CN115895084B - PE plastic and PE plastic heating bag - Google Patents
PE plastic and PE plastic heating bag Download PDFInfo
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- CN115895084B CN115895084B CN202211435583.1A CN202211435583A CN115895084B CN 115895084 B CN115895084 B CN 115895084B CN 202211435583 A CN202211435583 A CN 202211435583A CN 115895084 B CN115895084 B CN 115895084B
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- 229920003023 plastic Polymers 0.000 title claims abstract description 104
- 239000004033 plastic Substances 0.000 title claims abstract description 104
- 238000010438 heat treatment Methods 0.000 title claims abstract description 73
- 239000004698 Polyethylene Substances 0.000 claims abstract description 108
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 claims abstract description 49
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 25
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 229920001661 Chitosan Polymers 0.000 claims abstract description 16
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 16
- 239000004006 olive oil Substances 0.000 claims abstract description 16
- 235000008390 olive oil Nutrition 0.000 claims abstract description 16
- 229920000954 Polyglycolide Polymers 0.000 claims abstract description 13
- 239000004633 polyglycolic acid Substances 0.000 claims abstract description 13
- 239000004954 Polyphthalamide Substances 0.000 claims abstract description 7
- 229920006375 polyphtalamide Polymers 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 63
- 230000003197 catalytic effect Effects 0.000 claims description 38
- 239000012752 auxiliary agent Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 239000012968 metallocene catalyst Substances 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 15
- 238000013329 compounding Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 12
- 239000008103 glucose Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical group [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 229920002873 Polyethylenimine Polymers 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- ZPKSAIWDCQVXSQ-UHFFFAOYSA-N (4-aminophenoxy)boronic acid Chemical compound NC1=CC=C(OB(O)O)C=C1 ZPKSAIWDCQVXSQ-UHFFFAOYSA-N 0.000 claims description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 41
- 235000013305 food Nutrition 0.000 abstract description 16
- 230000004888 barrier function Effects 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000010411 cooking Methods 0.000 abstract description 3
- 239000005022 packaging material Substances 0.000 abstract description 3
- 231100000614 poison Toxicity 0.000 abstract description 3
- 239000003440 toxic substance Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 28
- -1 polyethylene Polymers 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 229920000573 polyethylene Polymers 0.000 description 14
- 230000001276 controlling effect Effects 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- ZSKXYSCQDWAUCM-UHFFFAOYSA-N 1-(chloromethyl)-2-dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1CCl ZSKXYSCQDWAUCM-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
Classifications
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- 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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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to the technical field of packaging materials, and particularly discloses PE plastic and a PE plastic heating bag, wherein the PE plastic is prepared by melt blending metallocene polyethylene, carboxymethyl chitosan, olive oil and high-molecular-weight polyglycolic acid, extruding and granulating; the PE plastic has the advantages of good transparency, good heat resistance, high molecular structure regularity, high crystallinity, regular and compact molecular chain arrangement, small segment pore, high rigidity and good gas molecular barrier property and processability. The application also provides a PE plastic heating bag which sequentially comprises an inner layer, a middle layer and an outer layer from inside to outside; the preparation raw materials of the inner layer, the middle layer and the outer layer are at least one of PE plastic, low-density polyethylene, metallocene polyethylene, an opening slipping agent and polyphthalamide; the PE plastic heating bag is high in safety, is used for heating and cooking food, does not release toxic substances and does not cause food pollution.
Description
Technical Field
The application relates to the technical field of packaging materials, in particular to PE plastic and a PE plastic heating bag.
Background
Plastic heating bag (also called retort pouch) is made of multi-layer film material, and is made into a certain size by dry-process compounding or coextrusion compounding. The plastic heating bag can withstand high-temperature damp-heat sterilization, and meets the requirements of good heat sealability, heat resistance, water resistance, high strength, high barrier property and the like. Compared with the traditional metal can container, the plastic heating bag has simpler production process and processing equipment, lower production cost and lower price; when in heating sterilization, the sterilization temperature can be reached faster, and the sterilization energy consumption is lower; in addition, the plastic heating bag is lighter and convenient to carry. With the development of the economy in China, the travel industry is vigorous, the demand of people for convenient foods such as soft cans, high-temperature steamed foods and the like is higher and higher, and the market of plastic heating bags is expanding continuously.
At present, plastic heating bags used in the food packaging industry mainly comprise heating bags of polyethylene, polypropylene, polyvinyl chloride, polystyrene and the like. The polyethylene heating bag is nontoxic, tasteless, transparent, good in chemical stability, good in water resistance and low in water absorption, so that the polyethylene heating bag is commonly used for moistureproof packaging. However, the surface of the polyethylene heating bag is nonpolar, the heat resistance is low, the air permeability is high, and the defects of difficult adhesion and printing, poor barrier property, poor fresh-keeping property, poor steaming and boiling resistance, poor oxidation resistance and the like of the product are commonly existed in the actual processing and application process. The existence of these problems has greatly limited the application and development of polyethylene packaging materials. In the related art, additives such as antioxidants, heat stabilizers and slipping agents are added to improve the performance defects of the polyethylene heating bag, but when food is steamed, the added additive components can permeate into the food to cause food pollution and further cause human health hazard. Based on the above statements, it is difficult to bond and print, and process, to improve polyethylene heating bags; the PE plastic and the PE plastic heating bag provided by the application have the defects of poor barrier property, poor fresh-keeping property, poor steaming and boiling resistance, poor oxidation resistance and the like.
Disclosure of Invention
In order to solve the problems that the polyethylene heating bag is difficult to adhere and print and difficult to process in the related art; the PE plastic and the PE plastic heating bag provided by the application have the defects of poor barrier property, poor fresh-keeping property, poor steaming and boiling resistance, poor oxidation resistance and the like.
In a first aspect, the application provides a PE plastic, which adopts the following technical scheme:
a PE plastic is prepared from the following raw materials in parts by weight: 100 parts of metallocene polyethylene, 3-8 parts of carboxymethyl chitosan, 2-12 parts of olive oil and 1-2 parts of high molecular weight polyglycolic acid
Preferably, the PE plastic is prepared by the following steps:
S1, under the action of a catalyst, taking ethylene monomer as a raw material, and carrying out polymerization reaction in a protective atmosphere to obtain metallocene polyethylene;
s2, putting metallocene polyethylene, carboxymethyl chitosan, olive oil and high-molecular-weight polyglycolic acid into a stirrer together, and heating and mixing to obtain a mixture;
and S3, adding the mixture into a double-screw extruder, carrying out melt blending, extruding and granulating to obtain the PE plastic.
By adopting the technical scheme, the application prepares the metallocene polyethylene, and prepares the required PE plastic by blending and modifying carboxymethyl chitosan, olive oil, high molecular weight polyglycolic acid and the metallocene polyethylene; the PE plastic has good transparency, good heat resistance, high molecular structure regularity, high crystallinity, regular and compact molecular chain arrangement, small segment pore, high rigidity and good gas molecular barrier property; the PE plastic provided by the application is used for preparing PE plastic heating bags, has good bonding and printing properties, can be tightly combined with raw materials such as auxiliary agents and the like, and improves the mechanical property, barrier property, poor steaming resistance and oxidation resistance of products.
Preferably, the metallocene polyethylene in the step S1 has a weight average molecular weight of 12-18 ten thousand, a molecular weight distribution width index of 2.7-5, and a density of 0.907-0.921g/cm 3.
By adopting the technical scheme, the metallocene polyethylene prepared by the application has the advantages of no odor and smell, good chemical stability, good heat resistance and cold resistance, higher rigidity and toughness, high mechanical strength and good machining performance.
Preferably, the heating and mixing conditions in the step S2 are as follows: heating to 120-140 ℃, stirring at 200-300r/min, and heating and mixing for 4-12min.
Preferably, the twin screw extruder parameters in step S3 are: the temperature range from the feeding section to the machine head is 160-190 ℃, and the rotating speed of the screw is 80-100r/min.
By adopting the technical scheme, the preparation process parameters of PE plastic are improved and controlled, so that the finally obtained PE plastic is excellent in comprehensive performance and low in preparation cost.
Preferably, the catalyst is a compound catalyst, and comprises a metallocene catalyst, a catalytic auxiliary agent and a catalytic carrier.
Preferably, the mass ratio of the metallocene catalyst, the catalyst auxiliary agent and the catalyst carrier is 8-12:1:40.
Preferably, the metallocene catalyst is zirconocene dichloride.
Preferably, the catalyst auxiliary agent is a compound of triethylaluminum and 4-aminophenylboric acid in a mass ratio of 1:5.8.
Preferably, the catalytic support is carbonized porous Al 2O3.
By adopting the technical scheme, the metallocene catalyst and the catalytic auxiliary agent are compounded to be jointly used for ethylene polymerization catalysis, and the catalytic carrier is used for loading the metallocene catalyst and the catalytic auxiliary agent, so that the catalyst strength can be remarkably improved, the catalytic area can be increased, and the catalytic activity and the catalytic efficiency can be improved; the method is used for ethylene polymerization catalysis, and has the advantages of small addition amount, high catalysis speed, high molecular weight, high crystallinity, and excellent mechanical property and processability of the obtained polyethylene.
Preferably, the carbonized porous Al 2O3 is prepared by the following method:
(1) Mixing alumina powder with deionized water to form slurry with the mass fraction of 40-60%;
(2) Adding glucose and polyethyleneimine into the slurry obtained in the step (1), stirring and dissolving, placing the mixture at 100-150 ℃ and 1.8-2.5MPa for 1-5 hours, filtering, and drying to obtain modified alumina;
(3) And (3) placing the modified alumina in a protective atmosphere, calcining for 3-6 hours at 620-680 ℃, and cooling and grinding to obtain carbonized porous Al 2O3.
Preferably, the mass ratio of the slurry, the glucose and the polyethyleneimine in the step (2) is 100:18:1-5.
Preferably, the particle size of carbonized porous Al 2O3 after grinding in the step (3) is less than 1 μm.
By adopting the technical scheme, the application utilizes glucose and polyethyleneimine to heat the alumina slurry, and finally the carbonized porous Al 2O3 is obtained by calcination; the pore diameter channel and the porosity of the carbonized porous Al 2O3 are controlled and prepared by limiting the proportion of reaction raw materials and regulating and controlling the reaction conditions; the obtained carbonized porous Al 2O3 has strong binding force with the catalyst, effectively increases the catalytic area of the catalyst, and improves the catalytic activity and the utilization rate of the catalyst.
Preferably, the catalyst is prepared by the following method: fully dissolving zirconocene dichloride in hot water, controlling the stirring speed to be 30-60r/min, adding a catalytic auxiliary agent and a catalytic carrier while stirring, keeping the temperature to be 80-100 ℃, immersing for 4-6h, controlling the temperature to be 110-130 ℃, and vacuum drying the product to obtain the catalyst.
By adopting the technical scheme, the catalyst promoter and the catalyst carrier are fully immersed and dried by preparing the zirconocene dichloride solution, so that the loading effect of the zirconocene dichloride and the catalyst promoter can be effectively improved, and the obtained catalyst has the advantages of good particle morphology, large specific surface area, high porosity and high catalytic ethylene polymerization activity; the catalyst is used for ethylene polymerization with little consumption, and the production cost is reduced.
In a second aspect, the application provides a PE plastic heating bag, which adopts the following technical scheme:
A PE plastic heating bag is prepared from PE plastic.
Preferably, the PE plastic heating bag sequentially comprises an inner layer, a middle layer and an outer layer from inside to outside; the inner layer, the middle layer and the outer layer are prepared from at least one of PE plastic, low-density polyethylene, metallocene polyethylene, an opening slipping agent and polyphthalamide.
Preferably, the low density polyethylene is model 2426H and/or 2520D;
The metallocene polyethylene is 3505MC and/or 2710EP.
Preferably, the outer layer is prepared from the following raw materials in parts by weight: 50 parts of PE plastic, 40 parts of metallocene polyethylene 3505MC, and 10 parts of low-density polyethylene 2426H;
The middle layer is prepared from the following raw materials in parts by weight: 30 parts of PE plastic, 20 parts of metallocene polyethylene 2710EP, 40 parts of metallocene polyethylene 3505MC, and 10 parts of low-density polyethylene 2426H;
The inner layer is prepared from the following raw materials in parts by weight: 40 parts of PE plastic, 30 parts of metallocene polyethylene 3505MC, 20 parts of low-density polyethylene 2520D, 10 parts of low-density polyethylene 2426H, 1.5 parts of an opening slipping agent and 2 parts of polyphthalamide.
By adopting the technical scheme, the proportion of different raw materials is controlled, the PE plastic, the commercial metallocene polyethylene and the low-density polyethylene are compounded to prepare the outer layer, the middle layer and the inner layer of the PE plastic heating bag, and the PE plastic heating bag is prepared by compounding the PE plastic heating bag after three layers of coextrusion, and the PE plastic heating bag has excellent heat resistance and cold resistance, can be frozen at the temperature of minus 45 ℃ for a long time, and can be sterilized at the temperature of 135 ℃ for 30 minutes or 140 ℃ for 5 minutes; the PE plastic heating bag has the advantages of good moisture resistance, good heat sealing property, high heat sealing strength, good heat sealing dimensional stability, no deformation, good impact resistance and good pinhole resistance, is used for food packaging, can effectively prolong the quality and fresh-keeping period of food, and has high safety, is used for heating and cooking food, does not release toxic substances and does not cause food pollution.
Preferably, the PE plastic heating bag is prepared by the following method:
According to the formula, the raw materials of the outer layer, the middle layer and the inner layer are respectively and uniformly mixed, are melted and extruded by a multi-layer co-extruder, enter an annular co-extrusion die head to form a three-layer film for extrusion, and are sheared after co-extrusion compounding to obtain the required PE plastic heating bag.
Preferably, the extrusion process parameters are: the melting temperature is 158-165 ℃, the die head temperature is 164-168 ℃, the screw rotating speed is 70-90r/min, and the traction speed is 8.0-12m/min.
By adopting the technical scheme, the PE plastic heating bag has the advantages of simple preparation process, mild preparation conditions, high product quality and high yield, and is suitable for industrial production.
In summary, the application has the following beneficial effects:
1. According to the application, ethylene is used as a raw material, and a catalyst is added in the polymerization reaction, so that the reaction speed is effectively increased by adding the catalyst; the polymerization degree of polyethylene is further improved by compounding the metallocene catalyst and the catalyst auxiliary agent and utilizing the catalyst auxiliary agent to cooperate with the catalytic performance of the metallocene catalyst; by adding the catalytic carrier into the catalyst, the porous structure of the catalytic carrier can increase the contact area between the catalyst and reactants when the catalyst is loaded, further promote the reaction and improve the polymerization degree of polyethylene; the obtained metallocene polyethylene has the advantages of no odor and smell, good chemical stability, good heat resistance and cold resistance, higher rigidity and toughness, high mechanical strength and good machining performance.
2. According to the application, carboxymethyl chitosan, olive oil, high molecular weight polyglycolic acid and metallocene polyethylene are used for blending modification to prepare the required PE plastic; the PE plastic has good transparency, good heat resistance, high molecular structure regularity, high crystallinity, regular and compact molecular chain arrangement, small segment pore, high rigidity and good gas molecular barrier property; the PE plastic provided by the application is used for preparing PE plastic heating bags, has good bonding and printing properties, can be tightly combined with raw materials such as auxiliary agents and the like, and improves the mechanical property, barrier property, poor steaming resistance and oxidation resistance of products.
3. The PE plastic heating bag is prepared by controlling the proportion of different raw materials and compounding the PE plastic, the commercially available metallocene polyethylene and the low-density polyethylene to prepare the outer layer, the middle layer and the inner layer materials of the PE plastic heating bag, and the PE plastic heating bag is prepared by compounding the PE plastic heating bag after three layers of coextrusion; the PE plastic heating bag has the advantages of good moisture resistance, good heat sealing property, high heat sealing strength, good heat sealing dimensional stability, no deformation, good impact resistance and good pinhole resistance, is used for food packaging, can effectively prolong the quality and fresh-keeping period of food, and has high safety, is used for heating and cooking food, does not release toxic substances and does not cause food pollution.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation examples 1-3 and comparative preparation example 1 provide a method for preparing a catalytic support carbonized porous Al 2O3.
Preparation example 1
Carbonized porous Al 2O3 is prepared by the following method:
(1) Alumina powder with the particle size of 1 mu m is mixed with deionized water to form slurry with the mass fraction of 40%;
(2) Adding glucose and polyethyleneimine into the slurry obtained in the step (1), stirring and dissolving, placing at 100 ℃ and 1.8MPa for 5 hours, filtering, and drying to obtain modified alumina, wherein the mass ratio of the slurry to the glucose to the polyethyleneimine is 100:18:1;
(3) And (3) placing the modified alumina in an argon atmosphere, calcining for 6 hours at 620 ℃, cooling and grinding to obtain carbonized porous Al 2O3 with the particle size smaller than 1 mu m.
Preparation example 2
Carbonized porous Al 2O3 is prepared by the following method:
(1) Mixing alumina powder with the particle size of 100 mu m with deionized water to form slurry with the mass fraction of 50%;
(2) Adding glucose and polyethyleneimine into the slurry obtained in the step (1), stirring and dissolving, placing at 125 ℃ and 2.2MPa for 3 hours, filtering, and drying to obtain modified alumina, wherein the mass ratio of the slurry to the glucose to the polyethyleneimine is 100:18:3;
(3) And (3) placing the modified alumina in an argon atmosphere, calcining for 4 hours at 650 ℃, cooling and grinding to obtain carbonized porous Al 2O3 with the particle size smaller than 1 mu m.
Preparation example 3
Carbonized porous Al 2O3 is prepared by the following method:
(1) Mixing alumina powder with the particle size of 180 mu m with deionized water to obtain slurry with the mass fraction of 60%;
(2) Adding glucose and polyethyleneimine into the slurry obtained in the step (1), stirring and dissolving, placing at 150 ℃ and 2.5MPa for 1 hour, filtering, and drying to obtain modified alumina, wherein the mass ratio of the slurry to the glucose to the polyethyleneimine is 100:18:5;
(3) And (3) placing the modified alumina in an argon atmosphere, calcining at 680 ℃ for 3 hours, cooling and grinding to obtain carbonized porous Al 2O3 with the particle size smaller than 1 mu m.
Comparative preparation example 1
Carbonized porous Al 2O3 is prepared by the following method:
(1) Mixing alumina powder with the particle size of 100 mu m with deionized water to form slurry with the mass fraction of 50%;
(2) Adding glucose into the slurry obtained in the step (1), stirring and dissolving, placing at 125 ℃ and 2.2MPa for 3 hours, filtering, and drying to obtain modified alumina, wherein the mass ratio of the slurry to the glucose is 100:21;
(3) And (3) placing the modified alumina in an argon atmosphere, calcining for 4 hours at 650 ℃, cooling and grinding to obtain carbonized porous Al 2O3 with the particle size smaller than 1 mu m.
Preparation examples 4-7 and comparative preparation examples 2-5 provide catalysts and methods of preparing the same.
Preparation example 4
The catalyst is prepared by compounding a metallocene catalyst, a catalytic auxiliary agent and a catalytic carrier in a mass ratio of 8:1:40;
wherein the metallocene catalyst is zirconocene dichloride;
the catalyst auxiliary agent is a compound of triethylaluminum and 4-aminophenylboric acid in a mass ratio of 1:5.8;
the catalytic support was prepared from preparation 1;
The catalyst is prepared by the following steps: fully dissolving zirconocene dichloride in hot water, controlling the stirring speed to be 30r/min, adding a catalytic auxiliary agent and a catalytic carrier while stirring, keeping the temperature at 80 ℃, immersing for 6 hours, controlling the temperature at 110 ℃, and vacuum drying the product to obtain the catalyst.
Preparation example 5
The catalyst is prepared by compounding a metallocene catalyst, a catalytic auxiliary agent and a catalytic carrier in a mass ratio of 10:1:40;
wherein the metallocene catalyst is zirconocene dichloride;
the catalyst auxiliary agent is a compound of triethylaluminum and 4-aminophenylboric acid in a mass ratio of 1:5.8;
the catalytic support was prepared from preparation 2;
The catalyst is prepared by the following steps: fully dissolving zirconocene dichloride in hot water, controlling the stirring speed to be 45r/min, adding a catalytic auxiliary agent and a catalytic carrier while stirring, keeping the temperature to be 90 ℃, immersing for 5 hours, controlling the temperature to be 120 ℃, and vacuum drying the product to obtain the catalyst.
Preparation example 6
The catalyst is prepared by compounding a metallocene catalyst, a catalytic auxiliary agent and a catalytic carrier in a mass ratio of 12:1:40;
wherein the metallocene catalyst is zirconocene dichloride;
the catalyst auxiliary agent is a compound of triethylaluminum and 4-aminophenylboric acid in a mass ratio of 1:5.8;
the catalytic support was prepared from preparation 3;
The catalyst is prepared by the following steps: fully dissolving zirconocene dichloride in hot water, controlling the stirring speed to be 60r/min, adding a catalytic auxiliary agent and a catalytic carrier while stirring, keeping the temperature to be 100 ℃, immersing for 4 hours, controlling the temperature to be 130 ℃, and vacuum drying the product to obtain the catalyst.
Comparative preparation example 2
The preparation example 5 is different from the preparation example only in that the catalyst auxiliary agent is a compound of triethylbutylaluminum and 4-aminophenylboric acid in a mass ratio of 1:1.
Comparative preparation example 3
The same as in preparation example 5 was followed except that the catalyst auxiliary was triethylbutylaluminum.
Comparative preparation example 4
The same as in preparation example 5 was found only in that the catalyst auxiliary was 4-aminophenylboronic acid.
Comparative preparation example 5
The same as in preparation example 5 was true except that the catalytic carrier was prepared from comparative preparation example 1.
Comparative preparation example 6
The same as in preparation example 5, except that the catalytic carrier was prepared by the following method:
(1) Mixing alumina powder with the particle size of 100 mu m with deionized water to form slurry with the mass fraction of 50%;
(2) Placing the slurry obtained in the step (1) at 125 ℃ and 2.2MPa for 3 hours, filtering and drying;
(3) And (3) placing the dried aluminum oxide in an argon atmosphere, calcining for 4 hours at 650 ℃, cooling and grinding to obtain carbonized porous Al 2O3 with the particle size smaller than 1 mu m.
Examples 1-3 provide a PE plastic and a preparation method thereof.
Example 1
The PE plastic is characterized by being prepared from the following raw materials: 100kg of metal polyethylene, 3kg of carboxymethyl chitosan, 12kg of olive oil and 1kg of high molecular weight polyglycolic acid;
A PE plastic made by the steps of:
s1, fully replacing a stainless steel reaction kettle with 2L of volume by high-purity nitrogen, adding 0.3g of the catalyst in preparation example 4 into the reaction kettle, heating to 83 ℃, introducing hydrogen to ensure that the pressure in the reaction kettle is 0.2MPa, then injecting ethylene to ensure that the system pressure is 0.9MPa, keeping the temperature and the pressure of a reaction system constant, cooling after polymerization for 1h, discharging and drying to obtain metallocene polyethylene;
s2, putting 100kg of metallocene polyethylene, 3kg of carboxymethyl chitosan, 12kg of olive oil and 1kg of high molecular weight polyglycolic acid into a stirrer together, controlling the heating temperature to 120 ℃, and heating and mixing for 12min at the stirring speed of 200r/min to obtain a mixture; s3, adding the mixture into a double-screw extruder, carrying out melt blending, extruding and granulating to obtain PE plastic, wherein the temperatures from a feeding section to a machine head section are respectively as follows: 170 ℃, 175 ℃, 180 ℃, 185 ℃, 180 ℃, 170 ℃; the screw speed was 90r/min.
Example 2
The PE plastic is characterized by being prepared from the following raw materials: 100kg of metallocene polyethylene, 5kg of carboxymethyl chitosan, 7kg of olive oil and 1.5kg of high molecular weight polyglycolic acid;
A PE plastic made by the steps of:
S1, fully replacing a stainless steel reaction kettle with 2L of volume by high-purity nitrogen, adding 0.4g of the catalyst in preparation example 5 into the reaction kettle, heating to 87 ℃, introducing hydrogen to ensure that the pressure in the reaction kettle is 0.3MPa, then injecting ethylene to ensure that the system pressure is 1.0MPa, keeping the temperature and the pressure of a reaction system constant, carrying out polymerization for 1.2 hours, cooling, discharging and drying to obtain metallocene polyethylene;
S2, putting 100kg of metallocene polyethylene, 5kg of carboxymethyl chitosan, 7kg of olive oil and 1.5kg of high molecular weight polyglycolic acid into a stirrer together, controlling the heating temperature to 130 ℃, and heating and mixing for 8min at the stirring speed of 250r/min to obtain a mixture; s3, adding the mixture into a double-screw extruder, carrying out melt blending, extruding and granulating to obtain PE plastic, wherein the temperatures from a feeding section to a machine head section are respectively as follows: 170 ℃, 175 ℃, 180 ℃, 185 ℃, 180 ℃, 170 ℃; the screw speed was 90r/min.
Example 3
The PE plastic is characterized by being prepared from the following raw materials: 100kg of metallocene polyethylene, 8kg of carboxymethyl chitosan, 2kg of olive oil and 2kg of high molecular weight polyglycolic acid;
A PE plastic made by the steps of:
S1, fully replacing a stainless steel reaction kettle with 2L of volume by high-purity nitrogen, adding 0.5g of the catalyst in preparation example 6 into the reaction kettle, heating to 90 ℃, introducing hydrogen to ensure that the pressure in the reaction kettle is 0.4MPa, injecting ethylene to ensure that the system pressure is 1.1MPa, keeping the temperature and the pressure of a reaction system constant, carrying out polymerization for 1.5 hours, cooling, discharging and drying to obtain metallocene polyethylene;
S2, putting 100kg of metallocene polyethylene, 8kg of carboxymethyl chitosan, 2kg of olive oil and 2kg of high molecular weight polyglycolic acid into a stirrer together, controlling the heating temperature to 140 ℃, and heating and mixing for 4min at the stirring speed of 300r/min to obtain a mixture; s3, adding the mixture into a double-screw extruder, carrying out melt blending, extruding and granulating to obtain PE plastic, wherein the temperatures from a feeding section to a machine head section are respectively as follows: 170 ℃, 175 ℃, 180 ℃, 185 ℃, 180 ℃, 170 ℃; the screw speed was 90r/min.
Comparative example 1
The only difference from example 2 is that the catalyst in step S1 was the catalyst of comparative preparation 2.
Comparative example 2
The only difference from example 2 is that the catalyst in step S1 was the catalyst of comparative preparation 3.
Comparative example 3
The only difference from example 2 is that the catalyst in step S1 was the catalyst of comparative preparation 4.
Comparative example 4
The only difference from example 2 is that the catalyst in step S1 was the catalyst of comparative preparation 5.
Comparative example 5
The only difference from example 2 is that the catalyst in step S1 was the catalyst of comparative preparation 6.
Comparative example 6
The only difference from example 2 is that the olive oil in step S2 is changed to carboxymethyl chitosan.
Comparative example 7
The only difference from example 2 is that the carboxymethyl chitosan in step S2 was replaced with olive oil.
Examination of the properties of the metallocene polyethylene and PE plastics of examples 1-3 and comparative examples 1-7 gave the results shown in Table 1 below:
wherein, the metallocene polyethylene has the following properties:
activity of the catalyst: refers to the ratio of the total weight of the polyethylene obtained by polymerization and the catalyst addition amount in 1 hour;
Weight average molecular weight: measured by high temperature Gel Permeation Chromatography (GPC);
density: measured by a polyethylene density detector;
the PE plastic has the following properties:
Melt Mass Flow Rate (MFR): testing according to GB/T3682-2000, wherein the load is 2.16Kg;
Shear viscosity at 200 ℃ and critical shear rate at 200 ℃): the test was performed by capillary rheometer according to GB/T25278-2010.
Capillary diameter 1mm, length-diameter ratio 30:1; preheating the piston for 5-10min before the test; the precompression is less than 1KN;
The shear rate is from 50s -1、100s-1 … … to take value, and under each shear rate, the shear stress reaches the equilibrium point; shear viscosity at 200℃means that the shear rate was measured at 300s -1.
TABLE 1
As can be seen from the data shown in table 1:
from the comparison of the properties of example 2 and comparative examples 1-5, it is seen that:
the catalyst promoter and the catalyst carrier in the embodiment 2 of the application can obviously improve the polymerization activity and the weight average molecular weight of the finally prepared metallocene polyethylene;
From example 2 and comparative examples 6 to 7, it can be seen that:
According to the application, the carboxymethyl chitosan and the olive oil in the embodiment 2 act together, so that the processing performance of the finally prepared PE plastic can be obviously improved.
Example 4 provides a PE plastic heating bag and a preparation method thereof.
Example 4
The PE plastic heating bag sequentially comprises an inner layer, a middle layer and an outer layer from inside to outside;
wherein the outer layer is prepared from the following raw materials: 50kg of PE plastic, 40kg of metallocene polyethylene 3505MC and 10kg of low-density polyethylene 2426H;
The middle layer is prepared from the following raw materials: 30kg of PE plastic, 20kg of metallocene polyethylene 2710EP, 40kg of metallocene polyethylene 3505MC, and 10kg of low-density polyethylene 2426H;
the inner layer is prepared from the following raw materials: 40kg of PE plastic, 30kg of metallocene polyethylene 3505MC, 20kg of low-density polyethylene 2520D, 10kg of low-density polyethylene 2426H, 1.5 parts of oleamide and 2 parts of polyphthalamide;
wherein PE plastic was prepared in example 2.
A PE plastic heating bag is prepared by the following method:
According to the formula amount, the raw materials of the outer layer, the middle layer and the inner layer are respectively and uniformly mixed, and the mixture is melted and extruded by a multi-layer co-extruder and then enters an annular co-extrusion die head to form a three-layer film for extrusion, and the three-layer film is sheared after co-extrusion compounding to prepare the required PE plastic heating bag, wherein the extrusion process parameters are as follows: the melting temperature is 165 ℃, the die head temperature is 165 ℃, the screw rotating speed is 80r/min, and the traction speed is 1m/min.
Comparative example 8
The same as in example 4, except that PE plastic is produced from comparative example 7
Comparative example 9
The plastic heating bag sequentially comprises an inner layer, a middle layer and an outer layer from inside to outside;
wherein the outer layer is prepared from the following raw materials: metallocene polyethylene 3505MC 90kg, low density polyethylene 2426h 10kg;
The middle layer is prepared from the following raw materials: metallocene polyethylene 2710EP 50kg, metallocene polyethylene 3505MC 40kg, low density polyethylene 2426H 10kg;
The inner layer is prepared from the following raw materials: 70kg of metallocene polyethylene 3505MC, 20kg of low-density polyethylene 2520D, 10kg of low-density polyethylene 2426H, 1.5 parts of oleamide and 2 parts of polyphthalamide.
A plastic heating bag is prepared by the following method:
According to the formula amount, the raw materials of the outer layer, the middle layer and the inner layer are respectively and uniformly mixed, and the mixture is melted and extruded by a multi-layer co-extruder and then enters an annular co-extrusion die head to form a three-layer film for extrusion, and the three-layer film is sheared after co-extrusion compounding to prepare the required PE plastic heating bag, wherein the extrusion process parameters are as follows: the melting temperature is 165 ℃, the die head temperature is 165 ℃, the screw rotating speed is 80r/min, and the traction speed is 1m/min.
The performance of PE plastic heating bags in example 4 and comparative examples 8-9 was tested according to national standard GB/T10004-2008, composite film, bag resistant to digestion, giving the results shown in Table 2 below:
Table 2:
as can be seen from the data shown in table 2: the PE plastic prepared in the embodiment 2 of the application is compounded with the commercial metallocene polyethylene and the low-density polyethylene to prepare the PE plastic heating bag with the best comprehensive performance. The comprehensive performance is far superior to PE plastic heating bags prepared by compounding only commercial metallocene polyethylene and low-density polyethylene.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (7)
1. The PE plastic is characterized by being prepared from the following raw materials in parts by weight: 100 parts of metallocene polyethylene, 3-8 parts of carboxymethyl chitosan, 2-12 parts of olive oil and 1-2 parts of high molecular weight polyglycolic acid;
The PE plastic is prepared by the following steps:
S1, under the action of a catalyst, taking ethylene monomer as a raw material, and carrying out polymerization reaction in a protective atmosphere to obtain metallocene polyethylene;
s2, putting metallocene polyethylene, carboxymethyl chitosan, olive oil and high-molecular-weight polyglycolic acid into a stirrer together, and heating and mixing to obtain a mixture;
s3, adding the mixture into a double-screw extruder, carrying out melt blending, extruding and granulating to obtain PE plastic;
The catalyst is a compound catalyst and comprises a metallocene catalyst, a catalytic auxiliary agent and a catalytic carrier; the mass ratio of the metallocene catalyst to the catalyst auxiliary agent to the catalyst carrier is 8-12:1:40;
The metallocene catalyst is zirconocene dichloride; the catalyst auxiliary agent is a compound of triethylaluminum and 4-aminophenylboric acid in a mass ratio of 1:5.8; the catalytic carrier is carbonized porous Al 2O3.
2. The PE plastic according to claim 1, characterized in that the carbonized porous Al 2O3 is produced by the following method:
(1) Mixing alumina powder with deionized water to form slurry with the mass fraction of 40-60%;
(2) Adding glucose and polyethyleneimine into the slurry obtained in the step (1), stirring and dissolving, placing the mixture at 100-150 ℃ and 1.8-2.5MPa for 1-5 hours, filtering, and drying to obtain modified alumina;
(3) And (3) placing the modified alumina in a protective atmosphere, calcining for 3-6 hours at 620-680 ℃, and cooling and grinding to obtain carbonized porous Al 2O3.
3. A PE plastic heating pouch, characterized in that it is manufactured from a PE plastic according to any of claims 1-2.
4. A PE plastic heating bag according to claim 3, characterized in that it comprises, in order from inside to outside, an inner layer, a middle layer and an outer layer; the inner layer, the middle layer and the outer layer are prepared by adding at least one of low-density polyethylene, metallocene polyethylene, an opening slipping agent and polyphthalamide on the basis of PE plastic.
5. The PE plastic heating bag of claim 4, characterized in that the low density polyethylene is model 2426H and/or 2520D;
The metallocene polyethylene is 3505MC and/or 2710EP.
6. The PE plastic heating bag according to claim 4, wherein the outer layer is made of the following raw materials in parts by weight: 50 parts of PE plastic, 40 parts of metallocene polyethylene 3505MC and 10 parts of low-density polyethylene 2426H;
The middle layer is prepared from the following raw materials in parts by weight: 30 parts of PE plastic, 20 parts of metallocene polyethylene 3505MC, 40 parts of metallocene polyethylene 2710EP and 10 parts of low-density polyethylene 2426H;
The inner layer is prepared from the following raw materials in parts by weight: 40 parts of PE plastic, 30 parts of metallocene polyethylene 3505MC, 20 parts of low-density polyethylene 2520D, 10 parts of low-density polyethylene 2426H, 1.5 parts of an opening slipping agent and 2 parts of polyphthalamide.
7. The PE plastic heating bag according to claim 6, characterized in that it is produced by the following method:
According to the formula, the raw materials of the outer layer, the middle layer and the inner layer are respectively and uniformly mixed, the melting temperature is set to be 165 ℃, the raw materials are melted and extruded by a multi-layer co-extruder and then enter an annular co-extrusion die head to form a three-layer film for extrusion, and the three-layer film is sheared after co-extrusion compounding to obtain the required PE plastic heating bag.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1080990A (en) * | 1996-07-19 | 1998-03-31 | Kureha Chem Ind Co Ltd | Composite film with gas barrier property |
| CN105131398A (en) * | 2015-09-11 | 2015-12-09 | 陆思烨 | Antimicrobial and mildew resistant preservative film and preparation method thereof |
| CN109467792A (en) * | 2018-02-05 | 2019-03-15 | 江南大学 | A kind of toughening enhancing Fully-degradable ethylene master batch and preparation method thereof |
| CN111775526A (en) * | 2020-06-19 | 2020-10-16 | 重庆嘉峰彩印有限公司 | High-temperature water-boiling PE film and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1080990A (en) * | 1996-07-19 | 1998-03-31 | Kureha Chem Ind Co Ltd | Composite film with gas barrier property |
| CN105131398A (en) * | 2015-09-11 | 2015-12-09 | 陆思烨 | Antimicrobial and mildew resistant preservative film and preparation method thereof |
| CN109467792A (en) * | 2018-02-05 | 2019-03-15 | 江南大学 | A kind of toughening enhancing Fully-degradable ethylene master batch and preparation method thereof |
| CN111775526A (en) * | 2020-06-19 | 2020-10-16 | 重庆嘉峰彩印有限公司 | High-temperature water-boiling PE film and preparation method and application thereof |
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