CN117162615A - Co-extrusion self-adhesion biodegradable barrier composite film and preparation method thereof - Google Patents
Co-extrusion self-adhesion biodegradable barrier composite film and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 80
- 230000004888 barrier function Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 33
- 238000001125 extrusion Methods 0.000 title claims description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 52
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 47
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 39
- 239000004626 polylactic acid Substances 0.000 claims abstract description 39
- 230000001681 protective effect Effects 0.000 claims abstract description 32
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 31
- -1 polybutylene terephthalate Polymers 0.000 claims abstract description 31
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 24
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 22
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 22
- 239000000853 adhesive Substances 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 239000004014 plasticizer Substances 0.000 claims description 11
- 238000004806 packaging method and process Methods 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 238000013329 compounding Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000000314 lubricant Substances 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000006065 biodegradation reaction Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 78
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 42
- 229920001896 polybutyrate Polymers 0.000 description 29
- 238000012545 processing Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000002985 plastic film Substances 0.000 description 6
- 229920006255 plastic film Polymers 0.000 description 6
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- BSKJUAKMZZKMKC-UHFFFAOYSA-N 1,2-ditert-butyl-3,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C(C)(C)C)C(C(C)(C)C)=C1C(C)C BSKJUAKMZZKMKC-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Extrusion Moulding Of Plastics Or The Like (AREA)
- Laminated Bodies (AREA)
Abstract
The application discloses a coextrusion self-adhesive biodegradation barrier composite film, which comprises a middle layer and protective outer layers arranged on two opposite sides of the middle layer; the protective outer layer is attached to the middle layer in a self-bonding mode; the middle layer is made of polyvinyl alcohol which can be processed by thermoplastic; the protective outer layer is made of a polybutylene terephthalate/polylactic acid composite material modified by maleic anhydride grafting. According to the application, the thermoplastic polyvinyl alcohol is used as the middle layer, and the polybutylene terephthalate/polylactic acid composite material modified by grafting maleic anhydride is used as the protective outer layer, so that the excellent barrier property of the middle layer can be effectively ensured, the production cost of the composite film can be reduced, and the biodegradation can be realized.
Description
Technical Field
The application belongs to the technical field of high polymer materials, and particularly relates to a coextrusion self-adhesive biodegradable barrier composite film and a preparation method thereof.
Background
The product of the barrier plastic film material is mainly used for shielding small molecular gas, liquid, vapor, fragrance and the like, and has the effects of guaranteeing quality, preserving freshness, preserving flavor and prolonging shelf life of foods. In the packaging industry, especially in food and medicine packaging, the use of barrier film packaging materials is increasingly emphasized, and the barrier plastic film packaging materials have been rapidly developed in recent years due to the advantages of functionality, light weight, convenience in processing and transportation, and the like. Matrix resins of barrier plastic films conventionally used in the market at present mainly include nylon (PA), polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC), and Polyacrylonitrile (PAN). However, with the prevalence of plastic film materials, the white pollution caused by the plastic film materials is increasingly serious, and thus, research and development of barrier films having biodegradability have wide social and economic values. In contrast, in chinese patent No. CN200610173345.2, a high-barrier degradable medical multilayer composite packaging film is disclosed, which has a 10-12 layer structure, and uses modified polyester, modified polyamide and polyvinyl alcohol as barrier layers, and uses polyolefin to add photodegradants and biodegradable agents to achieve the purpose of controllable degradation. The film disclosed by the patent is degradable, but has a 10-12-layer integral structure, the preparation process is relatively complicated, the requirement on equipment is relatively high, and industrial application is difficult to realize, and meanwhile, the components of the patent contain non-degradable components which achieve the degradation effect by adding the photodegradable agent, so that the components of the whole film product are very complex, and the production cost of the film is greatly increased.
Disclosure of Invention
The application aims to solve the technical problems of complex structure, high production cost and the like of the biodegradable barrier composite film in the prior art; the co-extrusion self-adhesive biodegradable barrier composite film and the preparation method thereof are provided, so that the technical effect that the composite film has excellent barrier property and the production cost can be effectively reduced is achieved.
In order to achieve the above purpose, the application adopts the following technical scheme:
the coextrusion self-adhesive biodegradable barrier composite film comprises a middle layer and protective outer layers arranged on two opposite sides of the middle layer; the protective outer layer is attached to the middle layer in a self-bonding mode;
the middle layer is made of polyvinyl alcohol which can be processed by thermoplastic;
the protective outer layer is made of a polybutylene terephthalate/polylactic acid composite material modified by maleic anhydride grafting.
Further, the thermoplastically processable polyvinyl alcohol comprises the following components in parts by weight:
100 parts of polyvinyl alcohol, 25-35 parts of plasticizer, 1-3 parts of lubricant and 1-2 parts of antioxidant.
Further, the preparation method of the thermoplastically processable polyvinyl alcohol comprises the following steps: placing polyvinyl alcohol, plasticizer, lubricant and antioxidant into a mixer, uniformly mixing, placing into a double-screw extruder, melting and extruding, conveying by a crawler, granulating and drying to obtain the thermoplastic-processable polyvinyl alcohol.
Further, the plasticizer is a mixture obtained by mixing glycerin and polyethylene glycol according to the weight ratio of (1-5) to (1-3), and the lubricant is silicone powder with the weight average molecular weight of 70 ten thousand to 75 ten thousand.
Further, the preparation method of the polybutylene terephthalate/polylactic acid composite material modified by maleic anhydride grafting comprises the following steps:
A. placing polybutylene terephthalate and polylactic acid into a mixer for uniformly mixing to obtain a mixture;
B. adding maleic anhydride and di-tert-butyl diisopropyl peroxide into the mixture in the step A under the condition of stirring, and uniformly mixing to obtain a premix;
C. adding the premix into a double-screw extruder for melt extrusion, and then carrying out water-cooling drawing, granulating and drying to obtain the maleic anhydride grafted modified polybutylene terephthalate/polylactic acid composite material.
Further, in the step A, the addition amount of the polybutylene terephthalate adipic acid is 80-95 parts by weight, and the addition amount of the polylactic acid is 5-20 parts by weight.
Further, the addition amount of the maleic anhydride in the step B is 0.8-1.1% of the mixture by weight.
Further, the adding amount of the di-tert-butyl diisopropyl benzene peroxide in the step B is 0.08-0.11% of the mixture by weight.
The preparation method of the coextrusion self-adhesive biodegradable barrier composite film comprises the following steps:
respectively placing the thermoplastic processed polyvinyl alcohol and the polybutylene terephthalate/polylactic acid composite material modified by maleic anhydride grafting into a three-layer coextrusion extruder, and carrying out self-bonding compounding, extrusion, traction, cooling, curling and packaging through a three-layer coextrusion die head according to the A/B/A mode to obtain a composite film;
wherein, the thermoplastic polyvinyl alcohol is a middle layer, and the polybutylene terephthalate/polylactic acid composite material modified by maleic anhydride grafting is a protective outer layer.
Further, the total thickness of the composite film is 40-80 mu m, and the thickness of the protective outer layer is 5-10% of the total thickness of the composite film.
The beneficial effects of the application are as follows:
according to the application, the thermoplastic polyvinyl alcohol is used as the middle layer, and the polybutylene terephthalate/polylactic acid composite material modified by grafting maleic anhydride is used as the protective outer layer, so that the excellent barrier property of the middle layer can be effectively ensured, the production cost of the composite film can be reduced, and the biodegradation can be realized. The method comprises the following steps:
the polyvinyl alcohol molecule contains a large number of hydroxyl groups, and the intramolecular hydrogen bond and the intermolecular hydrogen bond lead the melting point to be higher than the decomposition temperature, so the polyvinyl alcohol does not have thermoplastic processability, but is endowed with extremely high oxygen barrier property, oil resistance, mechanical strength and biodegradability and is low in price. Therefore, the polyvinyl alcohol can be used as an intermediate layer for preparing the composite film after thermoplastic processing, and the excellent barrier property of the composite film can be effectively ensured.
The polybutylene terephthalate/polylactic acid composite material grafted and modified by maleic anhydride is used as the protective outer layer, so that the intermediate layer can be well protected, the barrier property of the intermediate layer can be fully exerted during use, and meanwhile, the polybutylene terephthalate/polylactic acid composite material grafted and modified by maleic anhydride has the bonding property, so that an adhesive layer is not required to be coated during preparation of a composite film, three-layer coextrusion extrusion equipment can be directly used for extrusion and then is used for compounding, the equipment requirement is lower, and meanwhile, the raw material cost can be reduced and biodegradation can be truly realized because no adhesive is required to be added.
The longitudinal tensile strength of the composite film prepared by the application is more than or equal to 24MPa, the transverse tensile strength is more than or equal to 22MPa, the elongation at break is more than or equal to 280%, the right-angle tearing strength is more than or equal to 100KN/m, and the oxygen permeability at normal temperature (23 ℃) is less than or equal to 40cm 3 /m 2 24 h.0.1 MPa. Can be used for chemical and pesticideAnd packaging without human body contact such as detergent, food, cosmetic, grain, etc.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be described more clearly and completely below. It will be apparent that the described embodiments are some, but not all, embodiments of the application. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present application fall within the protection scope of the present application. Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this application belongs.
The terms "first," "second," and the like in the description and in the claims, are not used for any order, quantity, or importance, but are used for distinguishing between different elements. Also, unless the context clearly indicates otherwise, singular forms "a," "an," or "the" and similar terms do not denote a limitation of quantity, but rather denote the presence of at least one. The terms "comprises," "comprising," or the like are intended to cover a feature, integer, step, operation, element, and/or component recited as being present in the element or article that "comprises" or "comprising" does not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. "upper", "lower", "left", "right", etc. are used merely to indicate relative positional relationships, which may also be changed when the absolute position of the object to be described is changed.
The main raw material sources in the following examples and comparative examples of the present application are as follows:
PBAT (polybutylene terephthalate) brand 2003F, melt mass flow rate of 5g/10min, tensile breaking strength of 20MPa and elongation at break of 580%;
PLA (polylactic acid) with the brand of 4032D, the mass flow rate of the melt of 7g/10min, the tensile breaking strength of 53MPa and the breaking elongation of 6 percent;
the PVA (polyvinyl alcohol) model is 1788, the polymerization degree is 1680-1720, and the alcoholysis degree is 86-90%;
PEG (polyethylene glycol), hydroxyl value 510-623mgKOH/g, molecular weight 180-200;
BIPB (di-t-butylperoxydiisopropylbenzene), model FARIDA BIPB96;
MAH (maleic anhydride), chemically pure, commercially available;
glycerol, analytically pure, commercially available;
the rest reagents are commercial products.
The detection method adopted in the detection of the performance of the corresponding raw materials/semi-products/products in each embodiment and comparative example of the application comprises the following steps:
grafting ratio of maleic anhydride graft modified polybutylene terephthalate/polylactic acid composite (PBAT/PLA-g-MAH): conventional nonaqueous acid-base titration;
melt mass flow rate: GB/T3682.1; wherein, the test conditions are: 190 ℃ and 2.16kg;
tensile break strength and elongation: GB/T1040.1;
right angle tear Strength of plastic film: QB/T1130;
gas permeation amount: GB/T1038.1.
The structural parameters of the three-layer coextrusion extruder in each embodiment and comparative example of the application are as follows: the screw diameter of the two outer layer extruders is 45mm, and the length-diameter ratio is 30/1; the screw diameter of the intermediate layer extruder is 50mm, and the length-diameter ratio is 30/1.
Example 1
The preparation method of the coextrusion self-adhesive biodegradable barrier composite film comprises the following steps:
(1) Preparation of polybutylene terephthalate/polylactic acid composite material modified with maleic anhydride grafting (PBAT/PLA-g-MAH)
80 parts by weight of PBAT and 20 parts by weight of PLA were poured into a mixer, and 0.9 parts by weight of maleic anhydride and 0.09 parts by weight of BIPB were added in a stirred state, and uniformly mixed to prepare a premix. And then pouring the premix into a feed hopper of a double-screw extruder, melting and extruding the premix by the double-screw extruder, cooling the draw bar by water, and granulating and drying the draw bar to obtain cylindrical particles (namely PBAT/PLA-g-MAH). The obtained PBAT/PLA-g-MAH melt has a mass flow rate of 1.2g/10min, a grafting ratio of 0.69%, a tensile breaking strength of 17MPa and an elongation at break of 300%.
(2) Preparation of thermoplastically processable polyvinyl alcohols
A mixture of 100 parts by weight PVA, 25 parts by weight plasticizer (including 20 parts by weight glycerin, 5 parts by weight polyethylene glycol), 1 part by weight silicone powder, 0.5 part by weight antioxidant 168, and 0.5 part by weight antioxidant 1098 was pre-mixed in a blender. And then pouring the premix into a hopper of a double-screw extruder, carrying out melt extrusion by the double-screw extruder, conveying by a crawler belt, and carrying out air cooling and granulating to prepare cylindrical particles (namely the thermoplastic processable polyvinyl alcohol). The resulting thermoplastically processable polyvinyl alcohol had a tensile strength of 36MPa and an elongation at break of 270%.
(3) Preparation of composite films
In a three-layer coextrusion extruder, two protective outer layers are PBAT/PLA-g-MAH, the middle layer is thermoplastic processable polyvinyl alcohol, and the composite film is prepared by self-bonding compounding, extrusion, traction, cooling, curling and packaging through a three-layer coextrusion die head according to the A/B/A mode. The temperature control of the protective outer layer of the three-layer extruder comprises processing temperature control from one region to five regions, wherein the processing temperature control from one region to five regions is 120 ℃, 170 ℃, 190 ℃ and 190 ℃ respectively; the temperature control of the middle layer of the three-layer extruder comprises processing temperature control of one region to five regions, wherein the processing temperature control of the one region to the five regions is 140 ℃, 170 ℃, 190 ℃ and 200 ℃ respectively; the die temperature was controlled to 190 ℃. The total thickness of the composite film is 80 mu m, the thickness of the middle layer is 70 mu m, and the thickness of the protective outer layers is 5 mu m respectively.
Example 2
The preparation method of the coextrusion self-adhesive biodegradable barrier composite film comprises the following steps:
(1) Preparation of polybutylene terephthalate/polylactic acid composite material modified with maleic anhydride grafting (PBAT/PLA-g-MAH)
95 parts by weight of PBAT and 5 parts by weight of PLA were poured into a mixer, and 1.0 parts by weight of maleic anhydride and 0.1 parts by weight of BIPB were added in a stirred state, and uniformly mixed to prepare a premix. And then pouring the premix into a feed hopper of a double-screw extruder, melting and extruding the premix by the double-screw extruder, cooling the draw bar by water, and granulating and drying the draw bar to obtain cylindrical particles (namely PBAT/PLA-g-MAH). The obtained PBAT/PLA-g-MAH melt has a mass flow rate of 1.4g/10min, a grafting rate of 0.72%, a tensile breaking strength of 13MPa and an elongation at break of 550%.
(2) Preparation of thermoplastically processable polyvinyl alcohols
A mixture of 100 parts by weight PVA, 35 parts by weight plasticizer (including 22 parts by weight glycerin, 13 parts by weight polyethylene glycol), 1 part by weight silicone powder, 1 part by weight antioxidant 168, and 1 part by weight antioxidant 1098 was pre-mixed in a blender. And then pouring the premix into a hopper of a double-screw extruder, carrying out melt extrusion by the double-screw extruder, conveying by a crawler belt, and carrying out air cooling and granulating to prepare cylindrical particles (namely the thermoplastic processable polyvinyl alcohol). The resulting thermoplastically processable polyvinyl alcohol had a tensile strength of 42MPa and an elongation at break of 320%.
(3) Preparation of composite films
In a three-layer coextrusion extruder, two protective outer layers are PBAT/PLA-g-MAH, the middle layer is thermoplastic processable polyvinyl alcohol, and the composite film is prepared by self-bonding compounding, extrusion, traction, cooling, curling and packaging through a three-layer coextrusion die head according to the A/B/A mode. The temperature control of the protective outer layer of the three-layer extruder comprises processing temperature control of one region to five regions, wherein the processing temperature control of the one region to the five regions is 120 ℃, 150 ℃, 160 ℃, 180 ℃ and 180 ℃ respectively; the temperature control of the middle layer of the three-layer extruder comprises processing temperature control of one region to five regions, wherein the processing temperature control of the one region to the five regions is 150 ℃, 180 ℃, 190 ℃ and 190 ℃ respectively; the die temperature was controlled to 200 ℃. The total thickness of the composite film is 40 mu m, the thickness of the middle layer is 20 mu m, and the thickness of the protective outer layers is 5 mu m respectively.
Example 3
The preparation method of the coextrusion self-adhesive biodegradable barrier composite film comprises the following steps:
(1) Preparation of polybutylene terephthalate/polylactic acid composite material modified with maleic anhydride grafting (PBAT/PLA-g-MAH)
90 parts by weight of PBAT and 10 parts by weight of PLA were poured into a mixer, and 1.1 parts by weight of maleic anhydride and 0.11 parts by weight of BIPB were added in a stirred state, and uniformly mixed to prepare a premix. And then pouring the premix into a feed hopper of a double-screw extruder, melting and extruding the premix by the double-screw extruder, cooling the draw bar by water, and granulating and drying the draw bar to obtain cylindrical particles (namely PBAT/PLA-g-MAH). The obtained PBAT/PLA-g-MAH melt has a mass flow rate of 1.5g/10min, a grafting ratio of 0.74%, a tensile breaking strength of 14MPa and an elongation at break of 420%.
(2) Preparation of thermoplastically processable polyvinyl alcohols
A mixture of 100 parts by weight PVA, 30 parts by weight plasticizer (including 20 parts by weight glycerin, 10 parts by weight polyethylene glycol), 3 parts by weight silicone powder, 0.5 part by weight antioxidant 168, and 0.5 part by weight antioxidant 1098 was pre-mixed in a blender. And then pouring the premix into a hopper of a double-screw extruder, carrying out melt extrusion by the double-screw extruder, conveying by a crawler belt, and carrying out air cooling and granulating to prepare cylindrical particles (namely the thermoplastic processable polyvinyl alcohol). The resulting thermoplastically processable polyvinyl alcohol has a tensile strength of 39MPa and an elongation at break of 280%.
(3) Preparation of composite films
In a three-layer coextrusion extruder, two protective outer layers are PBAT/PLA-g-MAH, the middle layer is thermoplastic processable polyvinyl alcohol, and the composite film is prepared by self-bonding compounding, extrusion, traction, cooling, curling and packaging through a three-layer coextrusion die head according to the A/B/A mode. The temperature control of the protective outer layer of the three-layer extruder comprises processing temperature control from one region to five regions, wherein the processing temperature control from one region to five regions is 120 ℃, 150 ℃, 160 ℃, 190 ℃ and 200 ℃ respectively; the temperature control of the middle layer of the three-layer extruder comprises processing temperature control of one region to five regions, wherein the processing temperature control of the one region to the five regions is 150 ℃, 180 ℃, 190 ℃ and 220 ℃ respectively; the die temperature was controlled to 210 ℃. The total thickness of the composite film is 60 mu m, the thickness of the middle layer is 40 mu m, and the thickness of the protective outer layers is 10 mu m respectively.
Example 4
The preparation method of the coextrusion self-adhesive biodegradable barrier composite film comprises the following steps:
(1) Preparation of polybutylene terephthalate/polylactic acid composite material modified with maleic anhydride grafting (PBAT/PLA-g-MAH)
85 parts by weight of PBAT and 15 parts by weight of PLA were poured into a mixer, and 0.8 parts by weight of maleic anhydride and 0.08 parts by weight of BIPB were added in a stirred state, and uniformly mixed to prepare a premix. And then pouring the premix into a feed hopper of a double-screw extruder, melting and extruding the premix by the double-screw extruder, cooling the draw bar by water, and granulating and drying the draw bar to obtain cylindrical particles (namely PBAT/PLA-g-MAH). The obtained PBAT/PLA-g-MAH melt has a mass flow rate of 1.3g/10min, a grafting rate of 0.63%, a tensile breaking strength of 15MPa and an elongation at break of 370%.
(2) Preparation of thermoplastically processable polyvinyl alcohols
A mixture of 100 parts by weight PVA, 30 parts by weight plasticizer (including 25 parts by weight glycerin, 5 parts by weight polyethylene glycol), 1 part by weight silicone powder, 0.5 part by weight antioxidant 168, and 0.5 part by weight antioxidant 1098 was pre-mixed in a blender. And then pouring the premix into a hopper of a double-screw extruder, carrying out melt extrusion by the double-screw extruder, conveying by a crawler belt, and carrying out air cooling and granulating to prepare cylindrical particles (namely the thermoplastic processable polyvinyl alcohol). The resulting thermoplastically processable polyvinyl alcohol had a tensile strength of 38MPa and an elongation at break of 300%.
(3) Preparation of composite films
In a three-layer coextrusion extruder, two protective outer layers are PBAT/PLA-g-MAH, the middle layer is thermoplastic processable polyvinyl alcohol, and the composite film is prepared by self-bonding compounding, extrusion, traction, cooling, curling and packaging through a three-layer coextrusion die head according to the A/B/A mode. The temperature control of the protective outer layer of the three-layer extruder comprises processing temperature control from one region to five regions, wherein the processing temperature control from one region to five regions is 120 ℃, 140 ℃, 170 ℃ and 190 ℃ respectively; the temperature control of the middle layer of the three-layer extruder comprises processing temperature control of one region to five regions, wherein the processing temperature control of the one region to the five regions is 150 ℃, 180 ℃, 190 ℃ and 210 ℃ respectively; the die temperature was controlled to 200 ℃. The total thickness of the composite film is 70 mu m, the thickness of the middle layer is 60 mu m, and the thickness of the protective outer layers is 5 mu m respectively.
Comparative example 1
A preparation method of a barrier composite film comprises the following steps:
(1) Preparation of polybutylene terephthalate adipate/polylactic acid composite (PBAT/PLA)
80 parts by weight of PBAT and 20 parts by weight of PLA are poured into a mixer to be uniformly mixed, and the premix is prepared. And then pouring the premix into a feed hopper of a double-screw extruder, melting and extruding the premix by the double-screw extruder, cooling the draw bar by water, and granulating and drying the draw bar to obtain cylindrical particles (namely PBAT/PLA). The obtained PBAT/PLA melt has a mass flow plastic ratio of 1g/10in, a tensile breaking strength of 16MPa and an elongation at break of 290%.
(2) Preparation of thermoplastically processable polyvinyl alcohols
A mixture of 100 parts by weight PVA, 25 parts by weight plasticizer (including 20 parts by weight glycerin, 5 parts by weight polyethylene glycol), 1 part by weight silicone powder, 0.5 part by weight antioxidant 168, and 0.5 part by weight antioxidant 1098 was pre-mixed in a blender. And then pouring the premix into a hopper of a double-screw extruder, carrying out melt extrusion by the double-screw extruder, conveying by a crawler belt, and carrying out air cooling and granulating to prepare cylindrical particles (namely the thermoplastic processable polyvinyl alcohol). The resulting thermoplastically processable polyvinyl alcohol had a tensile strength of 36MPa and an elongation at break of 270%.
(3) Preparation of composite films
In a three-layer coextrusion extruder, two protective outer layers are PBAT/PLA, the middle layer is thermoplastic processable polyvinyl alcohol, and the composite film is prepared by self-bonding compounding, extrusion, traction, cooling, crimping and packaging through a three-layer coextrusion die head in an A/B/A mode (the PBAT/PLA does not have the bonding performance because the PBAT/PLA does not carry out modification treatment, and the self-bonding cannot be realized during preparation). The temperature control of the protective outer layer of the three-layer extruder comprises processing temperature control from one region to five regions, wherein the processing temperature control from one region to five regions is 120 ℃, 170 ℃, 190 ℃ and 190 ℃ respectively; the temperature control of the middle layer of the three-layer extruder comprises processing temperature control of one region to five regions, wherein the processing temperature control of the one region to the five regions is 140 ℃, 170 ℃, 190 ℃ and 200 ℃ respectively; the die temperature was controlled to 190 ℃. The total thickness of the composite film is 80 mu m, the thickness of the middle layer is 70 mu m, and the thickness of the protective outer layers is 5 mu m respectively.
This comparative example 1 differs from example 1 above in that the polybutylene terephthalate adipate/polylactic acid composite material was not modified with maleic anhydride.
Performance test
In order to verify the properties of the composite films obtained in the above examples and comparative examples, the composite films obtained in the above examples and comparative examples were tested for tensile strength, elongation at break, right angle tear strength, oxygen transmission rate, and the like, and the test results are shown in table 1 below:
table 1 Performance data of the composite films obtained in each of examples and comparative examples
From the test data in Table 1, it is understood that the composite films obtained in examples 1 to 4 of the present application have excellent mechanical properties and oxygen barrier properties.
As can be seen from the number of comparative example 1, since the protective outer layer does not have self-adhesive property during preparation of the comparative example, a qualified three-layer composite film cannot be prepared, and the mechanical properties obtained during mechanical property detection after the completion of the compounding are poor.
Finally, it should be noted that: these embodiments are merely for illustrating the present application and do not limit the scope of the present application. Further, various other changes and modifications will be apparent to those skilled in the art from the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present application.
Claims (10)
1. The coextrusion self-bonding biodegradable barrier composite film is characterized by comprising a middle layer and protective outer layers arranged on two opposite sides of the middle layer; the protective outer layer is attached to the middle layer in a self-bonding mode;
the middle layer is made of polyvinyl alcohol which can be processed by thermoplastic;
the protective outer layer is made of a polybutylene terephthalate/polylactic acid composite material modified by maleic anhydride grafting.
2. The coextruded self-adhesive biodegradable barrier composite film according to claim 1, characterized in that the thermoplastically processable polyvinyl alcohol comprises the following components in parts by weight:
100 parts of polyvinyl alcohol, 25-35 parts of plasticizer, 1-3 parts of lubricant and 1-2 parts of antioxidant.
3. The coextruded self-adhesive biodegradable barrier composite film according to claim 2, characterized in that the thermoplastic processable polyvinyl alcohol is prepared by the following method: placing polyvinyl alcohol, plasticizer, lubricant and antioxidant into a mixer, uniformly mixing, placing into a double-screw extruder, melting and extruding, conveying by a crawler, granulating and drying to obtain the thermoplastic-processable polyvinyl alcohol.
4. The coextrusion self-adhesive biodegradable barrier composite film according to claim 2, wherein the plasticizer is a mixture of glycerin and polyethylene glycol in a weight ratio of (1-5) to (1-3), and the lubricant is silicone powder with a weight average molecular weight of 70-75 ten thousand.
5. The coextruded self-adhesive biodegradable barrier composite film according to claim 1, characterized in that the preparation method of the polybutylene terephthalate/polylactic acid composite material modified by maleic anhydride grafting comprises the following steps:
A. placing polybutylene terephthalate and polylactic acid into a mixer for uniformly mixing to obtain a mixture;
B. adding maleic anhydride and di-tert-butyl diisopropyl peroxide into the mixture in the step A under the condition of stirring, and uniformly mixing to obtain a premix;
C. adding the premix into a double-screw extruder for melt extrusion, and then carrying out water-cooling drawing, granulating and drying to obtain the maleic anhydride grafted modified polybutylene terephthalate/polylactic acid composite material.
6. The coextrusion self-adhesive biodegradable barrier composite film according to claim 5, wherein the polybutylene terephthalate is added in an amount of 80-95 parts by weight and the polylactic acid is added in an amount of 5-20 parts by weight in the step A.
7. The coextruded self-adhesive biodegradable barrier composite film according to claim 5, characterized in that the maleic anhydride is added in an amount of 0.8% to 1.1% by weight of the mixture in step B.
8. The coextruded self-adhesive biodegradable barrier composite film according to claim 5, characterized in that the added amount of di-t-butyldiisopropylbenzene peroxide in step B is 0.08-0.11% by weight of the mixture.
9. A coextruded self-adhesive biodegradable barrier composite film according to any one of claims 1-8, characterized in that the preparation method of said composite film comprises the following steps:
respectively placing the thermoplastic processed polyvinyl alcohol and the polybutylene terephthalate/polylactic acid composite material modified by maleic anhydride grafting into a three-layer coextrusion extruder, and carrying out self-bonding compounding, extrusion, traction, cooling, curling and packaging through a three-layer coextrusion die head according to the A/B/A mode to obtain a composite film;
wherein, the thermoplastic polyvinyl alcohol is a middle layer, and the polybutylene terephthalate/polylactic acid composite material modified by maleic anhydride grafting is a protective outer layer.
10. A coextruded self-adhesive biodegradable barrier composite film according to any one of claims 1-8, characterized in that the total thickness of the composite film is 40-80 μm, the thickness of the protective outer layer being 5% -10% of the total thickness of the composite film.
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