CN112078209A - Oxidizable biodegradable cross-linked polyolefin heat shrinkable film - Google Patents
Oxidizable biodegradable cross-linked polyolefin heat shrinkable film Download PDFInfo
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- B32B2307/00—Properties of the layers or laminate
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- B32B2307/7163—Biodegradable
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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Abstract
The invention discloses an oxidizable biodegradable cross-linked polyolefin heat shrinkable film; the preparation method of the oxidizable biodegradable cross-linked polyolefin heat shrinkable film comprises the steps of melting and extruding linear low-density polyethylene LLDPE, a slipping agent, ternary copolymer polypropylene and an opening agent, and performing electron beam radiation cross-linking, blowing, rolling and slitting to obtain a finished product; weighing raw materials of each layer according to the total raw materials, specifically comprising the following raw materials in a first outer layer: 1.5 to 5 percent of PP and 2 to 4 percent of opening agent; the middle layer comprises the following raw materials: 70-85% of LLDPE, 3-10% of LDPE and 2-4% of slipping agent; the second outer layer raw material is the same as the first outer layer raw material. The oxidative biodegradation time of the obtained film is 6-24 months. The invention improves the hot melting section performance of the heat shrinkable film by matching the raw materials with the electron beam crosslinking process, and has wide market prospect.
Description
Technical Field
The invention belongs to the technical field of heat shrinkable films, and particularly relates to an oxidizable biodegradable cross-linked polyolefin heat shrinkable film.
Background
The multilayer co-extrusion crosslinking shrink film is a novel high-shrinkage bidirectional stretching shrink film developed on the basis of a POF shrink film in recent years. The multi-layer co-extruded shrink film is radiated by a high-voltage electron beam to cause cross linking between molecules and convert a linear chain structure into a net structure, thereby changing the physical and mechanical properties of the product. The cross-linked film can be prepared into products with different performance requirements through different formula designs and cross-linking degree control in the production process, and is suitable for different packaging equipment and product packaging. The polyolefin loose-proof crosslinked thermal shrinkage film is mainly characterized in that: strong toughness, excellent anti-loosening performance, high shrinkage rate and low shrinkage force. The polyolefin anti-relaxation crosslinked heat-shrinkable film perfectly solves the problems of poor packaging effect and easy relaxation of products. There are currently only a few developed countries that have similar products internationally.
In order to make the heat shrinkable film for packaging more fit with a product and meet the space saving requirement of the packaged product in the production, transportation and sale processes, the product needs to be packaged in time at a high temperature state, which puts high requirements on the heat resistance of the heat shrinkable film. The current heat-shrinkable crosslinked film can not meet the hot packaging requirement of products basically. In addition, in order to relieve ecological pressure and environmental pressure, the demand for more and more degradable heat shrinkable films is obviously increased.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made in view of the above-mentioned technical drawbacks.
Accordingly, in one aspect of the present invention, the deficiencies of the prior art are overcome by the present invention which provides an oxidizable biodegradable crosslinked polyolefin heat shrinkable film.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of an oxidizable biodegradable cross-linked polyolefin heat shrinkable film comprises the steps of melting and extruding linear low-density polyethylene LLDPE, a slipping agent, terpolymer polypropylene and an opening agent, carrying out electron beam radiation cross-linking, carrying out blowing, rolling and slitting to obtain a finished product; weighing raw materials of each layer according to the total raw materials, specifically comprising the following raw materials in a first outer layer: 1.5 to 5 percent of PP and 2 to 4 percent of opening agent; the middle layer comprises the following raw materials: 70-85% of LLDPE, 3-10% of LDPE and 2-4% of slipping agent; the second outer layer raw material is the same as the first outer layer raw material.
As a preferable embodiment of the method for preparing the oxidizable biodegradable crosslinked polyolefin heat shrinkable film of the present invention, wherein: the slipping agent comprises one or more of low-density polyethylene LDPE resin, erucamide and/or oleamide.
As a preferable embodiment of the method for preparing the oxidizable biodegradable crosslinked polyolefin heat shrinkable film of the present invention, wherein: the slipping agent comprises one or more of low-density polyethylene LDPE resin, erucamide and oleamide.
As a preferable embodiment of the method for preparing the oxidizable biodegradable crosslinked polyolefin heat shrinkable film of the present invention, wherein: the radiation dose of the electron beam radiation crosslinking is 50-110 kGy.
As a preferable embodiment of the method for preparing the oxidizable biodegradable crosslinked polyolefin heat shrinkable film of the present invention, wherein: and in the electron beam radiation crosslinking, the acceleration voltage is 100keV, the dose is uniformly distributed, the depth is 20-40 mu m, and during irradiation, the POF heat shrinkage film passes through an irradiation window of an electron accelerator at a constant speed of 0.1-0.5 m/s and is blown by air or nitrogen.
As a preferable embodiment of the method for preparing the oxidizable biodegradable crosslinked polyolefin heat shrinkable film of the present invention, wherein: the melting is carried out at 170-220 ℃.
As a preferable embodiment of the method for preparing the oxidizable biodegradable crosslinked polyolefin heat shrinkable film of the present invention, wherein: the temperature of the extrusion is the same as the temperature of the melting.
As a preferable embodiment of the method for preparing the oxidizable biodegradable crosslinked polyolefin heat shrinkable film of the present invention, wherein: the melting is carried out at 180-200 ℃.
As a preferable embodiment of the method for preparing the oxidizable biodegradable crosslinked polyolefin heat shrinkable film of the present invention, wherein: and the inflation ratio and the stretching ratio of the inflation are 3-3.5: 1;
as another aspect of the present invention, the present invention provides an oxidizable biodegradable crosslinked polyolefin heat shrinkable film characterized in that: the oxidative biodegradation time of the film is 6-24 months.
The invention has the beneficial effects that:
through the optimization of raw materials and further through electron beam crosslinking, the hot-melting section performance of the heat shrinkable film is perfected, and the heat shrinkable film has wide market prospect.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1:
the heat-shrinkable film is composed of three layers of co-extruded and bonded films, namely an outer layer, a middle layer and an inner layer;
weighing raw materials of each layer according to the total raw materials, specifically comprising the following raw materials in a first outer layer: 2.5% pp and 3% opener; the middle layer comprises the following raw materials: 70% LLDPE, 5% LDPE and 3% slip agent; the second outer layer raw material is the same as the first outer layer raw material;
the production process comprises the following steps:
(1) and (3) extrusion molding: uniformly mixing the raw materials of the outer layer, the middle layer and the inner layer according to the weight percentage, conveying the mixture to each single-screw extruder through each hopper, extruding the master slice through a die head for three-layer superposition co-extrusion at the extruder temperature of 185 ℃; extruding the billet tube by adopting a flat extrusion blow-down method, wherein the high polymer is in a molten state;
(2) radiation crosslinking: irradiating the mother sheet obtained in the previous step, wherein the polymer molecules change in structure under the irradiation effect to generate cross-linking of C-C bonds, the irradiation equipment is a low-energy electron beam heater, the acceleration voltage is 100keV, the dose is uniformly distributed with the depth of 30 mu m, during irradiation, the POF heat shrinkage film passes through an electron accelerator irradiation window at a uniform speed of 0.2m/s, the irradiation dose is 75kGy through air blowing,
(3) secondary blowing: entering a heating box, heating to 195 ℃ for longitudinal stretching, and then utilizing compressed air for transverse blowing, wherein the blowing ratio and the stretching ratio are 3.3: 1;
(4) and rolling and cutting to obtain a finished product.
TABLE 1 LDPE, LLDPE raw material selection Table
Example 2:
the heat-shrinkable film is composed of three layers of co-extruded and bonded films, namely an outer layer, a middle layer and an inner layer;
weighing raw materials of each layer according to the total raw materials, specifically comprising the following raw materials in a first outer layer: 1.5-5% of pp and 2-4% of a mouth-opening agent; the middle layer comprises the following raw materials: 70-85% of LLDPE, 3-10% of LDPE and 2-4% of slipping agent; the second outer layer material was the same as the first outer layer material, and the number 4 in example 1 was selected for each material.
The production process comprises the following steps:
(1) and (3) extrusion molding: uniformly mixing the raw materials of the outer layer, the middle layer and the inner layer according to the weight percentage, conveying the mixture to each single-screw extruder through each hopper, extruding the master slice through a die head for three-layer superposition co-extrusion at the extruder temperature of 185 ℃; extruding the billet tube by adopting a flat extrusion blow-down method, wherein the high polymer is in a molten state;
(2) radiation crosslinking: irradiating the mother sheet obtained in the previous step, wherein the polymer molecules change in structure under the irradiation effect to enable C-C bonds to generate crosslinking, the irradiation equipment is a low-energy electron beam heater, the acceleration voltage is 100keV, the dose is uniformly distributed with the depth of 35 mu m, during irradiation, the POF heat shrinkage film passes through an electron accelerator irradiation window at a uniform speed of 0.25m/s, the POF heat shrinkage film is blown by air, the radiation dose is 65kGy,
(3) secondary blowing: entering a heating box, heating to 195 ℃ for longitudinal stretching, and then utilizing compressed air for transverse blowing, wherein the blowing ratio and the stretching ratio are 3.5: 1;
(4) and rolling and cutting to obtain a finished product.
Example 3:
the heat-shrinkable film is composed of three layers of co-extruded and bonded films, namely an outer layer, a middle layer and an inner layer;
weighing raw materials of each layer according to the total raw materials, specifically comprising the following raw materials in a first outer layer: 1.5-5% of pp and 2-4% of a mouth-opening agent; the middle layer comprises the following raw materials: 70-85% of LLDPE, 3-10% of LDPE and 2-4% of slipping agent; the second outer layer material was the same as the first outer layer material, and the number 3 in example 1 was selected for each material.
The production process comprises the following steps:
(1) and (3) extrusion molding: uniformly mixing the raw materials of the outer layer, the middle layer and the inner layer according to the weight percentage, conveying the mixture to each single-screw extruder through each hopper, wherein the temperature of the extruder is 190 ℃, and extruding a master slice through a die head for three-layer superposition co-extrusion; extruding the billet tube by adopting a flat extrusion blow-down method, wherein the high polymer is in a molten state;
(2) radiation crosslinking: irradiating the mother sheet obtained in the previous step, wherein the polymer molecules change in structure under the irradiation effect to enable C-C bonds to generate crosslinking, the irradiation equipment is a low-energy electron beam heater, the acceleration voltage is 100keV, the dose is uniformly distributed with the depth of 27 mu m, during irradiation, the POF heat shrinkage film passes through an electron accelerator irradiation window at a uniform speed of 0.2m/s, the irradiation dose is 82kGy through air blowing,
(3) secondary blowing: entering a heating box, heating to 193 ℃ for longitudinal stretching, and then utilizing compressed air for transverse blowing, wherein the blowing ratio and the stretching ratio are 3.5: 1;
(4) and rolling and cutting to obtain a finished product.
Example 4:
the heat-shrinkable film is composed of three layers of co-extruded and bonded films, namely an outer layer, a middle layer and an inner layer;
weighing raw materials of each layer according to the total raw materials, specifically comprising the following raw materials in a first outer layer: 1.5-5% of pp and 2-4% of a mouth-opening agent; the middle layer comprises the following raw materials: 70-85% of LLDPE, 3-10% of LDPE and 2-4% of slipping agent; the second outer layer material was the same as the first outer layer material, and the number 4 in example 1 was selected for each material.
The production process comprises the following steps:
(1) and (3) extrusion molding: uniformly mixing the raw materials of the outer layer, the middle layer and the inner layer according to the weight percentage, conveying the mixture to each single-screw extruder through each hopper, extruding the master slice through a die head for three-layer superposition co-extrusion at the extruder temperature of 185 ℃; extruding the billet tube by adopting a flat extrusion blow-down method, wherein the high polymer is in a molten state;
(2) radiation crosslinking: irradiating the mother sheet obtained in the previous step, wherein the polymer molecules change in structure under the irradiation effect to generate cross-linking of C-C bonds, the irradiation equipment is a low-energy electron beam heater, the acceleration voltage is 100keV, the dose is uniformly distributed with the depth of 30 mu m, during irradiation, the POF heat shrinkage film passes through an electron accelerator irradiation window at a uniform speed of 0.4m/s, the POF heat shrinkage film is blown by air, the irradiation dose is 53kGy,
(3) secondary blowing: entering a heating box, heating to 195 ℃ for longitudinal stretching, and then utilizing compressed air for transverse blowing, wherein the blowing ratio and the stretching ratio are 3.3: 1;
(4) and rolling and cutting to obtain a finished product.
Example 5:
the heat-shrinkable film is composed of three layers of co-extruded and bonded films, namely an outer layer, a middle layer and an inner layer;
weighing raw materials of each layer according to the total raw materials, specifically comprising the following raw materials in a first outer layer: 1.5-5% of pp and 2-4% of a mouth-opening agent; the middle layer comprises the following raw materials: 70-85% of LLDPE, 3-10% of LDPE and 2-4% of slipping agent; the second outer layer material was the same as the first outer layer material, and the number 3 in example 1 was selected for each material.
The production process comprises the following steps:
(1) and (3) extrusion molding: uniformly mixing the raw materials of the outer layer, the middle layer and the inner layer according to the weight percentage, conveying the mixture to each single-screw extruder through each hopper, wherein the temperature of the extruder is 190 ℃, and extruding a master slice through a die head for three-layer superposition co-extrusion; extruding the billet tube by adopting a flat extrusion blow-down method, wherein the high polymer is in a molten state;
(2) radiation crosslinking: irradiating the mother sheet obtained in the previous step, wherein the polymer molecules change in structure under the irradiation effect to enable C-C bonds to generate crosslinking, the irradiation equipment is a low-energy electron beam heater, the acceleration voltage is 100keV, the dose is uniformly distributed with the depth of 27 mu m, during irradiation, the POF heat shrinkage film passes through an electron accelerator irradiation window at a uniform speed of 0.35m/s, the POF heat shrinkage film is blown by air, the radiation dose is 95kGy,
(3) secondary blowing: entering a heating box, heating to 193 ℃ for longitudinal stretching, and then utilizing compressed air for transverse blowing, wherein the blowing ratio and the stretching ratio are 3.3: 1;
(4) and rolling and cutting to obtain a finished product.
The products of the above examples were tested for tensile properties using GB/T1040.1-2006, at a tensile rate of 50mm/min, with the results shown in the following Table.
The results of testing the heat shrinkable films obtained in examples 1 to 5 are shown in the following table.
According to the invention, a large amount of raw materials are selected preferably, the lower the MFR, the larger the relative molecular mass of LDPE, the more intermolecular entanglement points and the larger the shrinkage stress, and the stronger the impact resistance and tear resistance of the film blown by the LDPE and the higher the heat shrinkage rate. The degree of long chain branching is the largest factor affecting film transverse heat shrinkage relative to LDPE of similar molecular mass. The higher the degree of long chain branching, the more entanglement points between polymer chains, the higher the melt strength, and the higher the transverse heat shrinkage of the film. Through the optimization of raw materials and further through electron beam crosslinking, the hot-melting section performance of the heat shrinkable film is perfected, and the heat shrinkable film has wide market prospect.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A preparation method of an oxidizable biodegradable cross-linked polyolefin heat shrinkable film is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
melting and extruding linear low-density polyethylene LLDPE, a slipping agent, terpolymer polypropylene and an opening agent, and performing blowing, rolling and slitting after electron beam radiation crosslinking to obtain a finished product;
weighing raw materials of each layer according to the total raw materials, specifically comprising the following raw materials in a first outer layer: 1.5 to 5 percent of PP and 2 to 4 percent of opening agent; the middle layer comprises the following raw materials: 70-85% of LLDPE, 3-10% of LDPE and 2-4% of slipping agent; the second outer layer raw material is the same as the first outer layer raw material.
2. The method of making an oxidizable biodegradable cross-linked polyolefin heat shrinkable film of claim 1, wherein: the slipping agent comprises one or more of low-density polyethylene LDPE resin, erucamide and/or oleamide.
3. The method of making an oxidizable biodegradable cross-linked polyolefin heat shrinkable film of claim 1, wherein: the slipping agent comprises one or more of low-density polyethylene LDPE resin, erucamide and oleamide.
4. The method for preparing an oxidizable, biodegradable and crosslinked polyolefin heat shrinkable film according to any one of claims 1 to 3, wherein: the radiation dose of the electron beam radiation crosslinking is 50-110 kGy.
5. The method of making an oxidizable biodegradable cross-linked polyolefin heat shrinkable film of claim 4, wherein: and in the electron beam radiation crosslinking, the acceleration voltage is 100keV, the dose is uniformly distributed, the depth is 20-40 mu m, and during irradiation, the POF heat shrinkage film passes through an irradiation window of an electron accelerator at a constant speed of 0.1-0.5 m/s and is blown by air or nitrogen.
6. The method for preparing an oxidizable, biodegradable and crosslinked polyolefin heat shrinkable film according to any one of claims 1 to 5, wherein: the melting is carried out at 170-220 ℃.
7. The method of making an oxidizable biodegradable cross-linked polyolefin heat shrinkable film of claim 6, wherein: the temperature of the extrusion is the same as the temperature of the melting.
8. The method of making an oxidizable biodegradable crosslinked polyolefin heat shrinkable film of claim 6 or 7, wherein: the melting is carried out at 180-200 ℃.
9. The method of making an oxidizable biodegradable crosslinked polyolefin heat shrinkable film of claim 6 or 7, wherein: and the inflation ratio and the stretching ratio of the inflation are 3-3.5: 1.
10. an oxidizable biodegradable cross-linked polyolefin heat shrinkable film, characterized in that: the oxidative biodegradation time of the film is 6-24 months.
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