossil resources, biodegradable high
Molecular material turns into the study hotspot in current environment-friendly materials field.However, there is barrier property in traditional biodegradation material
Bad defect, it is especially poor to the barrier of vapor.
The content of the invention
Based on this, it is necessary to which there is provided a kind of high for the problem of barrier property existed for traditional biological degradable material is bad
Obstruct biodegradation material and preparation method thereof and application.
A kind of high-barrier biodegradation material, the raw material of the high-barrier biodegradation material include by weight with
Lower component：
The raw material of the high-barrier biodegradation material of the present invention are respectively provided with good characteristic：Acidifying high protein colloid has
Good film forming characteristics, material is fine and close in itself, and barrier property is good；It is preferred that the barrier of biodegradable resin be biological
Outstanding person in degraded polyester material；Bleaching shellac resin, rosin acid, animals and plants wax are the excellent natural lifes of film forming
Thing sill, can be applied to fruit or food fresh keeping industry；The introducing of nano-powder, can make up coated film it is microcosmic on
Physical pin or formation sheet intercalation configuration produce iris action to water vapour molecule, extend the diffusion road of water vapour molecule
Footpath.
The raw material functional group of the high-barrier biodegradation material of the present invention enriches.Specifically, bleaching shellac resin is hydroxyl
Contain carboxyl, three in fat and polyester mixture that aliphatic acid and hydroxy sesquiterpene acid are constituted, average each lac molecule
Individual ester bond, five hydroxyls and an aldehyde radical, due to containing these groups, spontaneous polymerization can occur for lac, or by with carboxylic
Condensation reaction and chain extension occur for the functional groups such as base, ester bond, peptide bond, amino, relative molecular mass increase, at the same time, material
Steam breathability is accordingly reduced.Rosin acid is the main component of natural rosin resins, is tricyclic diterpene class compound, contains
There are carboxyl-reactive gene and double bond, reacted with typical carboxyl and conjugated double bond, except itself being easy to oxidation and isomerization reaction
Outside, also with esterification, alcoholization, into carboxyl reactions such as salt, decarboxylation, ammonolysis, while also having disproportionation, hydrogenation, addition, pair of polymerization
Key reacts.The main component of dry vegetable oil is the glyceride of the unrighted acids such as leukotrienes, linoleic acid, is easy in atmosphere
The flexible solid film of oxidation drying formation high resilience, after oxygen in dry vegetable oil absorption air, occurs oxidation polymerization
Reaction, makes to be solidificated in applicator table into the molecule of space network in the dry vegetable oil molecular change that three-dimensional space is distributed
Face, is changed into solid-state, formation barrier is excellent, intensity is high, good toughness barrier film layer by liquid.Animals and plants wax main component is
High-grade aliphatic ester, hydrophobicity itself is very strong, at normal temperatures in solid-state, and the vapor that can effectively reduce edible film is passed through
Rate, safety non-toxic possesses outstanding vapor water barriers performance.
The high-barrier biodegradation material of the present invention is during each component material polymerization reaction, different molecular and function
Roll into a ball interphase interaction and formed with spatial network molecular structure and very fine and close material, reduce high polymer material under glassy state
The motion frequency of segment, reduces the frequency or reduction free volume of free volume appearance between macromolecular chain, reduction is even switched off can
The passage of water supply vapour molecule diffusion, so as to greatly improve the vapor water barriers performance of material.
In addition, the high-barrier biodegradation material of the present invention is coated in behind biodegradable plastic packaging base material surface, can
Dry under field conditions (factors), can also accelerate to complete drying by heating up.Reaction between its each group fractionated molecule or functional group, can also be with
The continuity of time and proceed.The high-barrier biodegradation material of the present invention is mainly derived from natural animal-plant and natural dynamic plant
Thing product and the biodegradable resin prepolymer obtained by microbial fermentation or chemical synthesis, safety non-toxic, manufacturing process
Simply, there is cost advantage, can be applied to biodegradable plastic packaging there is provided excellent vapor water barriers performance, be a kind of environment
Friendly new bio sill.
In one of the embodiments, the biodegradable resin prepolymer is selected from end carboxyl propylene carbonate pre-polymerization
Thing, end carboxyl ethylene carbonate prepolymer, end carboxyl butylene carbonate prepolymer, end carboxyl carbon dioxide-base isolation-type thermoplasticity
Polyurethane prepolymer, end carboxyl bio-based Nylon pre-polymer and end carboxyl bio-based ethylene glycol terephthalate are pre-
At least one of polymers.
In one of the embodiments, the nano-powder in the nano-powder dispersion emulsion is selected from by coupling agent surface
One kind in modified nano kaoline, nano imvite, nano-graphene, nano aluminium oxide and nano silicon-based oxide, institute
The solid content for stating nano-powder dispersion emulsion is 40%~50%.
In one of the embodiments, the dry vegetable oil is selected from least one of tung oil, Chinese catalpa oil and linseed oil.
In one of the embodiments, the animals and plants wax in beeswax, citrus wax and palm wax at least
It is a kind of.
In one of the embodiments, the water-repelling agent is selected from trim,ethylchlorosilane and perfluorooctyl ethylene base dimethoxy
One kind in silane.
A kind of preparation method of high-barrier biodegradation material is also provided, comprised the following steps：
By the acidifying high protein colloid of 25~35 parts by weight, the biodegradable resin prepolymer of 15~20 parts by weight, 0.5
The chain extender and water of~1.5 parts by weight are warming up to 60 DEG C~100 DEG C after mixing, gel composite is obtained after reaction completely, its
In, the mass fraction that the water accounts for the acidifying high protein colloid is 30%~40%；
The gel composite and the albumen enzyme catalyst of 0.02~0.06 parts by weight are mixed, 30 DEG C~60 are cooled to
DEG C, obtain pretreated gel composite after reaction completely；
By the pretreated gel composite and the bleaching shellac resin solution of 35~45 parts by weight, 3~7 parts by weight
Rosin acid, the crosslinking agent of 0.01~0.07 parts by weight, 0.02~0.06 parts by weight organotin catalysts mix, boosting
To 2.0MPa~3.5MPa, 80 DEG C~95 DEG C are warming up to, cross-linking modified gel composite is obtained after reaction completely；
And by the cross-linking modified gel composite and the nano-powder dispersion emulsion of 2~6 parts by weight, 2~6 parts by weight
Dry vegetable oil, the animals and plants wax of 1~3 parts by weight, the water-repelling agent of 1~3 parts by weight, 2~6 parts by weight alcohol ethers solvent mix
It is even, obtain the high-barrier biodegradation material after reaction completely.
In the preparation method of the high-barrier biodegradation material of the present invention, due to the process in each component material polymerization reaction
In, different molecular and functional group's interphase interaction and formed with spatial network molecular structure and very fine and close material, reduction
Free volume occurs between the motion frequency of high polymer material segment under glassy state, reduction macromolecular chain frequency or reduce free body
Product, reduces the passage for being even switched off being available for water vapour molecule to spread, so as to greatly improve the vapor water barriers performance of material.
In one of the embodiments, the acidifying high protein colloid is prepared from using following steps：
Animal gelatin albumen or soybean protein isolate are carried out at Acid hydrolysis afterwards by boiling water boiling to denaturation is dehydrated
Reason, obtains fat-free high protein after being purified；
And be ground after the fat-free high protein is mixed with water, the mass ratio of the high protein and water is
1：1~1：2, until D97≤300nm of powder colloid material, obtains being acidified high protein colloid.
In one of the embodiments, the bleaching shellac resin solution is prepared from using following steps：
Sticklac is crushed successively, screens, rinse, concentration extraction and bleaching, it is former to remove the lac
Natural pigment in glue, obtains resin particle glue；
And mix the resin particle glue and absolute ethyl alcohol, the mass ratio of the resin particle glue and the absolute ethyl alcohol is
1：8~1：10, obtain bleaching shellac resin solution.
In addition, a kind of biodegradable plastic packaging film is also provided, including above-mentioned high-barrier biodegradation material.
In the biodegradable plastic packaging film including above-mentioned high-barrier biodegradation material of the present invention, due in each group
During point material polymerization reaction, different molecular and functional group's interphase interaction and formed with spatial network molecular structure and
The motion frequency of high polymer material segment under very fine and close material, reduction glassy state, free volume goes out between reducing macromolecular chain
Existing frequency or reduction free volume, reduces the passage for being even switched off being available for water vapour molecule to spread, so as to greatly improve biology
The vapor water barriers performance of degraded plastic packaging film.
Brief description of the drawings
Fig. 1 is the flow chart of the preparation method of the high-barrier biodegradation material of an embodiment.
Embodiment
In order to facilitate the understanding of the purposes, features and advantages of the present invention, below in conjunction with embodiment,
The present invention will be described in further detail.It should be appreciated that embodiment described herein is only to explain this hair
It is bright, it is not intended to limit the present invention.
Unless otherwise defined, all of technologies and scientific terms used here by the article is with belonging to technical field of the invention
The implication that technical staff is generally understood that is identical.Term used in the description of the invention herein is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein " and/or " including one or more
The arbitrary and all combination of related Listed Items.
The raw material of the high-barrier biodegradation material of one embodiment includes following components by weight：
Wherein, acidifying high protein colloid has good film forming characteristics, and material is fine and close in itself, and barrier property is good.
More preferably, biodegradable resin prepolymer is selected from end carboxyl propylene carbonate (PPC) prepolymer, end carboxyl carbonic acid
Ethyl (PEC) prepolymer, end carboxyl butylene carbonate prepolymer, end carboxyl carbon dioxide-base isolation-type thermoplastic polyurethane bullet
Property body (end carboxyl carbon dioxide-base isolation-type TPU) prepolymer, end carboxyl bio-based Nylon pre-polymer and end carboxyl bio-based pair
At least one of PET prepolymer.The barrier of these biodegradable resins is Biodegradable polyester
Outstanding person in material, is conducive to the lifting of the high-barrier biodegradation material barrier.
Further more preferably, the number-average molecular weight of biodegradable resin prepolymer is 5000~10000.
More preferably, chain extender is selected from ethylene-methyl acrylate-glyceryl methacrylate terpolymer, benzene second
Alkene-glycidyl methacrylate copolymer, hexamethylene diisocyanate, methyl diphenylene diisocyanate, 2,4- first
Phenylene diisocyanate, 2,2 '-bis- (2- oxazolines), 1,3- phenyl-bis- (2- oxazolines), phenylethylene-maleic anhydride random copolymerization
One kind in thing, succinyl chloride and ethanedioly chloride.
More preferably, organotin catalysts are selected from least one of stannous octoate and dibutyl tin laurate.
Bleaching shellac resin is the excellent natural biological sill of film forming, can be applied to fruit or food fresh keeping row
Industry.
In addition, bleaching shellac resin is the fat and polyester mixture that hydroxy fatty acid and hydroxy sesquiterpene acid are constituted, put down
Contain a carboxyl, three ester bonds, five hydroxyls and an aldehyde radical in each lac molecule, due to containing these groups,
Spontaneous polymerization can occur for lac, or by occurring condensation reaction and chain extension, phase with the functional group such as carboxyl, ester bond, peptide bond, amino
To molecular mass increase, at the same time, the steam breathability of material is accordingly reduced.
Rosin acid is the main component of natural rosin resins, is tricyclic diterpene class compound, contains carboxyl-reactive base
Cause and double bond, react with typical carboxyl and conjugated double bond, in addition to itself being easy to oxidation and isomerization reaction, also with ester
Change, refine, into carboxyl reactions such as salt, decarboxylation, ammonolysis, while also having disproportionation, hydrogenation, addition, the double bond reaction of polymerization.Rosin
Resin acid is the excellent natural biological sill of film forming, can be applied to fruit or food fresh keeping industry.
More preferably, crosslinking agent in sodium citrate, dibenzoyl peroxide, sodium tripolyphosphate and epoxychloropropane extremely
Few one kind.
More preferably, the nano-powder in nano-powder dispersion emulsion is selected from the nanometer kaolinite being modified by coupling agent surface
One kind in soil, nano imvite, nano-graphene, nano aluminium oxide and nano silicon-based oxide (SiOx).Can be with during preparation
Using organic polymeric dispersants as decentralized medium, these nano-powders are mixed with macromolecule dispersing agent, agitated successively, ball
Mill and ultrasonic disperse, obtain nano-powder dispersion emulsion.
Further more preferably, the solid content of nano-powder dispersion emulsion is 40%~50%.In nano-powder dispersion emulsion
Nano-powder can make up coated film it is microcosmic on physical pin or formed sheet intercalation configuration to water vapour molecule produce
Raw iris action, extends the diffusion path of water vapour molecule.
More preferably, dry vegetable oil is selected from least one of tung oil, Chinese catalpa oil and linseed oil.Dry vegetable oil it is main into
Point it is the glyceride of the unrighted acids such as leukotrienes, linoleic acid, is easy to the soft of oxidation drying formation high resilience in atmosphere
Tough solid film, after oxygen in dry vegetable oil absorption air, occurs oxidative polymerization, make in three-dimensional space be distributed it is dry
Property vegetable oil molecule become the molecule of space network and be solidificated in applicator surface, solid-state is changed into by liquid, resistance is formed
Every property is excellent, intensity is high, good toughness barrier film layer.
More preferably, animals and plants wax is selected from least one of beeswax, citrus wax and palm wax.These species it is dynamic
Vegetable wax is the excellent natural biological sill of film forming, can be applied to fruit or food fresh keeping industry.
The main component of animals and plants wax is high-grade aliphatic ester, and hydrophobicity itself is very strong, at normal temperatures in solid-state, can be with
The moisture-vapor transmission of edible film is effectively reduced, safety non-toxic possesses outstanding vapor water barriers performance.
More preferably, the one kind of water-repelling agent in trim,ethylchlorosilane and perfluorooctyl ethylene base dimethoxysilane.
More preferably, alcohol ethers solvent is selected from propylene glycol monomethyl ether, propylene-glycol ethyl ether, propandiol butyl ether, ethylene glycol ethyl ethers ether acetic acid
At least one of ester and n-butanol.
The high-barrier biodegradation material of the present invention is during each component material polymerization reaction, different molecular and function
Roll into a ball interphase interaction and formed with spatial network molecular structure and very fine and close material, reduce high polymer material under glassy state
The motion frequency of segment, reduces the frequency or reduction free volume of free volume appearance between macromolecular chain, reduction is even switched off can
The passage of water supply vapour molecule diffusion, so as to greatly improve the vapor water barriers performance of material.
In addition, the high-barrier biodegradation material of the present invention is coated in behind biodegradable plastic packaging base material surface, can
Dry under field conditions (factors), can also accelerate to complete drying by heating up.Reaction between its each group fractionated molecule or functional group, can also be with
The continuity of time and proceed.The high-barrier biodegradation material of the present invention is mainly derived from natural animal-plant and natural dynamic plant
Thing product and the biodegradable resin prepolymer obtained by microbial fermentation or chemical synthesis, safety non-toxic, manufacturing process
Simply, there is cost advantage, can be applied to biodegradable plastic packaging there is provided excellent vapor water barriers performance, be a kind of environment
Friendly new bio sill.
Fig. 1 is referred to, the preparation method of the high-barrier biodegradation material of an embodiment comprises the following steps：
S100, by the acidifying high protein colloid of 25~35 parts by weight, the biodegradable resin pre-polymerization of 15~20 parts by weight
Thing, the chain extender of 0.5~1.5 parts by weight and water are warming up to 60 DEG C~100 DEG C after mixing, gel is obtained after reaction completely and is combined
Thing, wherein, the mass fraction that water accounts for acidifying high protein colloid is 30%~40%.
More preferably, acidifying high protein colloid is prepared from using following steps：
S110, by animal gelatin albumen or soybean protein isolate by boiling water boiling to denaturation is dehydrated, acid system is carried out afterwards
Hydrolysis process, obtains fat-free high protein after being purified.
S120, fat-free high protein is mixed with water after be ground, the mass ratio of high protein and water is 1：1~1：
2, until D97≤300nm of powder colloid material, obtains being acidified high protein colloid.
Wherein, D97 represents that the cumulative particle sizes distribution number of a sample reaches particle diameter corresponding when 97%.Its physics meaning
Justice is that particle diameter accounts for 97% less than its particle.D97 is commonly used to represent the size indicator of powder thickness.
Specifically, can add each above-mentioned component in reactor, it is warming up to after 60 DEG C~100 DEG C, at the uniform velocity stirs
0.5h~1h, makes each component reaction completely, so that acidifying high protein colloid and biodegradable resin prepolymer are with double helix
Form is wound mutually gel space network structure, becomes gel composite.
S200, the obtained gel composites of step S100 and the albumen enzyme catalyst of 0.02~0.06 parts by weight mixed,
30 DEG C~60 DEG C are cooled to, pretreated gel composite is obtained after reaction completely.
Specifically, after albumen enzyme catalyst is added in gel composite, turn down the temperature of reactor to 30 DEG C~
60 DEG C, 5min~15min is at the uniform velocity stirred afterwards, makes reaction complete.Pretreatment by albumen enzyme catalyst to gel composite,
The activation energy that protein participates in subsequent chemical reaction is reduced, reaction is easier to make for.
S300, the bleaching shellac resin by the obtained pretreated gel composites of step S200 and 35~45 parts by weight
Solution, the rosin acid of 3~7 parts by weight, the crosslinking agent of 0.01~0.07 parts by weight, the organotin of 0.02~0.06 parts by weight
Catalyst is mixed, and boosts to 2.0MPa~3.5MPa, is warming up to 80 DEG C~95 DEG C, and cross-linking modified gel is obtained after reaction completely and is answered
Compound.
More preferably, bleaching shellac resin solution is prepared from using following steps：
S310, Sticklac is crushed successively, screens, rinse, concentration extraction and bleaching, it is former to remove lac
Natural pigment in glue, obtains resin particle glue.
S320, resin particle glue and absolute ethyl alcohol mixed, the mass ratio of resin particle glue and absolute ethyl alcohol is 1：8~1：10,
Obtain bleaching shellac resin solution.
Specifically, after each above-mentioned component is mixed, the pressure of reactor can be adjusted to 2.0MPa~3.5MPa, heated up
To 80 DEG C~95 DEG C, under 100r/min~150r/min stirring condition, 1h~1.5h is stirred, makes reaction complete.
Bleaching shellac resin is the fat and polyester mixture of hydroxy fatty acid and hydroxy sesquiterpene acid, average each lac
Molecule contains a carboxyl, three ester bonds, five hydroxyls and an aldehyde radical, and due to these functional groups, lac can be with step
The functional groups such as carboxyl, ester bond, peptide bond, amino in the pretreated gel composite that S200 is obtained occur chain extension, grafting and
Cross-linking reaction.Rosin acid is tricyclic diterpene class compound, containing carboxyl-reactive gene and double bond, can occur typical carboxyl
With conjugated double bond reaction.By previous reaction, while the increase of material relative molecular mass and cross-linked structure introducing, it passes through
" free volume " passage that molecule segment motion is supplied to water vapour molecule to pass through is greatly decreased and reduced, and makes material water vapour saturating
The property crossed accordingly is reduced.
S400, by the scattered breast of the obtained cross-linking modified gel composites of step S300 and the nano-powder of 2~6 parts by weight
Liquid, the dry vegetable oil of 2~6 parts by weight, the animals and plants wax of 1~3 parts by weight, the water-repelling agent of 1~3 parts by weight, 2~6 parts by weight
Alcohol ethers solvent mix, reaction completely after obtain high-barrier biodegradation material.
Specifically, after each above-mentioned component is mixed, speed is kept stirring for for 300r/min~500r/min, during stirring
Between be 0.5h~1h, make reaction completely, obtain the high-barrier biodegradation material of emulsion form.The emulsion is evenly applied to other
Biodegradable plastic packaging material surface, through drying process, that is, forms the biodegradable film layer of high-barrier.
By be blended introduce nano-powder, can make up coated film it is microcosmic on physical pin, or formed sheet intercalation
Structure produces iris action to water vapour molecule, extends the diffusion path of water vapour molecule.The dry vegetable oil of blended introducing,
Main component is the glyceride of the unrighted acids such as leukotrienes, linoleic acid, is easy to oxidation drying in atmosphere and is formed rich in bullet
Property flexible solid film, after the oxygen in dry vegetable oil absorption air, occur oxidative polymerization, make in three-dimensional space distribution
Dry vegetable oil molecular change be solidificated in applicator surface into the molecule of space network, form that barrier is excellent, intensity
The high, Obstruct membrane of good toughness.The natural animal-plant wax main component of blended introducing is high-grade aliphatic ester, and hydrophobicity itself is non-
It is in solid-state under Chang Qiang, normal temperature, can effectively reduces the moisture-vapor transmission of coating film layer.
High-barrier biodegradation material application prepared by such scheme is coated in the table of biodegradable plastic packaging material product
Face, plastic film (PLA/PBAT composites) specification is：130 × 130 × 0.07mm, coating thickness be 0.010mm~
0.015mm, moisture-vapor transmission test is carried out by gained sample, and test condition is 38 DEG C, humidity 90%RH, and test result is：
Moisture-vapor transmission ＜ 0.24g/m224h, and the barrier function film standard (HG/T higher to barrier
I type function film moisture-vapor transmission≤2g/m is required in 4302-2012)224h, II type function film moisture-vapor transmission
≤4g/m2·24h.As a result show that the high-barrier biodegradation material of the present invention possesses excellent vapor water barriers performance.
In the preparation method of the high-barrier biodegradation material of the present invention, due to the process in each component material polymerization reaction
In, different molecular and functional group's interphase interaction and formed with spatial network molecular structure and very fine and close material, reduction
Free volume occurs between the motion frequency of high polymer material segment under glassy state, reduction macromolecular chain frequency or reduce free body
Product, reduces the passage for being even switched off being available for water vapour molecule to spread, so as to greatly improve the vapor water barriers performance of material.
In addition, the biodegradable plastic packaging film of an embodiment includes above-mentioned high-barrier biodegradation material.
In the biodegradable plastic packaging film including above-mentioned high-barrier biodegradation material of the present invention, due in each component
During material polymerization reaction, different molecular and functional group's interphase interaction and formed with spatial network molecular structure and non-
The motion frequency of high polymer material segment under Chang Zhimi material, reduction glassy state, free volume occurs between reducing macromolecular chain
Frequency or reduce free volume, the passage for being even switched off being available for water vapour molecule to spread is reduced, so as to greatly improve biological drop
Solve the vapor water barriers performance of plastic packaging film.
The present invention is described in further detail below in conjunction with comparative example and specific embodiment.
Embodiment 1
The raw material of the high-barrier biodegradation material of the present embodiment weigh each component by following parts by weight：
28 parts of acidifying glutin colloid, 15 parts of end carboxyl propylene carbonate (PPC) prepolymer, ethylene-methyl acrylate-
0.5 part of GMA terpolymer, 0.02 part of albumen enzyme catalyst, dibutyl tin laurate 0.02
Part, 35 parts of bleaching shellac resin solution, 3 parts of rosin acid, 0.01 part of dibenzoyl peroxide, nano silicon-based oxide
(SiOx) 2 parts of dispersion emulsion, 2 parts of linseed oil, 1 part of beeswax, 1 part of perfluorooctyl ethylene base dimethoxysilane, 2 parts of n-butanol.
The preparation method of the high-barrier biodegradation material of the present embodiment comprises the following steps：
By the acidifying high protein colloid of 28 parts by weight, end carboxyl propylene carbonate (PPC) prepolymer of 15 parts by weight, 0.5
The ethylene-methyl acrylate-glyceryl methacrylate terpolymer and water of parts by weight are warming up to 65 DEG C after mixing,
At the uniform velocity stirring reaction 1h, obtains gel composite, wherein, the mass fraction that water accounts for acidifying high protein colloid is 30%.
Gel composite and the albumen enzyme catalyst of 0.02 parts by weight are mixed, 40 DEG C, at the uniform velocity stirring reaction are cooled to
Stop stirring after 12min, obtain pretreated gel composite.
By pretreated gel composite and the bleaching shellac resin solution of 35 parts by weight, the rosin resin of 3 parts by weight
Acid, the dibutyl tin laurate of the dibenzoyl peroxide of 0.01 parts by weight, 0.02 parts by weight are mixed, and reactor pressure is adjusted to
2.6MPa, temperature rises to 92 DEG C, under 140r/min stirring condition, stirs 1.5h, obtains cross-linking modified gel composite.
By cross-linking modified gel composite and the nano silicon-based oxide of 2 parts by weight (SiOx) dispersion emulsion, 2 parts by weight
Linseed oil, the beeswax of 1 parts by weight, the perfluorooctyl ethylene base dimethoxysilane of 1 parts by weight, the n-butanol of 2 parts by weight are mixed,
Mixing speed is 300r/min, and mixing time is 1h, obtains high-barrier biodegradation material.
Embodiment 2
The raw material of the high-barrier biodegradation material of the present embodiment weigh each component by following parts by weight：
It is acidified 30 parts of glutin colloid, 20 parts of end carboxyl carbon dioxide-base isolation-type TPU prepolymers, styrene-methyl
0.8 part of glycidyl acrylate copolymer, 0.03 part of albumen enzyme catalyst, 0.03 part of stannous octoate, bleaching shellac resin are molten
40 parts of liquid, 5 parts of rosin acid, 0.03 part of sodium citrate, 4 parts of nano imvite dispersion emulsion, 4 parts of tung oil, citrus
2 parts of wax, 2 parts of perfluorooctyl ethylene base dimethoxysilane, 4 parts of propylene-glycol ethyl ether.
The preparation method of the high-barrier biodegradation material of the present embodiment comprises the following steps：
By the acidifying high protein colloid of 30 parts by weight, the end carboxyl carbon dioxide-base isolation-type TPU prepolymers of 20 parts by weight,
The styrene-t glycidyl ester copolymer and water of 0.8 parts by weight are warming up to 75 DEG C after mixing, and at the uniform velocity stir anti-
0.8h is answered, gel composite is obtained, wherein, the mass fraction that water accounts for acidifying high protein colloid is 35%.
Gel composite and the albumen enzyme catalyst of 0.03 parts by weight are mixed, 45 DEG C, at the uniform velocity stirring reaction are cooled to
Stop stirring after 10min, obtain pretreated gel composite.
By pretreated gel composite and the bleaching shellac resin solution of 40 parts by weight, the rosin resin of 5 parts by weight
Acid, the stannous octoate of the sodium citrate of 0.03 parts by weight, 0.03 parts by weight are mixed, and reactor pressure is adjusted to 3.0MPa, temperature liter
To 88 DEG C, under 120r/min stirring condition, 1.2h is stirred, cross-linking modified gel composite is obtained.
By cross-linking modified gel composite and the nano imvite dispersion emulsion of 4 parts by weight, the tung oil of 4 parts by weight, 2 weight
The citrus wax, the perfluorooctyl ethylene base dimethoxysilane of 2 parts by weight, the propylene-glycol ethyl ether of 4 parts by weight of part are mixed,
Mixing speed is 400r/min, and mixing time is 0.8h, obtains high-barrier biodegradation material.
Embodiment 3
The raw material of the high-barrier biodegradation material of the present embodiment weigh each component by following parts by weight：
33 parts of acid soy protein isolate colloid, 25 parts of end carboxyl ethylene carbonate (PEC) prepolymer, styrene-Malaysia
1 part of acid anhydrides random copolymer, 0.04 part of albumen enzyme catalyst, 0.04 part of dibutyl tin laurate, bleaching shellac resin solution
45 parts, 7 parts of rosin acid, 0.05 part of sodium tripolyphosphate, 6 parts of nano aluminium oxide dispersion emulsion, Chinese catalpa oil 6 parts, 3 parts of palm wax,
3 parts of trim,ethylchlorosilane, 6 parts of ethyl cellosolve acetate.
The preparation method of the high-barrier biodegradation material of the present embodiment comprises the following steps：
By the acid soy protein isolate colloid of 33 parts by weight, end carboxyl ethylene carbonate (PEC) pre-polymerization of 25 parts by weight
Thing, the atactic styrene-maleic anhydride copolymer of 1 parts by weight and water are warming up to 85 DEG C after mixing, at the uniform velocity stirring reaction 0.6h,
Gel composite is obtained, wherein, the mass fraction that water accounts for acidifying high protein colloid is 40%.
Gel composite and the albumen enzyme catalyst of 0.04 parts by weight are mixed, 50 DEG C, at the uniform velocity stirring reaction are cooled to
Stop stirring after 6min, obtain pretreated gel composite.
By pretreated gel composite and the bleaching shellac resin solution of 45 parts by weight, the rosin resin of 7 parts by weight
Acid, the dibutyl tin laurate of the sodium tripolyphosphate of 0.05 parts by weight, 0.04 parts by weight are mixed, and reactor pressure is adjusted to
3.3MPa, temperature rises to 83 DEG C, under 100r/min stirring condition, stirs 1h, obtains cross-linking modified gel composite.
By cross-linking modified gel composite and the nano aluminium oxide dispersion emulsion of 6 parts by weight, the Chinese catalpa oil of 6 parts by weight, 3 weight
The palm wax, the trim,ethylchlorosilane of 3 parts by weight, the ethyl cellosolve acetate of 5 parts by weight of part are mixed, and mixing speed is
500r/min, mixing time is 0.6h, obtains high-barrier biodegradation material.
Comparative example 1
Traditional HDPE films, film thickness is 0.015mm.
Comparative example 2
Traditional PVDC films, film thickness is 0.015mm.
Comparative example 3
Biodegradable PLA/PBAT films, film thickness is 0.015mm.
Performance test
High-barrier biodegradation material prepared by embodiment 1~3 is coated in the surface of biodegradable plastic packaging material product,
Plastic film (PLA/PBAT composites) specification is：130 × 130 × 0.07mm, coating thickness is 0.015mm.
According to《GB 1037-88 plastic sheetings and the cup type method of sheet material water vapor permeability test method》Testing example 1~3
The high-barrier biodegradation material of preparation is applied to above-mentioned plastic film and the moisture-vapor transmission of comparative example 1~3.
Test condition is：38 DEG C of temperature, humidity 90%RH.
Test result such as table 1：
Table 1
Can be seen that by the data of table 1 embodiment 1~3 high-barrier biodegradation material moisture-vapor transmission compared with
It is small, show that the high-barrier biodegradation material of embodiment 1~3 possesses excellent vapor water barriers performance.
The moisture-vapor transmission of the thin-film material of comparative example 1~3 is larger, shows that the water of the thin-film material of comparative example 1~3 steams
Gas barrier is poor.
In addition, the moisture-vapor transmission of the high-barrier biodegradation material of embodiment 1~3 is much smaller than comparative example 1~3
The moisture-vapor transmission of thin-film material, shows that the vapor water barriers performance of the high-barrier biodegradation material of embodiment 1~3 is far excellent
In the vapor water barriers performance of the thin-film material of comparative example 1~3.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and it describes more specific and detailed, but simultaneously
Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that coming for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of high-barrier biodegradation material, it is characterised in that the raw material of the high-barrier biodegradation material is included by weight
Measure the following components of part meter：
2. high-barrier biodegradation material according to claim 1, it is characterised in that the biodegradable resin pre-polymerization
Thing is selected from end carboxyl propylene carbonate prepolymer, end carboxyl ethylene carbonate prepolymer, end carboxyl butylene carbonate prepolymer, end
Carboxyl carbon dioxide-base isolation-type TPUE prepolymer, end carboxyl bio-based Nylon pre-polymer and end carboxyl
At least one of bio-based ethylene glycol terephthalate prepolymer.
3. high-barrier biodegradation material according to claim 1, it is characterised in that in the nano-powder dispersion emulsion
Nano-powder be selected from the nano kaoline being modified by coupling agent surface, nano imvite, nano-graphene, nano aluminium oxide
With one kind in nano silicon-based oxide, the solid content of the nano-powder dispersion emulsion is 40%~50%.
4. high-barrier biodegradation material according to claim 1, it is characterised in that the dry vegetable oil is selected from paulownia
At least one of oil, Chinese catalpa oil and linseed oil.
5. high-barrier biodegradation material according to claim 1, it is characterised in that the animals and plants wax be selected from beeswax,
At least one of citrus wax and palm wax.
6. high-barrier biodegradation material according to claim 1, it is characterised in that the water-repelling agent is selected from trimethyl chlorine
One kind in silane and perfluorooctyl ethylene base dimethoxysilane.
7. a kind of preparation method of high-barrier biodegradation material, it is characterised in that comprise the following steps：
By the acidifying high protein colloid of 25~35 parts by weight, the biodegradable resin prepolymer of 15~20 parts by weight, 0.5~
The chain extender and water of 1.5 parts by weight are warming up to 60 DEG C~100 DEG C after mixing, gel composite is obtained after reaction completely, wherein,
The mass fraction that the water accounts for the acidifying high protein colloid is 30%~40%；
The gel composite and the albumen enzyme catalyst of 0.02~0.06 parts by weight are mixed, 30 DEG C~60 DEG C are cooled to, instead
Pretreated gel composite is obtained after answering completely；
By the pretreated gel composite and the bleaching shellac resin solution of 35~45 parts by weight, the pine of 3~7 parts by weight
Botany bar gum acid, the organotin catalysts of the crosslinking agent of 0.01~0.07 parts by weight, 0.02~0.06 parts by weight are mixed, and are boosted to
2.0MPa~3.5MPa, is warming up to 80 DEG C~95 DEG C, cross-linking modified gel composite is obtained after reaction completely；
And by the cross-linking modified gel composite and the nano-powder dispersion emulsion of 2~6 parts by weight, 2~6 parts by weight it is dry
Property vegetable oil, the animals and plants wax of 1~3 parts by weight, the water-repelling agent of 1~3 parts by weight, 2~6 parts by weight alcohol ethers solvent mix,
The high-barrier biodegradation material is obtained after reaction completely.
8. the preparation method of high-barrier biodegradation material according to claim 7, it is characterised in that the high egg of acidifying
White glue body is prepared from using following steps：
Animal gelatin albumen or soybean protein isolate are subjected to Acid hydrolysis processing afterwards by boiling water boiling to denaturation is dehydrated,
Fat-free high protein is obtained after being purified；
And be ground after the fat-free high protein is mixed with water, the mass ratio of the high protein and water is 1：1
~1：2, until D97≤300nm of powder colloid material, obtains being acidified high protein colloid.
9. the preparation method of high-barrier biodegradation material according to claim 7, it is characterised in that the bleaching shellac
Resin solution is prepared from using following steps：
Sticklac is crushed successively, screens, rinse, concentration extraction and bleaching, to remove in the Sticklac
Natural pigment, obtain resin particle glue；
And mix the resin particle glue and absolute ethyl alcohol, the mass ratio of the resin particle glue and the absolute ethyl alcohol is 1：8
~1：10, obtain bleaching shellac resin solution.
10. a kind of biodegradable plastic packaging film, it is characterised in that including high-barrier according to any one of claims 1 to 6
Biodegradation material.
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