CN109401225A - A kind of biodegradable preservative film and preparation method thereof - Google Patents
A kind of biodegradable preservative film and preparation method thereof Download PDFInfo
- Publication number
- CN109401225A CN109401225A CN201811189636.XA CN201811189636A CN109401225A CN 109401225 A CN109401225 A CN 109401225A CN 201811189636 A CN201811189636 A CN 201811189636A CN 109401225 A CN109401225 A CN 109401225A
- Authority
- CN
- China
- Prior art keywords
- preservative film
- parts
- biodegradable
- temperature
- film according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2401/08—Cellulose derivatives
- C08J2401/26—Cellulose ethers
- C08J2401/28—Alkyl ethers
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0058—Biocides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to biodegradated polymer materal technical fields, more particularly to a kind of biodegradable preservative film and preparation method thereof, raw material is mainly made of 50-65 portions of PBAT, 15-30 portions of modified starches, 20-40 parts of polylactic acid, 3-10 parts of Biodegradable aliphatic-aromatic copolyesters, 3-10 parts of methylhydroxypropylcellulose ethers, 2-8 parts of nano talcs, 0.1-0.5 parts of chain extenders, 0.2-0.8 parts of antioxidant and 0.2-0.6 parts of lubricants.The present invention greatly reduces cost, to be conducive to large-scale production and application while improving preservative film toughness of products, plasticity, intensity and degradability by the synergistic effect of each component.
Description
Technical field
The present invention relates to biodegradated polymer materal technical fields, and in particular to a kind of biodegradable preservative film and its
Preparation method.
Background technique
With the continuous development of China's economy, the demand of the packaging materials such as preservative film is also increasing.Traditional preservative film
Material is mainly derived from the petroleum based materials such as polyethylene (PE), is difficult after discarded processed.If by the way of burning
Reason can then generate a large amount of toxic by-products；If handled by the way of burying, due to conventional petroleum sill degradation cycle
Very long, some is even more than 100 years, this can bring about serious " white pollution " problem.Therefore, environment amenable biology
Degradation material is the hot spot studied at present.
Polylactic acid (PLA) is a kind of thermoplasticity biodegradable material, intensity and modulus with higher, in recent years by people
Be considered as a kind of environmental-friendly packaging material with great potential.But polylactic acid is semi-crystalline polymer, vitrifying
The shortcomings that transition temperature is high, and there are poor toughness, brittleness greatly, poor heat resistance, to affect its processing performance and application；It is another
Thermoplastic biodegradable material is polyadipate/butylene terephthalate (PBAT), has preferable ductility, extension at break
Rate and impact property, but likewise, pure PBAT there is also hardness it is partially soft, film forming is poor the disadvantages of.Starch is that nature is only secondary
In the second largest natural biological copolymer of cellulose, extremely low cost and Wholly-degradable cause people and greatly close
Note.The existing much research in terms of polylactic acid and starch blending material and report both at home and abroad.For example, Chinese patent
CN102408690A discloses a kind of thermoplastic starch modified polylactic acid material, forms starch by simple be directly blended and gathers
The co-mixing system of lactic acid, but starch is incompatible with polylactic acid, co-mixing system interface adhesion is poor, causes product toughness, plastic
Property etc. physical mechanical properties reduce；Chinese patent CN101831155A discloses a kind of preparation side of starch/polylactic acid mixture
Method, used chain extender are to have virose diisocyanate compound, limit its in disposable food packing and
Application in terms of tableware；For another example Chinese patent CN101781448A discloses a kind of enhanced polylactic acid of fully biodegradable
Acid/starch blend preparation method, this method improve the mechanics of blend and resistance to by adding thermoplastic elastic toughener
Hot property, but used thermoplastic elastic toughener is liquid rubber or thermoplastic elastomer (TPE), for not biodegradable composition,
Affect blend can degradable property.Therefore there are still following defects: (1) starch for current starch conversion poly-lactic acid material
The heat resisting temperature of itself is limited, and starch is made in process carbonization to occur and decompose because temperature is excessively high；(2) polylactic acid with
The compatibility of starch is not good enough, causes the physical mechanical properties such as the toughness, intensity, plasticity of material poor.For this purpose, the prior art
Mostly by adding various high-cost auxiliary agents to improve the performance of product, will lead to product in this way, cost has risen considerably, and
And the degradability of material is caused to reduce；In addition, the prior art using coating method increase preservative film anti-microbial property, i.e., at
One layer of antimicrobial coating is coated on the film of type, using solidifying.Although this mode simple process, coating can be with
Environment changes the passage with the time and anti-microbial property is caused to decline, and the antibacterial time limit is short.
Summary of the invention
It is an object of the invention to provide a kind of biodegradable preservative film and its system aiming at the shortcomings in the prior art
Preparation Method, prepared preservative film are obviously improved on plasticity, toughness, intensity and degradability, Er Qieyuan
Various additives dosage is few in material, and modified starch dosage is more, reduces costs while improving product comprehensive performance.
The purpose of the present invention is achieved through the following technical solutions:
A kind of biodegradable preservative film is provided, is mainly made of raw material from the following weight:
Wherein, the modified starch is by 45-60 portions of tapiocas, 45-60 parts of distilled water, 2-8 parts of glycerol and 0.2-1 parts
Made of maleic anhydride is modified by gelatinization.
Wherein, the modified starch is by 45-60 portions of tapiocas, 45-60 parts of distilled water, 2-8 parts of glycerol and 0.2-1 parts
Made of maleic anhydride is modified by gelatinization.By carrying out gelatinization modification to tapioca, para arrowroot is on the one hand substantially increased
The surface compatability and plasticizing capacity of powder, enable it is compatible with polylactic acid and PBAT well, so that improves product can
Plasticity, toughness and tensile strength, another aspect modified starch heat resisting temperature get a promotion, and solve tapioca in process
It is middle that the problem of carbonization is decomposed occurs because temperature is excessively high.Modified starch usage amount of the invention is larger, and raw material is cheap and easy to get, energy
Cost is enough significantly reduced, although the dosage for increasing modified starch will also result in its object while improving product degradability
The decline of mechanical performance is managed, but the present invention can guarantee not influencing product properties by the synergistic effect of other components
Under the premise of, it is reduced cost also.
In above-mentioned technical proposal, a kind of biodegradable preservative film is mainly made of raw material from the following weight:
Further include the antibacterial agent of 0.8-1.5 parts by weight in above-mentioned technical proposal, the antibacterial agent by nisin and
Tea polyphenols are according to weight ratio (2-3): (1-3) is compounded.
In above-mentioned technical proposal, the Biodegradable aliphatic-aromatic copolyester and methylhydroxypropylcellulose ether
Weight ratio is (0.5-2): 1.It is improved using methylhydroxypropylcellulose ether and Biodegradable aliphatic-aromatic copolyester altogether
The plasticity and toughening effect of mixed object, while making it have excellent mechanical performance and processability, both raw materials are all
It is completely biodegradable material, the degradation property without will affect product；Specifically, being conducive to by the amount ratio of the two
The compatibility in blend between each component is improved, the comprehensive performance of product is further increased.
In above-mentioned technical proposal, the Biodegradable aliphatic-aromatic copolyester be poly terephthalic acid-co- oneself two
Sour butanediol ester, poly terephthalic acid-co- ethylene glycol adipate, poly terephthalic acid-co- EGS ethylene glycol succinate and poly-
At least one of terephthalic acid (TPA)-co- succinic acid-butanediol ester.
In above-mentioned technical proposal, the average grain diameter of the nano talc is 50-80nm.The nanoscale of the particle size range is sliding
Mountain flour particle can improve dispersion and interfacial adhesion problem in high temperature resistant substrate, and then be conducive to improve the strong of composite material
Degree and toughness；In addition, also to control the partial size and dosage of nano talc, when dosage is very few, product is not achieved and finally uses
The requirement of performance, when dosage is excessive, because nano-scale particle is easy to influence product due to occurring to reunite when high-temperature fusion is blended
Can, while can also dramatically increase material cost.
In above-mentioned technical proposal, the chain extender is that marque is in ADR-4368C, ADR-4368CS and ADR-4370
At least one.The chain extender can be with the functional group reactions in polylactic acid chain, so that polylactic acid molecule chain forms long-branched knot
Structure increases its molecular weight simultaneously, and the lactic acid composite material finally prepared not only greatly strengthens toughness, but also has better
Thermal stability；The antioxidant is at least one of tert-butylhydroquinone, catechol and hydroquinone；The lubrication
Agent is zinc stearate, N, any one in N'- ethylenebisstearamide and polyethylene wax, lubricant plays improvement polymer
Rheological property effect.
The present invention also provides a kind of above-mentioned preparation methods of biodegradable preservative film, comprising the following steps:
Step a, formula ratio is pressed, under the conditions of 20-25 DEG C, after tapioca and distilled water are mixed and stirred for uniformly, is added
Enter glycerol and maleic anhydride, and be stirred continuously the mixture to form colloidal, is subsequently placed in water-bath or oil bath pan and is added
Heat gelatinization, heating temperature are 85-100 DEG C, and time 10-30min obtains thick colloid, then by drying, crushing, are obtained
It is spare to modified starch；
Step b, formula ratio is pressed, weighs modified starch, PBAT, polylactic acid, biodegradable fatty race-aromatic copolyester respectively
Ester, methylhydroxypropylcellulose ether and nano talc, dry 4-5h at 75-85 DEG C, make the moisture content of each component≤
0.08%, be conducive to each component and carry out dry-mixed and subsequent melt polymerization reaction；Then by drying in addition to nano talc
Component be stirred dry-mixed to uniform, obtain premix, be subsequently added into the chain extender of formula ratio, antioxidant, lubricant and
Antibacterial agent continues to stir evenly, obtains blend；
Step c, screw extruder is added by spout in blend, and the nano talc of drying is added in screw downstream
Enter screw extruder to squeeze out through high-temperature fusion, then be cooled down after Blown Film to get the preservative film is arrived, wherein screw extruder
The temperature of each heating region is as follows:
Screw rod front: 175-180 DEG C, screw rod middle part: 170-175 DEG C, screw rod rear portion: 155-160 DEG C, nozzle temperature 180-
185℃。
In above-mentioned technical proposal, in step a, after thick colloid is toasted 10-30min at 100-120 DEG C, it will dry
Solid be crushed to 100-300 mesh, obtain modified starch.
In above-mentioned technical proposal, in step c, the feeding revolving speed of screw extruder is 0.8-1.4rpm, by the temperature of feeding section
Degree control is at 60-90 DEG C, to prevent the premature melting of chain extender and generation gel.In addition, nano talc is in spiral shell in step c
Screw extruder is added in bar downstream, and other components are to nano-talc powder particles during can avoiding melt blending to the maximum extent
Shearing and dispersion process impact.
Beneficial effects of the present invention:
A kind of biodegradable preservative film of the invention and preparation method thereof, wherein raw material mainly by 50-65 parts of PBAT,
15-30 portions of modified starches, 20-40 parts of polylactic acid, 3-10 parts of Biodegradable aliphatic-aromatic copolyesters, 3-10 parts of methyl hydroxyls
Propyl cellulose ether, 2-8 part nano talc, 0.1-0.5 parts of chain extenders, 0.2-0.8 parts of antioxidant and 0.2-0.6 parts of lubricants
It is made.Compared with prior art, the invention has the following advantages that
(1) present invention carries out gelatinization modification to tapioca using special process, substantially increases the surface of tapioca
Compatibility and plasticizing capacity, enable it is compatible with polylactic acid and PBAT well, to improve the flexibility of product, tension
Intensity and plasticity are stretched, and modified starch heat resisting temperature gets a promotion, makes tapioca in process will not be because of temperature
It spends high and carbonization occurs and decomposes；
(2) present invention further utilizes methylhydroxypropylcellulose ether and Biodegradable aliphatic-aromatic copolyester,
Firm connection layer is formed between fiber and aliphatic-aromatic copolyester, so that the intensity and ductility of material are improved, and this
Two kinds of raw materials are all Biodegradable materials；On the other hand, pass through control modified starch, methylhydroxypropylcellulose ether and biology
Degrading aliphatic-aromatic copolyester three amount ratio, further increases the compatibility in blend between each component；
(3) nano talc is used in inventive formulation, nanoscale talcum powder particle can improve in high temperature resistant base
Dispersion and interfacial adhesion problem in material, and then be conducive to improve the intensity and toughness of composite material；By nano talc in spiral shell
Screw extruder is added in bar downstream, and other components are to nano-talc powder particles during can avoiding melt blending to the maximum extent
Shearing and dispersion process impact；
(4) additionally use chain extender in inventive formulation, in Screw Extrusion, chain extender can in polylactic acid chain
Functional group reactions, so that polylactic acid molecule chain forms long-branched structure, increases its molecular weight simultaneously, the biology finally prepared can
Degradable material not only greatly strengthens toughness, but also has better thermal stability；
(5) it is added to antibacterial agent in inventive formulation, which is dissolved in polylactic acid and PBAT co-mixing system, makes lactic acid chain
Coccus peptide and tea polyphenols are embedded in polymer surfaces securely, coating method compared with prior art, and antibacterial effect is more lasting；
(6) in raw material of the invention, relative to polylactic acid and PBAT, the usage amount of various additives is less, and is modified shallow lake
The content of powder is higher, by the synergistic effect of each component, thus improving preservative film toughness of products, plasticity, intensity and can
While degradability, cost is greatly reduced, and preparation process is simple, easily controllable, be conducive to large-scale production and application.
Specific embodiment
The invention will be further described with the following Examples.
Embodiment 1:
A kind of preservative film of the present embodiment, preparation method are following (following each component is in parts by weight):
Step a, after at 20 °C, 50 portions of tapiocas and 50 parts of distilled water are mixed and stirred for uniformly, 4 parts are added
Glycerol, 0.6 part of maleic anhydride, and it is stirred continuously the mixture to form colloidal；It is subsequently placed in water-bath or oil bath pan and carries out
Heat Gelatinization, heating temperature are 95 DEG C, and time 25min obtains thick colloid；Thick colloid is placed in baking oven, is dried
Dry temperature is 100 DEG C, after toasting 15min, the solid of drying is crushed to 200 mesh, obtains modified starch.
Step b, 20 portions of modified starches, 50 parts of PBAT, 25 parts of polylactic acid, 3 parts of biodegradable fatty race-fragrance are weighed respectively
Race's copolyesters, 5 parts of methylhydroxypropylcellulose ethers and 5 parts of nano talcs (average grain diameter 50nm), dry 4h at 75 DEG C,
Make moisture content≤0.08% of each component；Then the component in addition to nano talc of drying is stirred dry-mixed to equal
It is even, obtain premix；It is subsequently added into 0.2 part of chain extender ADR-4368C, 0.4 part of tert-butylhydroquinone, 0.2 part of stearic acid
Zinc and 1 part of antibacterial agent, continue to stir evenly, obtain blend；
In the step, Biodegradable aliphatic-aromatic copolyester be poly terephthalic acid-co- tetramethylene adipate,
Poly terephthalic acid-co- ethylene glycol adipate and poly terephthalic acid-co- EGS ethylene glycol succinate are 2 according to weight ratio:
The mixture of 2:1 compounding；Antibacterial agent is compounded by nisin and tea polyphenols according to weight ratio 3:1.
Step c, screw extruder is added by spout in blend, and the nano talc of drying is added in screw downstream
Enter screw extruder to squeeze out through high-temperature fusion, then be cooled down after Blown Film to get preservative film is arrived.In the step, Screw Extrusion
The feeding revolving speed of machine is 1.4rpm, by the control of the temperature of feeding section at 60 DEG C, the temperature setting of each heating region of screw extruder
It is as shown in table 1:
The temperature of each heating region of 1. screw extruder of table
Embodiment 2:
A kind of preservative film of the present embodiment, preparation method are following (following each component is in parts by weight):
Step a, under the conditions of 22 DEG C, after 45 portions of tapiocas and 55 parts of distilled water are mixed and stirred for uniformly, 2 parts are added
Glycerol, 0.4 part of maleic anhydride, and it is stirred continuously the mixture to form colloidal；It is subsequently placed in water-bath or oil bath pan and carries out
Heat Gelatinization, heating temperature are 85 DEG C, and time 30min obtains thick colloid；Thick colloid is placed in baking oven, is dried
Dry temperature is 110 DEG C, after toasting 20min, the solid of drying is crushed to 100 mesh, obtains modified starch.
Step b, weigh respectively 15 portions of modified starches, 60 parts of PBAT, 35 parts of polylactic acid, 5 parts of poly terephthalic acid-co- oneself
Naphthalate, 3 parts of methylhydroxypropylcellulose ethers and 6 parts of nano talcs (average grain diameter 70nm), dry at 78 DEG C
Dry 5h, makes moisture content≤0.08% of each component；Then the component in addition to nano talc of drying is stirred dry-mixed
To uniform, premix is obtained；It is subsequently added into 0.1 part of chain extender ADR-4370,0.2 part of hydroquinone, 0.4 part of N, the Asia N'- second
Base bis-stearamides and 1.2 parts of antibacterial agents, continue to stir evenly, obtain blend；
In the step, antibacterial agent is compounded by nisin and tea polyphenols according to weight ratio 1:1.
Step c, screw extruder is added by spout in blend, and the nano talc of drying is added in screw downstream
Enter screw extruder to squeeze out through high-temperature fusion, then be cooled down after Blown Film to get preservative film is arrived.In the step, Screw Extrusion
The feeding revolving speed of machine is 1.0rpm, by the control of the temperature of feeding section at 90 DEG C, the temperature setting of each heating region of screw extruder
It is as shown in table 2:
The temperature of each heating region of 2. screw extruder of table
Embodiment 3:
A kind of preservative film of the present embodiment, preparation method are following (following each component is in parts by weight):
Step a, under the conditions of 25 DEG C, after 60 portions of tapiocas and 45 parts of distilled water are mixed and stirred for uniformly, 8 parts are added
Glycerol, 1 part of maleic anhydride, and it is stirred continuously the mixture to form colloidal；It is subsequently placed in water-bath or oil bath pan and is added
Heat gelatinization, heating temperature are 100 DEG C, and time 10min obtains thick colloid；Thick colloid is placed in baking oven, is dried
Temperature is 120 DEG C, after toasting 10min, the solid of drying is crushed to 230 mesh, obtains modified starch.
Step b, 25 portions of modified starches, 56 parts of PBAT, 30 parts of polylactic acid, 10 parts of biodegradable fatty race-virtues are weighed respectively
Fragrant race's copolyesters, 10 parts of methylhydroxypropylcellulose ethers and 8 parts of nano talcs (average grain diameter 60nm), dry at 80 DEG C
4.5h makes moisture content≤0.08% of each component, is then stirred the component in addition to nano talc of drying dry-mixed
To uniform, premix is obtained, 0.2 part of chain extender ADR-4368C, 0.1 part of chain extender ADR-4370,0.3 part of spy are subsequently added into
Butylhydroquinone, 0.5 part of catechol and 0.6 part of polyethylene wax, continue to stir evenly, obtain blend；
In the step, Biodegradable aliphatic-aromatic copolyester is poly terephthalic acid-co- EGS ethylene glycol succinate
The mixture compounded with poly terephthalic acid-co- succinic acid-butanediol ester according to weight ratio 1:2.
Step c, screw extruder is added by spout in blend, and the nano talc of drying is added in screw downstream
Enter screw extruder to squeeze out through high-temperature fusion, then be cooled down after Blown Film to get preservative film is arrived.In the step, Screw Extrusion
The feeding revolving speed of machine is 0.8rpm, by the control of the temperature of feeding section at 80 DEG C, the temperature setting of each heating region of screw extruder
It is as shown in table 3:
The temperature of each heating region of 3. screw extruder of table
Embodiment 4:
A kind of preservative film of the present embodiment, preparation method are following (following each component is in parts by weight):
Step a, under the conditions of 21 DEG C, after 56 portions of tapiocas and 60 parts of distilled water are mixed and stirred for uniformly, 6 parts are added
Glycerol, 0.2 part of maleic anhydride, and it is stirred continuously the mixture to form colloidal；It is subsequently placed in water-bath or oil bath pan and carries out
Heat Gelatinization, heating temperature are 90 DEG C, and time 15min obtains thick colloid；Thick colloid is placed in baking oven, is dried
Dry temperature is 105 DEG C, after toasting 30min, the solid of drying is crushed to 300 mesh, obtains modified starch；
Step b, 30 portions of modified starches, 65 parts of PBAT, 40 parts of polylactic acid, 8 parts of biodegradable fatty race-fragrance are weighed respectively
Race's copolyesters, 7 parts of methylhydroxypropylcellulose ethers and 3 parts of nano talcs (average grain diameter 80nm), dry 4h at 85 DEG C,
Make moisture content≤0.08% of each component, is then stirred the component in addition to nano talc of drying dry-mixed to equal
It is even, premix is obtained, 0.2 part of chain extender ADR-4368C, 0.2 part of chain extender ADR-4368CS, 0.1 part of chain extension are subsequently added into
It is equal to continue stirring for agent ADR-4370,0.4 part of catechol, 0.2 part of hydroquinone, 0.3 part of zinc stearate and 0.8 part of antibacterial agent
It is even, obtain blend；
In the step, Biodegradable aliphatic-aromatic copolyester is poly terephthalic acid-co- tetramethylene adipate
The mixture compounded with poly terephthalic acid-co- EGS ethylene glycol succinate according to weight ratio 3:2；Antibacterial agent is by streptococcus lactis
Peptide and tea polyphenols are compounded according to weight ratio 2:1.
Step c, screw extruder is added by spout in blend, and the nano talc of drying is added in screw downstream
Enter screw extruder to squeeze out through high-temperature fusion, then be cooled down after Blown Film to get preservative film is arrived.In the step, Screw Extrusion
The feeding revolving speed of machine is 1.2rpm, by the control of the temperature of feeding section at 70 DEG C, the temperature setting of each heating region of screw extruder
It is as shown in table 4:
The temperature of each heating region of 4. screw extruder of table
Following performance detection is carried out respectively to the preservative film of embodiment 1 to 4:
1, tensile strength is tested:
According to the method for GB/T1040.1-2006, the sample of embodiment 1 to 4 is subjected to tensile strength test respectively.
2, elongation at break is tested:
According to the method for GB/T1040.1-2006, the sample of embodiment 1 to 4 is subjected to elongation at break test respectively.
3, tearing strength test:
According to the method for GB/T16578.1-2008, the sample of embodiment 1 to 4 is subjected to tearing strength test respectively.
4, degradation property is tested:
The sample of embodiment 1 to 4 is used into mounding respectively, dry known weight (W1) the sample embedment to constant weight is contained
Have and keep high humility in the containers of mixtures such as sand, gardens soil, be protected from light, after a period of time, takes out soil and bury sample, clean table
Face soil, it is dry to constant weight (W2), degradation rate: degradation rate=(W1-W2)/W1 × 100% is calculated according to calculation formula.
Test result is as shown in table 5:
The performance test of the preservative film of 5. embodiment 1 to 4 of table
It follows that preservative film of the invention has excellent plasticity, toughness, intensity and degradability, Er Qieyuan
Various additives dosage is few in material, and modified starch dosage is more, reduces costs while improving product properties.
The present embodiment is merely illustrative of the technical solution of the present invention, rather than limiting the scope of the invention, although ginseng
The present invention is explained in detail according to preferred embodiment, those skilled in the art should understand that, it can be to the present invention
Technical solution be modified or replaced equivalently, without departing from the spirit and scope of technical solution of the present invention.
Claims (10)
1. a kind of biodegradable preservative film, it is characterised in that: be mainly made of raw material from the following weight:
Wherein, the modified starch is by 45-60 portions of tapiocas, 45-60 parts of distilled water, 2-8 parts of glycerol and 0.2-1 parts of Malaysias
Made of acid anhydrides is modified by gelatinization.
2. a kind of biodegradable preservative film according to claim 1, it is characterised in that: mainly by the original of following parts by weight
Material is made:
3. a kind of biodegradable preservative film according to claim 1 or 2, it is characterised in that: further include 0.8-1.5 weight
The antibacterial agent of part, the antibacterial agent is by nisin and tea polyphenols according to weight ratio (2-3): (1-3) is compounded.
4. a kind of biodegradable preservative film according to claim 1, it is characterised in that: the biodegradable fatty race-
The weight ratio of aromatic copolyester and methylhydroxypropylcellulose ether is (0.5-2): 1.
5. a kind of biodegradable preservative film according to claim 1, it is characterised in that: the nano talc is averaged
Partial size is 50-80nm.
6. a kind of biodegradable preservative film according to claim 1, it is characterised in that: the biodegradable fatty race-
Aromatic copolyester be poly terephthalic acid-co- tetramethylene adipate, poly terephthalic acid-co- ethylene glycol adipate,
At least one of poly terephthalic acid-co- EGS ethylene glycol succinate and poly terephthalic acid-co- succinic acid-butanediol ester.
7. a kind of biodegradable preservative film according to claim 1, it is characterised in that: the chain extender is marque
For at least one of ADR-4368C, ADR-4368CS and ADR-4370；The antioxidant is tert-butylhydroquinone, adjacent benzene
At least one of diphenol and hydroquinone；The lubricant is zinc stearate, N,N' ethylene bis stearmide and polyethylene
Any one in wax.
8. a kind of preparation method of biodegradable preservative film as described in claim 3 to 7 any one, it is characterised in that:
The following steps are included:
Step a, formula ratio is pressed, under the conditions of 20-25 DEG C, after tapioca and distilled water are mixed and stirred for uniformly, is added sweet
Oil and maleic anhydride, and it is stirred continuously the mixture to form colloidal, it is subsequently placed in water-bath or oil bath pan and carries out heating paste
Change, heating temperature is 85-100 DEG C, and time 10-30min obtains thick colloid, then by drying, crushing, is changed
Property starch, it is spare；
Step b, press formula ratio, weigh respectively modified starch, PBAT, polylactic acid, Biodegradable aliphatic-aromatic copolyester,
Methylhydroxypropylcellulose ether and nano talc dry 4-5h at 75-85 DEG C, make moisture content≤0.08% of each component,
Then the component in addition to nano talc of drying is stirred dry-mixed to uniform, obtains premix, is subsequently added into and matches
Chain extender, antioxidant, lubricant and the antibacterial agent just measured, continue to stir evenly, obtain blend；
Step c, screw extruder is added by spout in blend, and spiral shell is added in screw downstream in the nano talc of drying
Bar extruder is squeezed out through high-temperature fusion, is then cooled down after Blown Film to get the preservative film is arrived, wherein screw extruder respectively adds
The temperature of thermal region is as follows:
Screw rod front: 175-180 DEG C, screw rod middle part: 170-175 DEG C, screw rod rear portion: 155-160 DEG C, nozzle temperature 180-185
℃。
9. a kind of preparation method of biodegradable preservative film according to claim 8, it is characterised in that:, will in step a
After thick colloid toasts 10-30min at 100-120 DEG C, the solid of drying is crushed to 100-300 mesh, obtains modified shallow lake
Powder.
10. a kind of preparation method of biodegradable preservative film according to claim 8, it is characterised in that: in step c,
The feeding revolving speed of screw extruder is 0.8-1.4rpm, and the temperature of feeding section is controlled at 60-90 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811189636.XA CN109401225B (en) | 2018-10-12 | 2018-10-12 | Biodegradable preservative film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811189636.XA CN109401225B (en) | 2018-10-12 | 2018-10-12 | Biodegradable preservative film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109401225A true CN109401225A (en) | 2019-03-01 |
| CN109401225B CN109401225B (en) | 2022-09-30 |
Family
ID=65467776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811189636.XA Active CN109401225B (en) | 2018-10-12 | 2018-10-12 | Biodegradable preservative film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109401225B (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109929228A (en) * | 2019-04-17 | 2019-06-25 | 谷水英 | Green biodegradable plastics film and its processing technology |
| CN110511544A (en) * | 2019-09-06 | 2019-11-29 | 三明百事达淀粉有限公司 | A kind of biodegradable breathable composite film and preparation method thereof |
| CN111361256A (en) * | 2020-04-08 | 2020-07-03 | 保定茂华塑料制品有限公司 | Biodegradable packaging film special for aviation and preparation method thereof |
| CN111719341A (en) * | 2020-06-27 | 2020-09-29 | 福建益百利包装材料有限公司 | PLA (polylactic acid) film coated paper and production process thereof |
| CN112708246A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Multi-component biodegradable mulching film and preparation method thereof |
| CN112876745A (en) * | 2021-02-04 | 2021-06-01 | 杭州之西科技有限公司 | Antibacterial biodegradable tableware and preparation method thereof |
| CN112940474A (en) * | 2021-02-04 | 2021-06-11 | 杭州之西科技有限公司 | Antibacterial puncture-resistant biodegradable packaging bag and preparation method thereof |
| CN113172975A (en) * | 2021-04-06 | 2021-07-27 | 温州银润包装有限公司 | Multilayer composite co-extrusion film and manufacturing process thereof |
| CN113234307A (en) * | 2021-06-29 | 2021-08-10 | 山东农业大学 | Full-degradable antibacterial food packaging film and preparation method thereof |
| CN113561590A (en) * | 2020-04-29 | 2021-10-29 | 广州市同源塑料制品有限公司 | Anaerobic fermentation co-extrusion degradation bag and preparation method thereof |
| CN114410078A (en) * | 2022-01-26 | 2022-04-29 | 上海海洋大学 | Slow-release degradable antibacterial preservative film and preparation method thereof |
| WO2022198282A1 (en) * | 2021-03-26 | 2022-09-29 | Great Wrap Pty Ltd | Film and method |
| CN115433442A (en) * | 2022-10-18 | 2022-12-06 | 扬州大学 | Biodegradable tough composite material and preparation method thereof |
| CN115477776A (en) * | 2022-09-28 | 2022-12-16 | 上海同新服材新材料科技有限公司 | Starch-based degradable antibacterial preservative film and preparation method and application thereof |
| CN115519809A (en) * | 2022-09-28 | 2022-12-27 | 广东汇发塑业科技有限公司 | Preparation method of high-barrier biodegradable mulching film and prepared mulching film |
| CN115678231A (en) * | 2022-11-14 | 2023-02-03 | 上海经海纬象生物材料有限公司 | Degradable heat shrinkable film and preparation method thereof |
| CN116875004A (en) * | 2023-08-23 | 2023-10-13 | 青岛周氏塑料包装有限公司 | PBAT master batch, preparation method thereof and PBAT preservative film |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860462A (en) * | 2015-01-23 | 2016-08-17 | 深圳王子新材料股份有限公司 | Polylactic acid based composite material and preparation method and application thereof |
| CN106751629A (en) * | 2017-01-24 | 2017-05-31 | 威海共达塑胶化工制品有限公司 | Complete biodegradable preservative film and preparation method thereof |
| CN106832807A (en) * | 2016-12-29 | 2017-06-13 | 武汉华丽生物股份有限公司 | A kind of controllable full-degradable mulch film of cellulose enhancing starch and preparation method thereof |
| CN106922799A (en) * | 2015-12-29 | 2017-07-07 | 青岛智通四海家具设计研发有限公司 | A kind of shrimps preservative film |
| CN108219396A (en) * | 2017-12-27 | 2018-06-29 | 杨红梅 | A kind of biodegradable polymer blend and its application |
-
2018
- 2018-10-12 CN CN201811189636.XA patent/CN109401225B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860462A (en) * | 2015-01-23 | 2016-08-17 | 深圳王子新材料股份有限公司 | Polylactic acid based composite material and preparation method and application thereof |
| CN106922799A (en) * | 2015-12-29 | 2017-07-07 | 青岛智通四海家具设计研发有限公司 | A kind of shrimps preservative film |
| CN106832807A (en) * | 2016-12-29 | 2017-06-13 | 武汉华丽生物股份有限公司 | A kind of controllable full-degradable mulch film of cellulose enhancing starch and preparation method thereof |
| CN106751629A (en) * | 2017-01-24 | 2017-05-31 | 威海共达塑胶化工制品有限公司 | Complete biodegradable preservative film and preparation method thereof |
| CN108219396A (en) * | 2017-12-27 | 2018-06-29 | 杨红梅 | A kind of biodegradable polymer blend and its application |
Non-Patent Citations (6)
| Title |
|---|
| 段久芳: "《天然高分子材料》", 30 September 2016 * |
| 潘道东: "《功能性食品添加剂》", 31 January 2006 * |
| 王文广: "《塑料配方设计》", 30 September 1998 * |
| 许冬生: "《纤维素衍生物》", 31 January 2001 * |
| 谢圣英: "《塑料材料》", 31 January 2010 * |
| 谭登峰: "木薯淀粉反应共混改性及马来酸淀粉酯/聚乳酸复合材料的研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109929228A (en) * | 2019-04-17 | 2019-06-25 | 谷水英 | Green biodegradable plastics film and its processing technology |
| CN110511544B (en) * | 2019-09-06 | 2021-06-11 | 三明百事达淀粉有限公司 | Biodegradable breathable composite membrane and preparation method thereof |
| CN110511544A (en) * | 2019-09-06 | 2019-11-29 | 三明百事达淀粉有限公司 | A kind of biodegradable breathable composite film and preparation method thereof |
| CN112708246B (en) * | 2019-10-25 | 2022-12-09 | 中国石油化工股份有限公司 | Multi-component biodegradable mulching film and preparation method thereof |
| CN112708246A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Multi-component biodegradable mulching film and preparation method thereof |
| CN111361256A (en) * | 2020-04-08 | 2020-07-03 | 保定茂华塑料制品有限公司 | Biodegradable packaging film special for aviation and preparation method thereof |
| CN113561590A (en) * | 2020-04-29 | 2021-10-29 | 广州市同源塑料制品有限公司 | Anaerobic fermentation co-extrusion degradation bag and preparation method thereof |
| CN111719341A (en) * | 2020-06-27 | 2020-09-29 | 福建益百利包装材料有限公司 | PLA (polylactic acid) film coated paper and production process thereof |
| CN112940474B (en) * | 2021-02-04 | 2022-04-12 | 杭州之西科技有限公司 | Antibacterial puncture-resistant biodegradable packaging bag and preparation method thereof |
| CN112940474A (en) * | 2021-02-04 | 2021-06-11 | 杭州之西科技有限公司 | Antibacterial puncture-resistant biodegradable packaging bag and preparation method thereof |
| CN112876745A (en) * | 2021-02-04 | 2021-06-01 | 杭州之西科技有限公司 | Antibacterial biodegradable tableware and preparation method thereof |
| WO2022198282A1 (en) * | 2021-03-26 | 2022-09-29 | Great Wrap Pty Ltd | Film and method |
| CN113172975A (en) * | 2021-04-06 | 2021-07-27 | 温州银润包装有限公司 | Multilayer composite co-extrusion film and manufacturing process thereof |
| CN113234307A (en) * | 2021-06-29 | 2021-08-10 | 山东农业大学 | Full-degradable antibacterial food packaging film and preparation method thereof |
| CN114410078A (en) * | 2022-01-26 | 2022-04-29 | 上海海洋大学 | Slow-release degradable antibacterial preservative film and preparation method thereof |
| CN115477776A (en) * | 2022-09-28 | 2022-12-16 | 上海同新服材新材料科技有限公司 | Starch-based degradable antibacterial preservative film and preparation method and application thereof |
| CN115519809A (en) * | 2022-09-28 | 2022-12-27 | 广东汇发塑业科技有限公司 | Preparation method of high-barrier biodegradable mulching film and prepared mulching film |
| CN115433442A (en) * | 2022-10-18 | 2022-12-06 | 扬州大学 | Biodegradable tough composite material and preparation method thereof |
| CN115433442B (en) * | 2022-10-18 | 2023-10-20 | 扬州大学 | Biodegradable tough composite material and preparation method thereof |
| CN115678231A (en) * | 2022-11-14 | 2023-02-03 | 上海经海纬象生物材料有限公司 | Degradable heat shrinkable film and preparation method thereof |
| CN116875004A (en) * | 2023-08-23 | 2023-10-13 | 青岛周氏塑料包装有限公司 | PBAT master batch, preparation method thereof and PBAT preservative film |
| CN116875004B (en) * | 2023-08-23 | 2024-03-26 | 青岛周氏塑料包装有限公司 | PBAT master batch, preparation method thereof and PBAT preservative film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109401225B (en) | 2022-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109401225A (en) | A kind of biodegradable preservative film and preparation method thereof | |
| CN112876745B (en) | Antibacterial biodegradable tableware and preparation method thereof | |
| CN109777048B (en) | Biomass composite material for toothbrush handle and preparation method thereof | |
| CN108795001B (en) | Biodegradable polymer composition and application thereof | |
| CN104119647B (en) | A kind of high-content of starch complete biodegradable composition and preparation method thereof | |
| CN112111133A (en) | Preparation method of polybutylene terephthalate adipate/polylactic acid/starch ternary blending film blowing resin | |
| WO2017121242A1 (en) | Plasticised biodegradable polyester film and preparation method therefor | |
| WO2008028356A1 (en) | Inorganic material combination reinforced, heat-resistant biodegradable masterbatch pellets and its preparation | |
| CN102653601A (en) | Preparation method of completely biodegradable plastic resin and film products thereof | |
| CN113845621B (en) | Compatibilizer and high-starch-content full-biodegradable film adopting compatibilizer | |
| CN104592730B (en) | A kind of polylactic acid/polyester alloy and preparation method thereof | |
| Castaño et al. | Physical, chemical and mechanical properties of pehuen cellulosic husk and its pehuen-starch based composites | |
| JP2002523597A (en) | PVA-containing composition | |
| CN110835417A (en) | Barrier degradable antibacterial food preservative film and preparation method and application thereof | |
| CN109401239B (en) | Biodegradable material for preservation box, preservation box and preparation method of biodegradable material | |
| CN1793229A (en) | Complete degradable material with polyalctic as carrier and preparation process thereof | |
| CN102250389B (en) | Biodegradable polymer material compatibilized and blended by lignocellulose and preparation method thereof | |
| Lim et al. | Structure and properties of biodegradable gluten/aliphatic polyester blends | |
| CN114889285A (en) | Low-temperature heat-sealing biodegradable composite film and preparation process thereof | |
| CN103183937B (en) | A kind of modified polylactic acid composite material and preparation method thereof | |
| CN113214615B (en) | Ternary complete biodegradable film and preparation method thereof | |
| Osman et al. | Effects of durian seed flour on processing torque, tensile, thermal and biodegradation properties of polypropylene and high density polyethylene composites | |
| CN103788603A (en) | Polylactic acid bidirectional stretching matte thin film and preparation method thereof | |
| CN112724622A (en) | Modified PGA material compatibilized by adopting intercalation structure and preparation method thereof | |
| CN102604344B (en) | Polycaprolactone/poly (butylene succinate) composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220909 Address after: 528000 Workshop 3 (Residence Declaration) Applicant after: GUANGDONG JUSU TECHNOLOGY Co.,Ltd. Address before: No. 2, Chenjieming Factory Building, Xibiantang Development Zone, Xi'an Village, Danzao Town, Nanhai District, Foshan City, Guangdong Province, 528000 Applicant before: GUANGDONG HUATENG BIOLOGICAL Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |