CN115302904A - Degradable heat shrinkable film and preparation method thereof - Google Patents

Degradable heat shrinkable film and preparation method thereof Download PDF

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Publication number
CN115302904A
CN115302904A CN202210875839.4A CN202210875839A CN115302904A CN 115302904 A CN115302904 A CN 115302904A CN 202210875839 A CN202210875839 A CN 202210875839A CN 115302904 A CN115302904 A CN 115302904A
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parts
film
layer
heat shrinkable
shrinkable film
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CN115302904B (en
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左娟
张文辉
毛龙
涂宗玲
陈赐辉
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Xiamen Ameson New Material Inc
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Xiamen Ameson New Material Inc
Xiamen University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2519/00—Labels, badges
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Abstract

The invention relates to a degradable heat shrinkable film and a preparation method thereof, wherein the film comprises an upper layer, a middle layer and a lower layer which are sequentially laminated, wherein the upper layer and the lower layer are outer layers, and the upper layer and/or the lower layer comprise (by weight parts) 70-90 parts of polystyrene, 1-10 parts of zinc oxide, 1-10 parts of nickel stearate, 1-3 parts of a chain extender and 1-3 parts of a slipping agent; the middle layer is a core layer and comprises, by weight, 70-90 parts of chitosan, 1-10 parts of nickel stearate, 1-10 parts of sodium alginate and 1-10 parts of a plasticizer. The degradable heat shrinkable film disclosed by the invention has the advantages that on the premise of keeping the self advantages of the oriented polystyrene film, the degradability of the material is greatly improved, the recovery problem of the oriented polystyrene film can be solved, and the degradable heat shrinkable film has environmental protection advantages and economic value.

Description

Degradable heat shrinkable film and preparation method thereof
Technical Field
The invention relates to the technical field of film preparation, in particular to a degradable heat shrinkable film and a preparation method thereof.
Background
The heat shrinkable film is a film material which is put into large scale at present and is used for commodity labels and outer packages in various industries. It has good shrinkage property, cold resistance and transparency. However, they are generally difficult to degrade and cause irreversible environmental pollution through film landfilling and incineration. With the shortage of global resources and the increasing deterioration of the environment, the society urgently needs a degradable heat shrinkable film material which is exquisite and environment-friendly.
The traditional heat-shrinkable film at present mainly adopts the following materials: polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polyvinylidene chloride (PVDC), polystyrene (PS), polyolefin (PO), polyethylene terephthalate (PET), and the like. However, with the development of the times, people hope that the heat shrinkable film material has certain degradability while having better heat shrinkable property and mechanical strength. For example, the modified polylactic acid film developed in patent application No. CN202111221469.4 has good biodegradability; also, linear Low Density Polyethylene (LLDPE) films as in patent application No. CN202010754524.5 are biodegradable and have more excellent tensile strength and impact resistance.
The oriented polystyrene film (OPS) is used as a recyclable and pollution-free environment-friendly material after combustion, and has the advantages of good toughness, high shrinkage rate, high transparency and the like. Although foreign enterprises have replaced PVC materials with OPS on a large scale, the domestic enterprises producing OPS films in batches are still a few. The current treatment of OPS film is mainly recycling and burning, but still leaves a large amount of film waste which is difficult to degrade, and causes white pollution. Therefore, industrially produced OPS films still have disadvantages.
Conventional oriented polystyrene films do not have degradation properties, or have negligible natural degradation, because the material is stretch-oriented during its preparation, which increases the mechanical and physical strength of the film, and also increases the crystallinity of the high polymer, which makes degradation difficult. Because the oriented polystyrene film has fine crystals and the transparency and the barrier property of the material are greatly improved, the oriented polystyrene film is not beneficial to the absorption of light and the activity of microorganisms. Therefore, the self-manufacturing process and properties of the oriented polystyrene film make the oriented polystyrene film difficult to degrade, and the existing film degradation scheme cannot solve the degradation problem of the oriented polystyrene film.
Disclosure of Invention
The invention aims to overcome the problem of difficult degradation of the existing oriented polystyrene film, and provides a degradable heat shrinkable film which is designed into an A/B/A structure by improving the structure of the film, wherein the core layer of the B film is made of chitosan, nickel stearate, sodium alginate and a plasticizer, and the outer layer of the B film is made of a material mainly comprising polystyrene.
The degradation effect of the conventional oriented polystyrene film under natural light is not obvious, and the zinc oxide is added to be used as an OPS film photocatalyst, so that the film is subjected to photodegradation. The mechanism is mainly as follows: when sunlight irradiates zinc oxide, photo-generated electrons and holes are generated, and can react with water and oxygen in the environment to obtain oxygen-containing groups with strong oxidizing property. The polymer chains in the film can react with the oxygen-containing groups to cause the breakage of the polymer chains; when oxygen-containing groups enter the polymer structure, the photodegradation is further promoted.
When a landfill treatment is used, the film cannot receive light efficiently, and thus degradation of the film is affected by the light. According to the invention, nickel stearate is added as a thermal-oxidative degradation agent of the OPS film, so that the film can be subjected to thermal degradation under the action of heat energy in the absence of illumination. The main mechanism is as follows: when in landfill, the additive generates oxygen-containing free radicals under the action of heat; the oxygen-containing radicals can oxidize high molecular compounds, thereby breaking molecular chains in the film, generating oxygen-containing radicals with strong oxidizing capability while generating thermal oxidation degradation reaction, and further decomposing residual substances after photodegradation.
The chitosan has degradability, and can obviously enhance the degradation rate of the film when added into the film material, but the strength of the corresponding film material can be greatly reduced, and the heat shrinkage performance can also be reduced. In order to solve the contradiction, the method of adding chitosan into the core layer and adding sodium alginate simultaneously are adopted, so that the light transmittance of the film is obviously enhanced, and the adverse effect of the core layer on the light transmittance of the whole film is counteracted; the core layer adopts the plasticizer, so that the structure of the film is changed, and the molecular plasticity in the film is improved, thereby enhancing the mechanical property of the whole film.
In the invention, because the outer layer material contains zinc oxide and nickel stearate, the compatibility of the outer layer material with the polymer is poor, so that the material is abraded and adhered during extrusion. The invention prolongs the molecular chain of the polymer and increases the molecular weight through the chain extender, so that the film is easier to be cured and molded to contain the powder particles. Meanwhile, the slipping agent is also adopted, and the incompatibility between the slipping agent and the polymer film is utilized, so that the slipping agent is transferred to the surface of the film during co-extrusion, the dynamic friction factor between the film and a machine can be reduced, and the effect of reducing abrasion is achieved.
The specific scheme is as follows:
a degradable heat shrinkable film comprises an upper layer, a middle layer and a lower layer which are sequentially laminated, wherein the upper layer and the lower layer are outer layers, and the upper layer and/or the lower layer comprise (by weight parts) 70-90 parts of polystyrene, 1-10 parts of zinc oxide, 1-10 parts of nickel stearate, 1-3 parts of a chain extender and 1-3 parts of a slipping agent;
the middle layer is a core layer and comprises, by weight, 70-90 parts of chitosan, 1-10 parts of nickel stearate, 1-10 parts of sodium alginate and 1-10 parts of a plasticizer.
Further, the upper layer and the lower layer consist of 75-85 parts of polystyrene, 3-8 parts of zinc oxide, 3-8 parts of nickel stearate, 1-3 parts of chain extender and 1-3 parts of slipping agent in parts by weight.
Furthermore, the middle layer comprises 70-80 parts of chitosan, 5-10 parts of nickel stearate, 3-5 parts of sodium alginate and 5-10 parts of plasticizer by weight.
Further, the weight ratio of the outer layer to the core layer is 1:0.2-1:1.
further, the chain extender is 2-imidazolidinone;
optionally, the slip agent is oleamide or erucamide;
optionally, the plasticizer is glycerol.
Further, the degradable heat shrinkable film is at 800W/m 2 The weight loss rate is 20-25% after the ultraviolet light with the intensity is irradiated for 240 h; the ratio of the area of the long mold in 28 days of biodegradation experiments is 25-26%; the average value of transverse heat shrinkage is 18-19%, and the average value of longitudinal heat shrinkage is 1.5-1.6%; the occurrence time of the transverse maximum heat shrinkage rate is 23.2 to 26.9s, and the occurrence time of the longitudinal maximum heat shrinkage rate is 19.9 to 22.8s.
The invention also provides a preparation method of the degradable heat shrinkable film, which comprises the following steps:
(1) Drying the polystyrene to obtain a treated mixed material; adding the chain extender, the zinc oxide and the slipping agent into the mixed material, and putting the mixed material into a high-speed stirrer for stirring to obtain an outer layer material;
(2) Dissolving chitosan and sodium alginate in an acetic acid solution, adding nickel stearate and a plasticizer, and stirring the obtained mixed solution in a vacuum defoaming machine to obtain a treated chitosan solution; standing, and adding alkali liquor to be neutral to obtain a core layer material;
(3) The core layer material is put into a middle hopper in the three-layer co-extrusion film blowing equipment, and the outer layer material is put into the other two hoppers; and finally extruding the film in a three-layer co-extrusion film blowing machine, cooling and shaping the film, and shaping the film by using a dryer to obtain the degradable heat shrinkable film.
Further, in the step (1), the polystyrene is dried and is dried for 5 to 10 hours at the temperature of between 45 and 50 ℃; the stirring speed of the high-speed stirrer is 300-600r/min, the temperature is 180-200 ℃, and the stirring time is 8-10min.
Further, the temperature of the extrusion in the step (3) is 170-190 ℃.
The invention also protects the application of the degradable heat shrinkable film on product outer packages and product labels.
Has the advantages that:
according to the invention, the degradable heat shrinkable film adopts a structure of an upper layer, a middle layer and a lower layer which are sequentially stacked, the upper layer and the lower layer can be subjected to photodegradation by adding zinc oxide, and nickel stearate is added to play a thermal catalytic degradation role so as to enhance the degradation effect.
And moreover, the core layer contains chitosan, so that the chitosan can be developed from the inside to the outside during degradation, holes and powder cracks are formed, and the degradation speed is accelerated.
Further, in order to protect the strength and the heat shrinkage performance of the film and reduce the adverse effect of zinc oxide, nickel stearate and chitosan on the mechanical performance, the invention adopts a chain extender and a slipping agent on the outer layer and adopts sodium alginate and a plasticizer on the core layer, so that the film has better strength and heat shrinkage performance integrally.
In a word, the degradable heat shrinkable film greatly improves the degradability of the material on the premise of keeping the self advantages of the oriented polystyrene, can solve the recovery problem of the oriented polystyrene film, and has environmental protection advantages and economic value.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
The chain extender used in the examples was 2-imidazolidinone; the slipping agent is oleamide; the plasticizer is glycerol.
The test methods used below included:
(1) Ultraviolet irradiation weight loss rate test
When the film is irradiated with ultraviolet light, the film undergoes an oxidation reaction, eventually releasing carbon dioxide and water, and the quality is reduced. The weight loss rate is the most visual index for reflecting the photodegradation of the film. The film was placed on a stage using UV light, 800W/m 2 Irradiating with ultraviolet light at intensity for 240h, and using an electronic balanceAnd measuring the weight loss rate.
(2) Ultraviolet irradiation for observing chalking phenomenon
When the film is irradiated with ultraviolet light, the film is deteriorated and powdering occurs. Cutting off a part of two films, cleaning the films in an ultrasonic cleaner for 10min, drying the surfaces by using a blower after the surfaces are cleaned, and observing the micro-morphology of a sample by using an electron scanning microscope; the sample is placed at 1600W/m 2 Irradiated under ultraviolet light of an intensity, and observed by an electron scanning microscope after the film is aged.
(3) Biodegradation test
Two films were cut to 10X 10cm respectively, according to GB/T4768-1995 2 The size and shape of the simulated piece had a humidity of 60%, an average temperature of 25 ℃ and a pH of 6.7. The medium was left for 28 days. (the substances in the medium include carbohydrates, nitrogen, mineral salts and water) the proportion of the total area of the mould part in the simulant was finally measured.
(4) Film Cold/Heat shrinkage Performance test
The reference standard ASTM D2732, equipment is FST-02 film thermal shrinkage tester. The shrinkage force test was performed using an oil bath method. Dividing the film to be tested into transverse samples and longitudinal samples, taking 6 samples in each direction, putting the samples into glycerol which is heated to 100 ℃ in advance, measuring the time of the maximum cold/heat shrinkage force of the film within 15-30s, carrying out 6 groups of tests, taking the average value of the heat shrinkage force, and calculating the average value of the heat shrinkage force and the time of the maximum heat shrinkage force.
Examples 1 to 5
Preparing a degradable heat shrinkable film (called degradable OPS film for short), wherein the dosage of each raw material is shown in table 1, and the steps are as follows:
(1) Placing polystyrene into a drying box according to the parts by weight, and pretreating for 6 hours at 50 ℃ to obtain a treated mixed material; and adding the chain extender, the zinc oxide and the slipping agent into the obtained mixed material, putting the mixed material into a high-speed stirrer, and stirring the mixed material for 10min at the temperature of 180 ℃ at the speed of 500r/min to obtain an outer-layer material.
(2) Dissolving chitosan and sodium alginate in acetic acid solution according to parts by weight, and then adding a plasticizer; putting the mixed solution into a vacuum defoaming machine and stirring to obtain a treated chitosan solution; standing for 10min, and treating with hot alkali solution to obtain neutral core material.
(3) And adjusting the ratio of the outer layer material to the core layer material to a preset value.
(4) Placing a core layer material into a middle hopper in the three-layer coextrusion film blowing equipment, and placing an outer layer material into the other two hoppers; finally extruding the mixture in a three-layer co-extrusion film blowing machine at the temperature of 180 ℃; and cooling and shaping the film, shaping the film by using a dryer, flattening the film, and trimming the edge to obtain a finished product.
TABLE 1 Scale for materials (parts by weight)
Figure BDA0003762474890000071
Comparative example 1
Referring to example 1, the OPS film was made according to the same co-extrusion process, except that the core layer material was different, and the outer layer material was substituted for the core layer of the same quality.
Comparative example 2
Referring to the embodiment 1, the difference is only that the core layer material is different, and the OPS film is prepared from 84 parts by weight of chitosan, 6 parts by weight of nickel stearate and 5 parts by weight of plasticizer according to the same co-extrusion process.
Performance detection
Taking the degradable OPS film prepared in example 1 and the common OPS film prepared in comparative example 1, observing the films through a microscope after ultraviolet light irradiation, the surfaces of the film samples of the degradable OPS film and the common OPS film are uniform and smooth before ultraviolet light irradiation, and agglomerated small particles are rarely seen.
The degradable OPS film passes through 1600W/m 2 After the ultraviolet light is irradiated, the surface of the film sample becomes unsmooth compared with the front surface, a large number of holes and defects are formed on the film sample, and an obvious chalking phenomenon is shown; whereas the ordinary OPS film has only a slightly rough surface and is substantially in a smooth state.
The combination of the properties of the two films is shown in Table 2.
TABLE 2 film Performance test results Table
Figure BDA0003762474890000081
Figure BDA0003762474890000091
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, and the same should be considered as the disclosure of the present invention as long as the idea of the present invention is not violated.

Claims (10)

1. A degradable heat shrinkable film characterized by: the composite material comprises an upper layer, a middle layer and a lower layer which are sequentially stacked, wherein the upper layer and the lower layer are outer layers, and the upper layer and/or the lower layer comprise (by weight parts) 70-90 parts of polystyrene, 1-10 parts of zinc oxide, 1-10 parts of nickel stearate, 1-3 parts of chain extender and 1-3 parts of slipping agent;
the middle layer is a core layer and comprises, by weight, 70-90 parts of chitosan, 1-10 parts of nickel stearate, 1-10 parts of sodium alginate and 1-10 parts of a plasticizer.
2. The degradable heat shrink film of claim 1, wherein: the upper layer and the lower layer are composed of, by weight, 75-85 parts of polystyrene, 3-8 parts of zinc oxide, 3-8 parts of nickel stearate, 1-3 parts of a chain extender and 1-3 parts of a slipping agent.
3. The degradable heat shrink film of claim 1, wherein: the middle layer comprises, by weight, 70-80 parts of chitosan, 5-10 parts of nickel stearate, 3-5 parts of sodium alginate and 5-10 parts of a plasticizer.
4. A degradable heat shrink film according to any one of claims 1 to 3 wherein: the weight ratio of the outer layer to the core layer is 1:0.2-1:1.
5. a degradable heat shrinkable film of any one of claims 1 to 3, wherein: the chain extender is 2-imidazolidinone;
optionally, the slip agent is oleamide or erucamide;
optionally, the plasticizer is glycerol.
6. A degradable heat shrink film according to any one of claims 1 to 3 wherein: the degradable heat shrinkable film is at 800W/m 2 The weight loss rate is 20-25% after the ultraviolet light with the intensity is irradiated for 240 h; the area proportion of the mildew in 28 days of biodegradation experiments is 25-26%; the average value of transverse heat shrinkage is 18-19%, and the average value of longitudinal heat shrinkage is 1.5-1.6%; the occurrence time of the transverse maximum heat shrinkage rate is 23.2 to 26.9s, and the occurrence time of the longitudinal maximum heat shrinkage rate is 19.9 to 22.8s.
7. A method of making a degradable heat shrinkable film according to any one of claims 1 to 6 wherein: the method comprises the following steps:
(1) Drying the polystyrene to obtain a treated mixed material; adding the chain extender, the zinc oxide and the slipping agent into the mixed material, and putting the mixed material into a high-speed stirrer for stirring to obtain an outer layer material;
(2) Dissolving chitosan and sodium alginate in an acetic acid solution, adding nickel stearate and a plasticizer, and stirring the obtained mixed solution in a vacuum defoaming machine to obtain a treated chitosan solution; standing, and adding alkali liquor to be neutral to obtain a core layer material;
(3) The core layer material is put into a middle hopper in the three-layer co-extrusion film blowing equipment, and the outer layer material is put into the other two hoppers; and finally extruding the mixture in a three-layer co-extrusion film blowing machine, cooling and shaping the mixture, and shaping the film by using a dryer to obtain the degradable heat shrinkable film.
8. The method for preparing degradable heat shrinkable film according to claim 7, wherein: in the step (1), polystyrene is dried and is dried for 5-10h at the temperature of 45-50 ℃; the stirring speed of the high-speed stirrer is 300-600r/min, the temperature is 180-200 ℃, and the stirring time is 8-10min.
9. The method for preparing degradable heat shrinkable film according to claim 7, wherein: the temperature of the extrusion in the step (3) is 170-190 ℃.
10. Use of the degradable heat shrinkable film of any one of claims 1 to 6 on a product overwrap, product label.
CN202210875839.4A 2022-07-25 2022-07-25 Degradable heat-shrinkable film and preparation method thereof Active CN115302904B (en)

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