CN109181284A - A kind of complete biodegradable high-barrier polyamide-based composite film material and preparation method thereof - Google Patents
A kind of complete biodegradable high-barrier polyamide-based composite film material and preparation method thereof Download PDFInfo
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- CN109181284A CN109181284A CN201810751645.7A CN201810751645A CN109181284A CN 109181284 A CN109181284 A CN 109181284A CN 201810751645 A CN201810751645 A CN 201810751645A CN 109181284 A CN109181284 A CN 109181284A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2400/00—Characterised by the use of unspecified polymers
- C08J2400/16—Biodegradable polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
Abstract
The invention discloses a kind of complete biodegradable high-barrier polyamide-based composite film materials and preparation method thereof, include biomass polyamide material: 50~95 parts, independent carbon source donor material: 0.1~25 part, polyvinyl alcohol: 0.1~40 part.Barrier material of the present invention has that cheap, barrier property is good, relative to existing inorganic fill barrier material, also has biodegradable and processability good, is easy to the advantages of receiving for market.
Description
Technical field
The present invention relates to a kind of complete biodegradable high-barrier polyamide-based composite film materials and preparation method thereof.
Background technique
In recent years, the development of the polymeric packaging material with high-barrier gas or solvent penetration causes people increasingly
More concerns.In high molecular material, some raw materials inherently have preferable barrier property.Such as: EVOH, PVDC, PVA, PA
Deng.Wherein PA has good non-polar gas and hydrocarbon solvent barrier property, and compared to PA, blocking oxygen penetration property is more preferably
EVOH resin, because its high price and it is easy to moisture absorption the defects of reduce its original market application advantage instead.To tie up barrier resins
The cost price of material is reduced on the basis of the barrier property held, many researchers, which use, in recent years has large surface area
With the nano-filled macromolecule of draw ratio.It is longer as that must be undergone when the diffusion of permeable molecule macromolecule existing for nanoscale twins
Path, so these high molecular nanometer sheet layer materials show better barrier property than former macromolecule.Stratified nano materials, such as
The montmorillonite of layer structure is scattered in the plastic basis materials such as polyolefin, its gas barrier properties can be improved, and can effectively block aqueous vapor, oxygen
Gas, solvent diffusion on base material penetrate and improve solvent resistance.But add the high molecule plastic processing fluidity of montmorillonite
It is deteriorated, crystal point is excessive and the disadvantages of unevenly often resulting in the opaque shade deviation of product after processing.Therefore it needs cheap, can give birth to
The complete biodegradable high-barrier polyamide-based composite film material that object is degraded and barrier property is excellent, provides raw matter plastics package row
Industry uses.
Summary of the invention
Based on the above the deficiencies in the prior art, technical problem solved by the invention be to provide it is a kind of cheap, can
Biodegradable and excellent barrier property complete biodegradable high-barrier polyamide-based composite film material and preparation method thereof.
In order to solve the above technical problem, the present invention provides following technical solutions:
A kind of complete biodegradable high-barrier polyamide-based composite film material includes mass component are as follows:
Biomass polyamide material: 50~95 parts；
Independent carbon source donor material: 0.1~25 part；
Polyvinyl alcohol: 0.1~40 part.
Preferably, the biomass polyamide material is nylon 9, nylon 10, nylon 11, nylon 56, nylon 61, nylon
66, one of nylon 69, nylon 410, nylon 510, nylon 512, nylon 610, nylon 612, nylon 8 10, nylon 1010 or
Several mixing.
Preferably, the independent carbon source donor material is starch-based resin, cellulose, albumen base resin, polylactic acid, gathers oneself
One of lactone, polyhydroxyalkanoates, poly butylene succinate, aliphatic aromatic copolyesters, poly (propylene carbonate) or
Several mixing.
Preferably, the polyvinyl alcohol molecule amount 10000~200000, alcoholysis degree 98~99.8.
Preferably, it also comprises the following components: plasticizer: 0.1~10 part；Antioxidant: 0.01~1 part.
Preferably, the plasticizer is polyalcohols, alcamines, amides, chlorine-containing compound class, polyol oligomers species
The mixing of one or more of plasticizer.
Preferably, the antioxidant is antioxidant 1098, antioxidant 1010, antioxidant 245, antioxidant TNP P, antioxidant
One or more of DLTP mixing.
The present invention also provides the preparation methods of above-mentioned complete biodegradable high-barrier polyamide-based composite film material, include
Following steps:
1) each component is passed through to high-speed mixer in mass ratio to be sufficiently mixed uniformly, at 80 DEG C be dried in vacuo 12h~
24h；
2) extruding pelletization is carried out to blend using double screw extruder, each bringing-up section temperature is set separately are as follows: first segment
150 DEG C~250 DEG C, 160 DEG C~250 DEG C of second segment, 170~290 DEG C of third section, the 4th section 180 DEG C~310 DEG C, the 5th section 190
DEG C~330 DEG C；
3) the complete biodegradable high-barrier polyamide-based composite material for completing to be granulated is true under the conditions of 50 DEG C~80 DEG C
The dry 12h of sky~for 24 hours, make moisture content≤0.1wt%, it is female both to have obtained complete biodegradable high-barrier polyamide-based composite material
Grain；
4) complete biodegradable high-barrier polyamide-based composite material master batch is blow molded into using Multi-layer co-extrusion film-blowing equipment
Multi-layer compound film material, setting Multi-layer co-extrusion film-blowing equipment barrier layer extruder first segment, second segment, third section temperature are divided into
150 DEG C~250 DEG C, 170~310 DEG C, 190 DEG C~330 DEG C adjust the inflation of die head air inlet gas pressure intensity control tubular-type embryo
It is 15 DEG C~25 DEG C than for 2:1~3:1, adjusting air ring temperature, obtains complete biodegradable through winding after air cooling and shaping
High-barrier polyamide-based composite film material finished product.
Compared with prior art, barrier material of the present invention is with cheap, barrier property is good, relative to existing
Inorganic fill barrier material, also have biodegradable and processability good, be easy to the advantages of receiving for market.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And it can be implemented in accordance with the contents of the specification, and in order to allow above and other objects, features and advantages of the invention can
It is clearer and more comprehensible, below in conjunction with preferred embodiment, detailed description are as follows.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, the attached drawing to embodiment is simply situated between below
It continues.
Fig. 1 is that the complete biodegradable high-barrier polyamide-based composite film material oxygen of the preferred embodiment of the present invention penetrates
Rate comparison diagram, wherein (a) is complete biodegradable high-barrier polyamide 11, polyvinyl alcohol (molecular weight 100000, alcoholysis degree
98.2) composite film material OTR oxygen transmission rate；It (b) is 56/ polyamide 61 of complete biodegradable high-barrier polyamide, polyvinyl alcohol
(molecular weight 150000, alcoholysis degree 98.2) composite film material OTR oxygen transmission rate；It (c) is complete biodegradable high-barrier polyamide
66/ polyamide 69, polyvinyl alcohol polyvinyl alcohol (molecular weight 200000, alcoholysis degree 98.5) composite film material OTR oxygen transmission rate；
(d) complete biodegradable high-barrier polyamide 810, polyvinyl alcohol (molecular weight 150000, alcoholysis degree 99.8) composite film material
OTR oxygen transmission rate.
Specific embodiment
The following detailed description of a specific embodiment of the invention, as part of this specification, by embodiment come
Illustrate that the principle of the present invention, other aspects of the present invention, feature and its advantage will become apparent by the detailed description.
Embodiment 1
1) in mass ratio by each component
Nylon 9: 95 parts；
Starch-based resin: 4.79 parts；
Polyvinyl alcohol (molecular weight 10000, alcoholysis degree 98): 0.1 part；
Polyol oligomer plasticizer: 0.1 part；
1098:0.01 parts of antioxidant；
It is sufficiently mixed uniformly by high-speed mixer, is dried in vacuo 12h at 80 DEG C.
2) extruding pelletization is carried out to blend using double screw extruder, each bringing-up section temperature is set separately are as follows: first segment
220 DEG C, 240 DEG C of second segment, 260 DEG C of third section, the 4th section 280 DEG C, the 5th section 300 DEG C.
3) the complete biodegradable high-barrier polyamide-based composite material for completing to be granulated is dried in vacuo under the conditions of 50 DEG C
For 24 hours, make moisture content≤0.1wt%, both obtain complete biodegradable high-barrier polyamide-based composite material master batch.
4) complete biodegradable high-barrier polyamide-based composite material master batch is blow molded into using Multi-layer co-extrusion film-blowing equipment
Multi-layer compound film material, setting Multi-layer co-extrusion film-blowing equipment barrier layer extruder first segment, second segment, third section temperature are divided into
220 DEG C, 260 DEG C, 300 DEG C, the blow-up ratio for adjusting die head air inlet gas pressure intensity control tubular-type embryo is 2:1, adjusts vane temperature
Degree be 15 DEG C, after air cooling and shaping through winding obtain complete biodegradable high-barrier polyamide-based composite film material at
Product.
Embodiment 2
1) in mass ratio by each component
10:90 parts of nylon；
Cellulose: 2.99 parts；
Polyvinyl alcohol (molecular weight 50000, alcoholysis degree 98): 5 parts；
Chlorine-containing compound plasticizer: 2 parts；
Antioxidant 1010: 0.01 part；
It is sufficiently mixed uniformly by high-speed mixer, is dried in vacuo 12h at 80 DEG C.
2) extruding pelletization is carried out to blend using double screw extruder, each bringing-up section temperature is set separately are as follows: first segment
250 DEG C, 270 DEG C of second segment, 290 DEG C of third section, the 4th section 310 DEG C, the 5th section 330 DEG C.
3) the complete biodegradable high-barrier polyamide-based composite material for completing to be granulated is dried in vacuo under the conditions of 80 DEG C
12h, makes moisture content≤0.1wt%, has both obtained complete biodegradable high-barrier polyamide-based composite material master batch.
4) complete biodegradable high-barrier polyamide-based composite material master batch is blow molded into using Multi-layer co-extrusion film-blowing equipment
Multi-layer compound film material, setting Multi-layer co-extrusion film-blowing equipment barrier layer extruder first segment, second segment, third section temperature are divided into
250 DEG C, 310 DEG C, 330 DEG C, the blow-up ratio for adjusting die head air inlet gas pressure intensity control tubular-type embryo is 2.5:1, adjusts vane
Temperature be 15 DEG C, after air cooling and shaping through winding obtain complete biodegradable high-barrier polyamide-based composite film material at
Product.
Embodiment 3
1) in mass ratio by each component
Nylon 11: 65 parts；
Starch-based resin: 5 parts；
Cellulose: 2.8 parts；
Polyvinyl alcohol (molecular weight 100000, alcoholysis degree 98.2): 20 parts；
Amide plasticizer: 2 parts；
245:0.2 parts of antioxidant；
It is sufficiently mixed uniformly by high-speed mixer, is dried in vacuo 12h at 80 DEG C.
2) extruding pelletization is carried out to blend using double screw extruder, each bringing-up section temperature is set separately are as follows: first segment
150 DEG C, 160 DEG C of second segment, 170 DEG C of third section, the 4th section 180 DEG C, the 5th section 190 DEG C.
3) the complete biodegradable high-barrier polyamide-based composite material for completing to be granulated is dried in vacuo under the conditions of 50 DEG C
For 24 hours, make moisture content≤0.1wt%, both obtain complete biodegradable high-barrier polyamide-based composite material master batch.
4) complete biodegradable high-barrier polyamide-based composite material master batch is blow molded into using Multi-layer co-extrusion film-blowing equipment
Multi-layer compound film material, setting Multi-layer co-extrusion film-blowing equipment barrier layer extruder first segment, second segment, third section temperature are divided into
150 DEG C, 170 DEG C, 190 DEG C, the blow-up ratio for adjusting die head air inlet gas pressure intensity control tubular-type embryo is 3:1, adjusts vane temperature
Degree be 25 DEG C, after air cooling and shaping through winding obtain complete biodegradable high-barrier polyamide-based composite film material at
Product.
It keeps starch-based resin, cellulose, amide plasticizer, the mass ratio of antioxidant 245 constant, change nylon 11 and gathers
The mass ratio of vinyl alcohol carries out OTR oxygen transmission rate test to obtained composite film material, obtains curve shown in Fig. 1 (a).
Embodiment 4
1) in mass ratio by each component
56:35 parts of nylon；
61:37.5 parts of nylon；
Albumen base resin: 7.8 parts；
Polyvinyl alcohol (molecular weight 150000, alcoholysis degree 98.2): 17.5 parts；
Alcohol amine plasticizer: 2 parts；
P:0.2 parts of antioxidant TNP；
It is sufficiently mixed uniformly by high-speed mixer, is dried in vacuo 12h at 80 DEG C.
2) extruding pelletization is carried out to blend using double screw extruder, each bringing-up section temperature is set separately are as follows: first segment
170 DEG C, 190 DEG C of second segment, 210 DEG C of third section, the 4th section 230 DEG C, the 5th section 250 DEG C.
3) the complete biodegradable high-barrier polyamide-based composite material for completing to be granulated is dried in vacuo under the conditions of 80 DEG C
12h, makes moisture content≤0.1wt%, has both obtained complete biodegradable high-barrier polyamide-based composite material master batch.
4) complete biodegradable high-barrier polyamide-based composite material master batch is blow molded into using Multi-layer co-extrusion film-blowing equipment
Multi-layer compound film material, setting Multi-layer co-extrusion film-blowing equipment barrier layer extruder first segment, second segment, third section temperature are divided into
170 DEG C, 210 DEG C, 250 DEG C, the blow-up ratio for adjusting die head air inlet gas pressure intensity control tubular-type embryo is 2:1, adjusts vane temperature
Degree be 15 DEG C, after air cooling and shaping through winding obtain complete biodegradable high-barrier polyamide-based composite film material at
Product.
It keeps albumen base resin, alcohol amine plasticizer, the mass ratio of antioxidant TNP P constant, changes nylon 56,61 and of nylon
The mass ratio of polyvinyl alcohol carries out OTR oxygen transmission rate test to obtained composite film material, obtains curve shown in Fig. 1 (b).
Embodiment 5
1) in mass ratio by each component
Nylon66 fiber: 40 parts；
Nylon 69: 35 parts；
Polylactic acid: 6.6 parts；
Polyvinyl alcohol (molecular weight 200000, alcoholysis degree 98.5): 15 parts；
Polyol plasticiser: 3 parts；
Anti-oxidant DLTP: 0.4 part；
It is sufficiently mixed uniformly by high-speed mixer, is dried in vacuo 12h at 80 DEG C.
2) extruding pelletization is carried out to blend using double screw extruder, each bringing-up section temperature is set separately are as follows: first segment
190 DEG C, 210 DEG C of second segment, 230 DEG C of third section, the 4th section 250 DEG C, the 5th section 270 DEG C.
3) the complete biodegradable high-barrier polyamide-based composite material for completing to be granulated is dried in vacuo under the conditions of 50 DEG C
For 24 hours, make moisture content≤0.1wt%, both obtain complete biodegradable high-barrier polyamide-based composite material master batch.
4) complete biodegradable high-barrier polyamide-based composite material master batch is blow molded into using Multi-layer co-extrusion film-blowing equipment
Multi-layer compound film material, setting Multi-layer co-extrusion film-blowing equipment barrier layer extruder first segment, second segment, third section temperature are divided into
190 DEG C, 230 DEG C, 270 DEG C, the blow-up ratio for adjusting die head air inlet gas pressure intensity control tubular-type embryo is 2.5:1, adjusts vane
Temperature be 15 DEG C, after air cooling and shaping through winding obtain complete biodegradable high-barrier polyamide-based composite film material at
Product.
It keeps polylactic acid, polyol plasticiser, anti-oxidant DLTP mass ratio constant, changes nylon66 fiber, nylon 69 and poly- second
The mass ratio of enol carries out OTR oxygen transmission rate test to obtained composite film material, obtains curve shown in Fig. 1 (c).
Embodiment 6
1) in mass ratio by each component
410:70 parts of nylon；
Polycaprolactone: 5.6 parts；
Polyvinyl alcohol (molecular weight 10000, alcoholysis degree 98.5): 20 parts；
Polyol oligomer plasticizer: 4 parts；
1098:0.4 parts of antioxidant；
It is sufficiently mixed uniformly by high-speed mixer, is dried in vacuo for 24 hours at 80 DEG C.
2) extruding pelletization is carried out to blend using double screw extruder, each bringing-up section temperature is set separately are as follows: first segment
220 DEG C, 240 DEG C of second segment, 260 DEG C of third section, the 4th section 280 DEG C, the 5th section 300 DEG C.
3) the complete biodegradable high-barrier polyamide-based composite material for completing to be granulated is dried in vacuo under the conditions of 80 DEG C
12h, makes moisture content≤0.1wt%, has both obtained complete biodegradable high-barrier polyamide-based composite material master batch.
4) complete biodegradable high-barrier polyamide-based composite material master batch is blow molded into using Multi-layer co-extrusion film-blowing equipment
Multi-layer compound film material, setting Multi-layer co-extrusion film-blowing equipment barrier layer extruder first segment, second segment, third section temperature are divided into
220 DEG C, 260 DEG C, 300 DEG C, the blow-up ratio for adjusting die head air inlet gas pressure intensity control tubular-type embryo is 3:1, adjusts vane temperature
Degree be 15 DEG C, after air cooling and shaping through winding obtain complete biodegradable high-barrier polyamide-based composite film material at
Product.
Embodiment 7
1) in mass ratio by each component
510:35 parts of nylon；
512:30 parts of nylon；
Polyhydroxyalkanoates: 10.2 parts；
Polyvinyl alcohol (molecular weight 50000, alcoholysis degree 99): 20 parts；
Chlorine-containing compound plasticizer: 4 parts；
Antioxidant 1010: 0.8 part；
It is sufficiently mixed uniformly by high-speed mixer, is dried in vacuo for 24 hours at 80 DEG C.
2) extruding pelletization is carried out to blend using double screw extruder, each bringing-up section temperature is set separately are as follows: first segment
220 DEG C, 240 DEG C of second segment, 260 DEG C of third section, the 4th section 280 DEG C, the 5th section 300 DEG C.
3) the complete biodegradable high-barrier polyamide-based composite material for completing to be granulated is dried in vacuo under the conditions of 80 DEG C
12h, makes moisture content≤0.1wt%, has both obtained complete biodegradable high-barrier polyamide-based composite material master batch.
4) complete biodegradable high-barrier polyamide-based composite material master batch is blow molded into using Multi-layer co-extrusion film-blowing equipment
Multi-layer compound film material, setting Multi-layer co-extrusion film-blowing equipment barrier layer extruder first segment, second segment, third section temperature are divided into
220 DEG C, 260 DEG C, 300 DEG C, the blow-up ratio for adjusting die head air inlet gas pressure intensity control tubular-type embryo is 2:1, adjusts vane temperature
Degree be 15 DEG C, after air cooling and shaping through winding obtain complete biodegradable high-barrier polyamide-based composite film material at
Product.
Embodiment 8
1) in mass ratio by each component
Nylon 610: 30 parts；
Nylon 612: 30 parts；
Poly butylene succinate: 15.2 parts；
Polyvinyl alcohol (molecular weight 100000, alcoholysis degree 99): 20 parts；
Amide plasticizer: 4 parts；
245:0.8 parts of antioxidant；
It is sufficiently mixed uniformly by high-speed mixer, is dried in vacuo for 24 hours at 80 DEG C.
2) extruding pelletization is carried out to blend using double screw extruder, each bringing-up section temperature is set separately are as follows: first segment
150 DEG C, 170 DEG C of second segment, 190 DEG C of third section, the 4th section 210 DEG C, the 5th section 230 DEG C.
3) the complete biodegradable high-barrier polyamide-based composite material for completing to be granulated is dried in vacuo under the conditions of 50 DEG C
For 24 hours, make moisture content≤0.1wt%, both obtain complete biodegradable high-barrier polyamide-based composite material master batch.
4) complete biodegradable high-barrier polyamide-based composite material master batch is blow molded into using Multi-layer co-extrusion film-blowing equipment
Multi-layer compound film material, setting Multi-layer co-extrusion film-blowing equipment barrier layer extruder first segment, second segment, third section temperature are divided into
150 DEG C, 190 DEG C, 230 DEG C, the blow-up ratio for adjusting die head air inlet gas pressure intensity control tubular-type embryo is 2.5:1, adjusts vane
Temperature be 25 DEG C, after air cooling and shaping through winding obtain complete biodegradable high-barrier polyamide-based composite film material at
Product.
Embodiment 9
1) in mass ratio by each component
10:51.5 parts of nylon 8；
Aliphatic aromatic copolyesters: 25 parts；
Polyvinyl alcohol (molecular weight 150000, alcoholysis degree 99.8): 12.5 parts；
Alcohol amine plasticizer: 10 parts；
P:1 parts of antioxidant TNP；
It is sufficiently mixed uniformly by high-speed mixer, is dried in vacuo for 24 hours at 80 DEG C.
2) extruding pelletization is carried out to blend using double screw extruder, each bringing-up section temperature is set separately are as follows: first segment
230 DEG C, 250 DEG C of second segment, 270 DEG C of third section, the 4th section 290 DEG C, the 5th section 310 DEG C.
3) the complete biodegradable high-barrier polyamide-based composite material for completing to be granulated is dried in vacuo under the conditions of 50 DEG C
12h, makes moisture content≤0.1wt%, has both obtained complete biodegradable high-barrier polyamide-based composite material master batch.
4) complete biodegradable high-barrier polyamide-based composite material master batch is blow molded into using Multi-layer co-extrusion film-blowing equipment
Multi-layer compound film material, setting Multi-layer co-extrusion film-blowing equipment barrier layer extruder first segment, second segment, third section temperature are divided into
230 DEG C, 270 DEG C, 310 DEG C, the blow-up ratio for adjusting die head air inlet gas pressure intensity control tubular-type embryo is 3:1, adjusts vane temperature
Degree be 15 DEG C, after air cooling and shaping through winding obtain complete biodegradable high-barrier polyamide-based composite film material at
Product.
It keeps aliphatic aromatic copolyesters, alcohol amine plasticizer, the mass ratio of antioxidant TNP P constant, changes nylon 8 10
With the mass ratio of polyvinyl alcohol, OTR oxygen transmission rate test is carried out to obtained composite film material, obtains curve shown in Fig. 1 (d).
Embodiment 10
1) in mass ratio by each component
Nylon 1010: 50 parts；
Poly (propylene carbonate): 5 parts；
Polyvinyl alcohol (molecular weight 200000, alcoholysis degree 99.8): 40 parts；
Polyol plasticiser: 4 parts；
Anti-oxidant DLTP: 1 part；
It is sufficiently mixed uniformly by high-speed mixer, is dried in vacuo for 24 hours at 80 DEG C.
2) extruding pelletization is carried out to blend using double screw extruder, each bringing-up section temperature is set separately are as follows: first segment
210 DEG C, 230 DEG C of second segment, 250 DEG C of third section, the 4th section 270 DEG C, the 5th section 290 DEG C.
3) the complete biodegradable high-barrier polyamide-based composite material for completing to be granulated is dried in vacuo under the conditions of 80 DEG C
12h, makes moisture content≤0.1wt%, has both obtained complete biodegradable high-barrier polyamide-based composite material master batch.
4) complete biodegradable high-barrier polyamide-based composite material master batch is blow molded into using Multi-layer co-extrusion film-blowing equipment
Multi-layer compound film material, setting Multi-layer co-extrusion film-blowing equipment barrier layer extruder first segment, second segment, third section temperature are divided into
210 DEG C, 250 DEG C, 290 DEG C, the blow-up ratio for adjusting die head air inlet gas pressure intensity control tubular-type embryo is 2:1, adjusts vane temperature
Degree be 15 DEG C, after air cooling and shaping through winding obtain complete biodegradable high-barrier polyamide-based composite film material at
Product.The bound of each raw material cited by the present invention and each raw material of the present invention, section value and technological parameter are (such as temperature
Degree, time etc.) bound, section value can realize the present invention, embodiment numerous to list herein.
The above is a preferred embodiment of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, it is noted that for those skilled in the art, without departing from the principle of the present invention, may be used also
To make several improvement and variation, these, which improve and change, is also considered as protection scope of the present invention.
Claims (8)
1. a kind of complete biodegradable high-barrier polyamide-based composite film material, which is characterized in that include mass component are as follows:
Biomass polyamide material: 50~95 parts；
Independent carbon source donor material: 0.1~25 part；
Polyvinyl alcohol: 0.1~40 part.
2. complete biodegradable high-barrier polyamide-based composite film material as described in claim 1, which is characterized in that described
Biomass polyamide material is nylon 9, nylon 10, nylon 11, nylon 56, nylon 61, nylon66 fiber, nylon 69, nylon 410, Buddhist nun
The mixing of one or more of dragon 510, nylon 512, nylon 610, nylon 612, nylon 8 10, nylon 1010.
3. complete biodegradable high-barrier polyamide-based composite film material as described in claim 1, which is characterized in that described
Independent carbon source donor material be starch-based resin, cellulose, albumen base resin, polylactic acid, polycaprolactone, polyhydroxyalkanoates,
The mixing of one or more of poly butylene succinate, aliphatic aromatic copolyesters, poly (propylene carbonate).
4. complete biodegradable high-barrier polyamide-based composite film material as described in claim 1, which is characterized in that described
Polyvinyl alcohol molecule amount 10000~200000, alcoholysis degree 98~99.8.
5. complete biodegradable high-barrier polyamide-based composite film material as described in claim 1, which is characterized in that also wrap
Include following component: plasticizer: 0.1~10 part；Antioxidant: 0.01~1 part.
6. complete biodegradable high-barrier polyamide-based composite film material as claimed in claim 5, which is characterized in that described
Plasticizer is one of polyalcohols, alcamines, amides, chlorine-containing compound class, polyol oligomers species plasticizer or several
The mixing of kind.
7. complete biodegradable high-barrier polyamide-based composite film material as claimed in claim 5, which is characterized in that described
Antioxidant is mixed for one or more of antioxidant 1098, antioxidant 1010, antioxidant 245, antioxidant TNP P, anti-oxidant DLTP
It closes.
8. the preparation of complete biodegradable high-barrier polyamide-based composite film material as described in any one of claims 1 to 7
Method, which is characterized in that comprise the following steps:
1) each component is passed through to high-speed mixer to be sufficiently mixed uniformly in mass ratio, 12h~for 24 hours is dried in vacuo at 80 DEG C；
2) extruding pelletization is carried out to blend using double screw extruder, each bringing-up section temperature is set separately are as follows: 150 DEG C of first segment
~250 DEG C, 160 DEG C~250 DEG C of second segment, 170~290 DEG C of third section, the 4th section 180 DEG C~310 DEG C, the 5th section 190 DEG C~
330℃；
3) by the complete biodegradable high-barrier polyamide-based composite material for completing to be granulated, vacuum is done under the conditions of 50 DEG C~80 DEG C
Dry 12h~for 24 hours, make moisture content≤0.1wt%, both obtains complete biodegradable high-barrier polyamide-based composite material master batch；
4) complete biodegradable high-barrier polyamide-based composite material master batch is blow molded into multilayer using Multi-layer co-extrusion film-blowing equipment
Composite film material, setting Multi-layer co-extrusion film-blowing equipment barrier layer extruder first segment, second segment, third section temperature are divided into 150
DEG C~250 DEG C, 170~310 DEG C, 190 DEG C~330 DEG C, adjust the blow-up ratio of die head air inlet gas pressure intensity control tubular-type embryo
For 2:1~3:1, adjusting air ring temperature is 15 DEG C~25 DEG C, obtains complete biodegradable height through winding after air cooling and shaping
Obstruct polyamide-based composite film material finished product.
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| CN110982259A (en) * | 2019-12-02 | 2020-04-10 | 东北林业大学 | Completely biodegradable high-barrier polyamide-based composite film material and preparation method thereof |
| CN114410042A (en) * | 2022-01-28 | 2022-04-29 | 孙琇芳 | Polyvinyl alcohol/polyamide slow water-soluble food packaging film |
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