阅读说明：本技术 一种生物可降解透气复合膜及其制备方法 (A kind of biodegradable breathable composite film and preparation method thereof ) 是由 林奇 彭超 吴惠民 邓德鸿 钟丽娟 黄水兰 于 2019-09-06 设计创作，主要内容包括：本发明涉及可降解透气复合膜技术领域,特别涉及一种生物可降解透气复合膜及其制备方法,其中,所述一种深恶可降解透气复合膜包括以下制备原料：PE树脂、变性多孔淀粉、PBAT树脂、相容剂、润滑剂、耐候剂、开口剂。本发明提供的一种生物可降解透气复合膜,采用PE和PBAT作为基体树脂,利用变性多孔淀粉的多孔和可生物降解特性,开发出一种生物可降解透气复合膜,解决传统透气复合膜孔洞孔径不均匀、透气性能不佳、无法降解等缺点,可广泛应用于果蔬、海鲜贮藏、运输等领域。(The present invention relates to degradable breathable composite film technical fields, in particular to a kind of biodegradable breathable composite film and preparation method thereof, wherein, it includes following preparing raw material that described one kind, which has a horror of degradable breathable composite film: PE resin, denaturation porous-starch, PBAT resin, compatilizer, lubricant, weather resisting agent, opening agent.A kind of biodegradable breathable composite film provided by the invention, using PE and PBAT as matrix resin, utilize the porous and biodegradability properties of denaturation porous-starch, develop a kind of biodegradable breathable composite film, it solves that traditional gas permeable composite membrane hole aperture is uneven, permeability is bad, the disadvantages of can not degrading, can be widely applied to the fields such as fruits and vegetables, seafood storage, transport.)

1. a kind of biodegradable breathable composite film, which is characterized in that prepare raw material including following: PE resin, the porous shallow lake of denaturation Powder, PBAT resin, compatilizer, lubricant, weather resisting agent, opening agent.

2. biodegradable breathable composite film according to claim 1, which is characterized in that the original including following parts by weight Material:

3. biodegradable breathable composite film according to claim 1 or 2, it is characterised in that: the denaturation porous-starch The preparation method comprises the following steps:

S100, porous-starch and water are added in reaction vessel and stirred, obtain starch suspension；

S200, it after starch suspension is heated to 50~70 DEG C while stirring, sequentially adds acetic anhydride and toluene-4-sulfonic acid stirs It mixes and reacts, obtain reaction product A；

S300, pH=7.1~7.8 for adjusting reaction product A, and 50~60 DEG C are adjusted the temperature to, it adds crosslinking agent and carries out instead It answers, obtains reaction product B；

S400, adjust reaction product B pH to neutrality after, washing, drying, crush obtain denaturation porous-starch.

4. biodegradable breathable composite film according to claim 3, it is characterised in that: the preparation side of the porous-starch Method are as follows:

S110, cassava ative starch and water are added in reaction vessel and stir to get suspension；

S120, by suspension 40~60 DEG C at a temperature of, while stirring heating make starch gelatinization, obtain gelatinized starch；

S130, it is freezed at a temperature of gelatinized starch is placed in -5 DEG C；

S140, the sample after freezing is taken out, acetone is added and is stirred, impregnates, then rotated and steam under the conditions of 50-80 DEG C Porous-starch can be obtained in hair, re-dry, grinding.

5. biodegradable breathable composite film according to claim 1, it is characterised in that: the PE resin is that blown film grade is low Density polyethylene.

6. biodegradable breathable composite film according to claim 1, it is characterised in that: the PBAT resin is to gather oneself two Acid/butylene terephthalate.

7. biodegradable breathable composite film according to claim 1, it is characterised in that: the lubricant is PE wax, firmly At least one of resin acid, EBS.

8. biodegradable breathable composite film according to claim 1, it is characterised in that: the compatilizer is POE-g- At least one of MAH, PE-g-MAH, EVA-g-MAH；The weather resisting agent is antioxidant 168 and ultraviolet absorbing agent UV531 Mixture.

9. biodegradable breathable composite film according to claim 1, it is characterised in that: the opening agent is titanium dioxide At least one of inorganic opening agent of silicon, talcum powder.

10. a kind of preparation method of -9 described in any item biodegradable breathable composite films according to claim 1, feature exist In, comprising the following steps:

Step 1: denaturation porous-starch, PE resin, PBAT resin, compatilizer, lubricant, weather resisting agent and opening agent are mixed simultaneously Discharging, obtains biodegradable breathable composite film mixture；

Step 2: after the biodegradable breathable composite film mixture is carried out melt blending in mixer, in twin-screw It squeezes out machine and carries out melting extrusion, obtain biodegradable breathable composite film modified materials；

It is filmed Step 3: the biodegradable breathable composite film modified materials are added in inflation film manufacturing machine, obtains the biology Degradable breathable composite film.

Technical field

The present invention relates to degradable breathable composite film technical field, in particular to a kind of biodegradable breathable composite film and Preparation method.

Background technique

In recent years, with the rapid development of logistics industry, fresh fruit of vegetables and seafood enter people's life also slowly from impossible Become possible, and this is also just being to rely on the more and more mature of preservation technology, and extend fruits and vegetables and seafood storage life and shelf Again and fresh-keeping packaging material, that is, breathable composite film has close relationship for the preservation technology of phase.

Traditional ventilated membrane mainly use inorganic mineral powder filling PE material preparation, ventilative principle be using inorganic particle with Interfacial separation between resin forms the hole for reaching certain pore size to reach ventilative purpose, this is easy for due to inorganic particle Reunion cause ventilated membrane pore-size distribution uneven, addition inorganic mineral powder easily causes stress concentration, causes ventilated membrane gas permeability Can be bad, and traditional gas permeable film is mostly disposable and is unable to natural degradation, is caused to form white garbage to environment Pollution.

Summary of the invention

Breathe freely that membrane aperture is uneven, permeability is bad in traditional ventilated membrane to solve to refer in above-mentioned background technique and The problem of can not degrading, the present invention provide a kind of biodegradable breathable composite film, including following prepare raw material: PE resin becomes Property porous-starch, PBAT resin, compatilizer, lubricant, weather resisting agent, opening agent.

On the basis of above scheme, further, the raw material including following parts by weight:

On the basis of above scheme, further, it is described denaturation porous-starch the preparation method comprises the following steps:

S100, porous-starch and water are added in reaction vessel and stirred, the water preferably uses distilled water, and the stirring is excellent It is selected as that porous-starch and water are stirred to obtain starch suspension；

S200, after starch suspension is heated to 50~70 DEG C while stirring, the heating method is preferably heating water bath, Moreover, which is preferably transferred to above-mentioned starch suspension in three-necked flask and carries out water-bath while stirring and add Heat, sequentially adds acetic anhydride and toluene-4-sulfonic acid is stirred and reacted, it is described sequentially add acetic anhydride and toluene-4-sulfonic acid after Stirring preferably be sufficiently stirred and 0.5~3h of sustained response, obtain reaction product A；

S300, pH=7.1~7.8 for adjusting reaction product A, the reality that pH value is adjusted in this step is preferably anhydrous slufuric acid Sodium and sodium hydroxide, and 50~60 DEG C are adjusted the temperature to, it adds crosslinking agent and is reacted, the crosslinking agent is preferably crosslinking agent CL, the reaction time are preferably 2~4h, obtain reaction product B；

S400, adjust reaction product B pH to neutrality after, washing, drying, crush obtain denaturation porous-starch, this step In, the reagent for adjusting pH is preferably sodium dihydrogen citrate.

On the basis of above scheme, further, the porous-starch the preparation method comprises the following steps:

S110, cassava ative starch and water are added in reaction vessel and are stirred, the water preferably uses distilled water, described to stir It mixes and preferably cassava ative starch and water is stirred, and obtain suspension；

S120, by suspension 40~60 DEG C at a temperature of, while stirring heating make starch gelatinization, obtain gelatinized starch, The time of the gelatinization is preferably 30~60min, and preferably carries out 20~40min of heat preservation again after being gelatinized；

S130, it is freezed at a temperature of gelatinized starch is placed in -5 DEG C, the time of the freezing is preferably 48h；

S140, the sample after freezing is taken out, acetone is added and is stirred, impregnates, the acetone is preferably that volume is dense Degree is 20% acetone soln, and continues 3~5h of stirring；Rotary evaporation under the conditions of 50-80 DEG C again, re-dry, grinding Porous-starch is obtained, the rotary evaporation preferably carries out at 50~80 DEG C of heating water bath.

On the basis of above scheme, further, the PE resin is blown film grade low density polyethylene (LDPE) (LDPE).

On the basis of above scheme, further, the PE resin is preferably that melt flow rate (MFR) is 2.8g/10min, Density 0.92g/cm³PE resin be blown film grade low density polyethylene (LDPE) (LDPE).

On the basis of above scheme, further, the PBAT resin is polyadipate/butylene terephthalate.

On the basis of above scheme, further, the PBAT resin is preferably that melt flow rate (MFR) is 2~5g/ 10min, polyadipate/butylene terephthalate of Relative biological degradation rate >=90%.

On the basis of above scheme, further, the lubricant is at least one of PE wax, stearic acid, EBS.

On the basis of above scheme, further, the compatilizer is POE-g-MAH, PE-g-MAH, EVA-g-MAH At least one of；The weather resisting agent is the mixture of antioxidant 168 and ultraviolet absorbing agent UV531.

On the basis of above scheme, further, the weight ratio of the antioxidant 168 and UV531 is (1~5): 1.

On the basis of above scheme, further, the opening agent is silica, in the inorganic opening agent of talcum powder It is at least one.

The present invention provides the preparation method of biodegradable breathable composite film described in one kind, comprising the following steps:

Step 1: denaturation porous-starch, PE resin, PBAT resin, compatilizer, lubricant, weather resisting agent and opening agent are mixed Merge discharging, obtains biodegradable breathable composite film mixture；

Step 2: after the biodegradable breathable composite film mixture is carried out melt blending in mixer, double Screw Extrusion machine carries out melting extrusion, obtains biodegradable breathable composite film modified materials；

It is filmed, obtains described Step 3: the biodegradable breathable composite film modified materials are added in inflation film manufacturing machine Biodegradable breathable composite film.

On the basis of above scheme, further, in the step 2, the running parameter of the mixer are as follows: close Refining temperature is 60~100 DEG C, and screw speed is 150~300r/min；The running parameter of double screw extruder are as follows: area's temperature is 50~65 DEG C, two area's temperature are 60~75 DEG C, and three area's temperature are 90~110 DEG C, and four area's temperature are 110~130 DEG C, five Qu Wendu It is 110~120 DEG C, die head temperature is 80~100 DEG C, and rate of feeding is 50~150r/min, and screw speed is 150~300r/ min。

On the basis of above scheme, further, in the step 3, the running parameter of the inflation film manufacturing machine are as follows: add Material 60~80 DEG C of section, 110~130 DEG C of middle section, 130~160 DEG C of leading portion, head temperature: 130~150 DEG C, screw speed be 50~ 100r/min。

A kind of biodegradable breathable composite film provided by the invention and preparation method thereof, compared with prior art, has Following technical principle and the utility model has the advantages that

Porous-starch is a kind of novel starch, with the three-dimensional network shape microstructure that hole is interconnected, the present invention Processing method is combined with freezing by being crosslinked, porous is carried out to starch and handles obtained porous-starch material, meanwhile, starch is With certain rigid natural macromolecular material, intermolecular there are hydrogen bonds, and intermolecular force is very strong, the property with polyalcohol Matter, therefore starch is high with viscosity, hydrophilic ability is strong, is easy the characteristics such as gelatinization, greatly limits its application, especially adds in plastics Application field in terms of work, and by carrying out denaturation treatment to starch, substitution reaction is occurred to starch hydroxyl using acetic anhydride, it should Reaction temperature is low, generate starch acetate stability it is preferable so that between starch molecule hydrogen bond action weaken, macromolecular chain can compared with It is moved under low temperature, reduces the melting temperature of starch, effectively improve the thermoplasticity and hydrophobicity of starch, be conducive to hot melt processing Performance is conducive to starch and occurs " half-cooked " phenomenon in degradable material, improve thermoplasticity and dredge by reducing starch melting temperature The aqueous compatibility for being conducive to improve starch and matrix resin, is conducive to uniformly forming and reduce since poor compatibility is led for aperture The stress of cause is concentrated or interface conditions, to improve application of the starch in degradation plastic；The addition of toluene-4-sulfonic acid simultaneously Promote the progress that acetic anhydride is reacted with starch hydroxy esterification.And the present invention uses PE and PBAT to utilize change as matrix resin Property porous-starch porous and biodegradability properties, addition compatilizer, other processing aids such as lubricant develop a kind of life Biodegradable breathable composite film, solves that traditional gas permeable composite membrane hole aperture is uneven, permeability is bad, degradation rate is low etc. lacks Point can be widely applied to the fields such as fruits and vegetables, seafood storage, transport.

Detailed description of the invention

In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is this hair Bright some embodiments for those of ordinary skill in the art without any creative labor, can be with It obtains other drawings based on these drawings.

Fig. 1 is a kind of SEM image for being denaturalized porous-starch provided by the invention；

Fig. 2 is a kind of SEM image of biodegradable breathable composite film provided by the invention；

Fig. 3 is the SEM image of traditional gas permeable composite membrane.

Specific embodiment

In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art Every other embodiment obtained without creative efforts, shall fall within the protection scope of the present invention.

The present invention also provides embodiments as follows:

In embodiment and comparative example below, each raw material prepares raw material using following:

PE resin: model 2426H, blown film grade low density polyethylene (LDPE) (LDPE), melt flow rate (MFR) 2.8g/10min, Density 0.92g/cm³, it is selected from Daqing petrochemical；

PBAT resin: for polyadipate/butylene terephthalate, model: CZF-06, melt flow rate (MFR) are 2~5g/ 10min, Relative biological degradation rate >=90% are selected from Suzhou Hanfeng New Material Co., Ltd.；

Starch material: tapioca, model: BEST-2, water content≤10% are selected from the limited public affairs of Sanming City Blockbuster starch Department；

Compatilizer: POE-g-MAH, PE-g-MAH, EVA-g-MAH are commercial product；

Lubricant: PE wax, stearic acid, EBS are commercial product；

Weather resisting agent: the mixture of antioxidant 168 and ultraviolet absorbing agent UV531, the antioxidant 168 and UV531 Weight ratio be (1~5): 1, both for commercial product, be selected from Guangzhou Yan Tai Chemical Co., Ltd.；

Opening agent: silica opening agent and talcum powder opening agent model are respectively M-519 and ST-6016, commercial product.