CN116813965B - High-toughness tensile polyolefin film and preparation process thereof - Google Patents
High-toughness tensile polyolefin film and preparation process thereof Download PDFInfo
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000006084 composite stabilizer Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 229920000728 polyester Polymers 0.000 claims abstract description 16
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 16
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 38
- -1 polyethylene Polymers 0.000 claims description 35
- 238000005406 washing Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 23
- 238000001125 extrusion Methods 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004698 Polyethylene Substances 0.000 claims description 16
- 239000004743 Polypropylene Substances 0.000 claims description 16
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 16
- 229920000573 polyethylene Polymers 0.000 claims description 16
- 229920001155 polypropylene Polymers 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 108010020346 Polyglutamic Acid Proteins 0.000 claims description 13
- 108010054442 polyalanine Proteins 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- 229920002643 polyglutamic acid Polymers 0.000 claims description 13
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 11
- 238000007664 blowing Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000010101 extrusion blow moulding Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000000071 blow moulding Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003607 modifier Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 7
- 238000010559 graft polymerization reaction Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 8
- 238000004806 packaging method and process Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 241000272168 Laridae Species 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
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Abstract
The invention relates to the technical field of film material preparation, in particular to a high-toughness tensile polyolefin film and a preparation process thereof. The invention prepares the polyolefin film by mixing, processing and forming polyolefin, polyester type thermoplastic elastomer, composite stabilizer and compatilizer, and then carries out surface graft polymerization on the surface of the polyolefin film through chlorination in-situ grafting reaction. According to the invention, a complex branched chain structure is grafted to the surface of the film by graft polymerization reaction on the surface of the polyolefin film, so that the flexibility of the material is improved; the modifier is added to modify the polyolefin film, so that the hydrophilicity of the surface of the polyolefin film is improved, the low surface energy and the hydrophobicity of the polyolefin film are effectively improved, and the utilization rate of the polyolefin material is improved.
Description
Technical Field
The invention relates to the technical field of film material preparation, in particular to a high-toughness tensile polyolefin film and a preparation process thereof.
Background
Polyolefin is a thermoplastic resin obtained by polymerizing or copolymerizing organic materials such as ethylene, propylene and the like independently, and has the characteristics of abundant raw materials, low price, easy processing and molding, excellent comprehensive performance and the like, thus being applicable to products such as films, pipes, plates, various molded products, wires and cables and the like, and particularly having huge demand in the packaging industry. The polyolefin film packaging bag prepared from the polyolefin material has great market prospect, and can be folded and arranged according to different requirements due to good plasticity and flexibility; due to good moisture resistance and air tightness, the packaged articles can be protected from moisture and oxidation; the portable packaging machine is light in weight, easy to carry and convenient for packaging small articles; in addition, the polyolefin film packaging bag has a smooth surface, is easy to print patterns and characters, has attractive appearance, and can increase the aesthetic value of packaged articles. Although polyolefin film packaging bags have many advantages, their development is limited by the problems of low strength, low bearable pressure, poor toughness, poor impact resistance, and high hydrophobicity.
In order to overcome the defects of the prior art, the invention provides a high-toughness tensile polyolefin film and a preparation process thereof.
Disclosure of Invention
The invention aims to provide a high-toughness tensile polyolefin film and a preparation process thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a process for preparing a high-toughness tensile polyolefin film, comprising the following steps:
step one: mixing polyolefin, polyester type thermoplastic elastomer, composite stabilizer and compatilizer, and fully stirring to prepare polyolefin mixture;
step two: extruding and blow molding the polyolefin mixture to prepare a polyolefin film;
step three: polishing the polyolefin film, cleaning and drying; then soaking the polyolefin film in the mixed liquid; then, in the environment of chlorine and ultraviolet lamp, the polyolefin film undergoes chlorination in-situ grafting reaction; washing the product with acetone after the reaction is finished, and drying to prepare a pretreatment film;
step four: adding the modifier into cyclohexane solvent, stirring to obtain mixed solution, immersing the pretreated membrane into the mixed solution for reaction, washing and drying after the reaction is finished to obtain the finished product.
More optimally, in the first step, the rotating speed is 2000-2500r/min and the time is 20-40min when the stirring is fully carried out.
More preferably, in the first step, the polyolefin mixture comprises the following components: 80-90 parts of polyolefin, 10-20 parts of polyester thermoplastic elastomer, 0.5-1.5 parts of composite stabilizer and 5-8 parts of compatilizer.
More preferably, in the first step, the polyolefin is a mixture of polyethylene and polypropylene, and the mass ratio is 1:1.5 to 2.5, wherein the composite stabilizer is a mixture of dodecyl hydroxy phenoxy methyl ketone and triphenyl phosphate according to the mass ratio of 1:1; the compatilizer is ethylene-methyl acrylate copolymer.
More preferably, in the second step, the extrusion blow molding process parameters are as follows: extrusion temperature: 165-175 ℃, extrusion speed: 30-150m/min, and blowing pressure: 0.3-0.6MPa.
More preferably, in the third step, the mixed liquid comprises methyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate and acrylic acid, and the mass ratio of the methyl methacrylate to the glycidyl methacrylate is: methyl methacrylate: glycidyl methacrylate: 2-hydroxyethyl acrylate: acrylic acid = 2:3-5:2:1.
more optimally, in the third step, deionized water is used for cleaning for 3-7min, and ethanol is used for cleaning for 4-8min; the drying temperature is 60-80 ℃; the soaking time is 100-200min; the chlorine flow is 3-6mmol/min, the reaction temperature is 85-95 ℃ and the reaction time is 3.5-4.5h.
More preferably, in the fourth step, the modifier is a mixture of polyethylene glycol, polyglutamic acid and polyalanine, and the mass ratio of the modifier is as follows: polyethylene glycol: polyglutamic acid: polyalanine = 0.5-1.5:2:2.
more preferably, in the fourth step, the reaction conditions are: the reaction temperature is 20-26 ℃ and the reaction time is 20-26h; cleaning conditions: the cleaning temperature is 50-70 ℃ and the cleaning time is 20-26h; drying conditions: the drying temperature is 20-26 ℃, and the drying time is 24-48h.
The invention has the beneficial effects that:
according to the invention, the polyolefin film is prepared by mixing, processing and forming the polyolefin, the polyester type thermoplastic elastomer, the composite stabilizer and the compatilizer, and then the surface grafting polymerization is carried out on the surface of the polyolefin film to improve the toughness and strength of the polyolefin film, and the modifying agent is used for modifying the surface of the polyolefin film to improve the hydrophilicity of the film and enhance the anti-biological pollution capability of the film.
The invention is characterized in that the polyolefin is a mixture of polyethylene and polypropylene, and the mass ratio is 1:1.5-2.5, blending the two polymers in the proportion, and obtaining the polyolefin film with good toughness and strength. In the third step, the chlorine flow is controlled to be 3-6mmol/min to carry out graft polymerization reaction in situ in the polyolefin film grafting monomer, and the grafting polymerization reaction can ensure that the grafting rate reaches the optimal value. In addition, the mixed solution reaction monomers comprise methyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate and acrylic acid, and the mass ratio is as follows: methyl methacrylate: glycidyl methacrylate: 2-hydroxyethyl acrylate: acrylic acid = 2:3-5:2:1, a step of; several monomers containing double bonds are physically blended, then grafted and polymerized to the surface of the polyolefin film, and the grafting and polymerization reaction in the range can ensure that the grafting rate is optimal, and a relatively complex polymerization branched chain structure is obtained so as to improve the toughness of the polyolefin film.
Because the polyolefin is a high polymer material with a linear structure, all the monomers have poor flexibility according to the same arrangement sequence; therefore, the invention grafts more complex branched chain structures on the surface of the polyolefin film by graft polymerization reaction, and the existence of branched chains leads the relative molecular chains to become loose, the intermolecular empty gaps to become large, and the binding force between the molecules to be weakened, thereby obviously improving the toughness of the polyolefin film. In addition, the swelling property of the polyolefin is utilized, the polyolefin is moderately swelled through the cyclohexane solvent, and then the mixture of the polyethylene glycol, the polyglutamic acid and the polyalanine serving as the modifier is added to modify the polyolefin film, so that the hydrophilicity of the surface of the polyolefin film is improved, the low surface energy and the hydrophobicity of the polyolefin film are effectively improved, and the utilization rate of the polyolefin material is improved.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely in connection with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The raw material sources are as follows:
polyethylene, supplied by Shanghai North plastic foreign International trade company, model number: DMDA-8008H; polypropylene, provided by Dongguan city Jintai New Material science and technology Co., ltd., model is: GH41; the polyester type thermoplastic elastomer is provided by the plastic raw material company of the gull of Dongguan city, and has the model number of: 4556; ethylene-methyl acrylate copolymer, supplied by gull plasticization limited, dongguan city, under the trade name: 2116AC; polyethylene glycol, supplied by the sea-safe petrochemical plant in Jiangsu province, model is: PEG4000; polyglutamic acid, supplied by Shandong Liyang Biotechnology Co., ltd., model number: 123, a step of; polyalanine, supplied by Shandong polymer chemistry Co., ltd., model number: food grade.
Example 1: step one: mixing 32 parts of polyethylene, 48 parts of polypropylene, 10 parts of polyester type thermoplastic elastomer, 1.0 part of composite stabilizer and 5 parts of ethylene-methyl acrylate copolymer, and stirring for 40min at a rotating speed of 2500r/min to prepare a polyolefin mixture;
step two: extruding and blow molding the polyolefin mixture at the extrusion temperature of 175 ℃ and the extrusion speed of 150m/min under the condition of blowing pressure of 0.6MPa to prepare a polyolefin film;
step three: polishing the polyolefin film, then washing the polyolefin film with deionized water for 7min, washing the polyolefin film with ethanol for 8min, and drying the polyolefin film at 80 ℃; the polyolefin film was then laminated to methyl methacrylate: glycidyl methacrylate: 2-hydroxyethyl acrylate: the mass ratio of the acrylic acid is 2:3:2:1, soaking the mixture in the mixed liquid for 200min; introducing chlorine with the flow rate of 4mmol/min under the environment of an ultraviolet lamp, and reacting for 4.5 hours at the temperature of 95 ℃; washing the product with acetone after the reaction is finished, and drying at 80 ℃ to prepare a pretreatment film;
step four: polyethylene glycol: polyglutamic acid: the mass ratio of the polyalanine is 1:2:2 adding the modifier into cyclohexane solvent, stirring fully to obtain mixed solution, immersing the pretreated film into the mixed solution, reacting at 24 ℃ for 26 hours, washing at 70 ℃ for 26 hours after the reaction is finished, and drying at 26 ℃ for 48 hours to obtain the finished product.
Example 2: step one: mixing 32 parts of polyethylene, 48 parts of polypropylene, 10 parts of polyester type thermoplastic elastomer, 1.0 part of composite stabilizer and 5 parts of ethylene-methyl acrylate copolymer, and stirring at a rotating speed of 2375r/min for 35min to prepare a polyolefin mixture;
step two: carrying out extrusion blow molding on the polyolefin mixture under the conditions that the extrusion temperature is 172 ℃, the extrusion speed is 120m/min and the blowing pressure is 0.52MPa, so as to prepare a polyolefin film;
step three: polishing the polyolefin film, then washing the polyolefin film with deionized water for 6min, washing the polyolefin film with ethanol for 7min, and drying the polyolefin film at 75 ℃; the polyolefin film was then laminated to methyl methacrylate: glycidyl methacrylate: 2-hydroxyethyl acrylate: the mass ratio of the acrylic acid is 2:3:2:1, soaking the mixture in the mixed liquid for 175min; introducing chlorine with the flow rate of 4mmol/min under the environment of an ultraviolet lamp, and reacting for 4.25 hours at 92 ℃; washing the product with acetone after the reaction is finished, and drying at 75 ℃ to prepare a pretreatment film;
step four: polyethylene glycol: polyglutamic acid: the mass ratio of the polyalanine is 1:2:2 adding the modifier into cyclohexane solvent, stirring fully to obtain mixed solution, immersing the pretreated film into the mixed solution, reacting at 23 ℃ for 24 hours, washing at 65 ℃ for 24 hours after the reaction is finished, and drying at 24 ℃ for 42 hours to obtain the finished product.
Example 3: step one: mixing 32 parts of polyethylene, 48 parts of polypropylene, 10 parts of polyester type thermoplastic elastomer, 1.0 part of composite stabilizer and 5 parts of ethylene-methyl acrylate copolymer, and stirring at a rotating speed of 2250r/min for 30min to prepare a polyolefin mixture;
step two: carrying out extrusion blow molding on the polyolefin mixture under the conditions that the extrusion temperature is 170 ℃, the extrusion speed is 90m/min and the blowing pressure is 0.45MPa, so as to prepare a polyolefin film;
step three: polishing the polyolefin film, then washing with deionized water for 5min, washing with ethanol for 6min, and drying at 70 ℃; the polyolefin film was then laminated to methyl methacrylate: glycidyl methacrylate: 2-hydroxyethyl acrylate: the mass ratio of the acrylic acid is 2:3:2:1, soaking the mixture in the mixed liquid for 150min; introducing chlorine with the flow rate of 4mmol/min under the environment of an ultraviolet lamp, and reacting for 4 hours at 90 ℃; washing the product with acetone after the reaction is finished, and drying at 70 ℃ to prepare a pretreatment film;
step four: polyethylene glycol: polyglutamic acid: the mass ratio of the polyalanine is 1:2:2 adding the modifier into cyclohexane solvent, stirring fully to obtain mixed solution, immersing the pretreated film into the mixed solution, reacting at 22 ℃ for 23 hours, washing at 60 ℃ for 23 hours after the reaction is finished, and drying at 23 ℃ for 36 hours to prepare the finished product.
Example 4: step one: mixing 32 parts of polyethylene, 48 parts of polypropylene, 10 parts of polyester type thermoplastic elastomer, 1.0 part of composite stabilizer and 5 parts of ethylene-methyl acrylate copolymer, and stirring at a rotating speed of 2125r/min for 25min to prepare a polyolefin mixture;
step two: carrying out extrusion blow molding on the polyolefin mixture under the conditions that the extrusion temperature is 167 ℃, the extrusion speed is 60m/min and the blowing pressure is 0.37MPa, so as to prepare a polyolefin film;
step three: polishing the polyolefin film, then washing the polyolefin film with deionized water for 4min, washing the polyolefin film with ethanol for 5min, and drying the polyolefin film at 65 ℃; the polyolefin film was then laminated to methyl methacrylate: glycidyl methacrylate: 2-hydroxyethyl acrylate: the mass ratio of the acrylic acid is 2:3:2:1, soaking the mixture in the mixed liquid for 125min; introducing chlorine with the flow rate of 4mmol/min under the environment of an ultraviolet lamp, and reacting for 3.75h at 87 ℃; washing the product with acetone after the reaction is finished, and drying at 65 ℃ to prepare a pretreatment film;
step four: polyethylene glycol: polyglutamic acid: the mass ratio of the polyalanine is 1:2:2 adding the modifier into cyclohexane solvent, stirring fully to obtain mixed solution, immersing the pretreated film into the mixed solution, reacting at 21 ℃ for 21h, cleaning at 55 ℃ for 21h after the reaction is finished, and drying at 21 ℃ for 30h to obtain the finished product.
Example 5: step one: mixing 32 parts of polyethylene, 48 parts of polypropylene, 10 parts of polyester type thermoplastic elastomer, 1.0 part of composite stabilizer and 5 parts of ethylene-methyl acrylate copolymer, and stirring at a rotating speed of 2000r/min for 20min to prepare a polyolefin mixture;
step two: carrying out extrusion blow molding on the polyolefin mixture under the conditions that the extrusion temperature is 165 ℃, the extrusion speed is 30m/min and the blowing pressure is 0.3MPa, so as to prepare a polyolefin film;
step three: polishing the polyolefin film, then washing with deionized water for 3min, washing with ethanol for 4min, and drying at 60 ℃; the polyolefin film was then laminated to methyl methacrylate: glycidyl methacrylate: 2-hydroxyethyl acrylate: the mass ratio of the acrylic acid is 2:3:2:1, soaking the mixture in the mixed liquid for 100min; introducing chlorine with the flow rate of 4mmol/min under the environment of an ultraviolet lamp, and reacting for 3.5h at the temperature of 85 ℃; washing the product with acetone after the reaction is finished, and drying at 60 ℃ to prepare a pretreatment film;
step four: polyethylene glycol: polyglutamic acid: the mass ratio of the polyalanine is 1:2:2 adding the modifier into cyclohexane solvent, stirring fully to obtain mixed solution, immersing the pretreated film into the mixed solution, reacting for 20 hours at 20 ℃, cleaning for 20 hours at 50 ℃ after the reaction is finished, and drying for 24 hours at 20 ℃ to obtain the finished product.
Comparative example 1: in the first step, the mass ratio of polyethylene to polypropylene is changed to 1:1, the rest is the same as in example 1, the specific steps are as follows: step one: mixing 40 parts of polyethylene, 40 parts of polypropylene, 10 parts of polyester type thermoplastic elastomer, 1.0 part of composite stabilizer and 5 parts of ethylene-methyl acrylate copolymer, and stirring for 40min at a rotating speed of 2500r/min to prepare a polyolefin mixture;
step two: extruding and blow molding the polyolefin mixture at the extrusion temperature of 175 ℃ and the extrusion speed of 150m/min under the condition of blowing pressure of 0.6MPa to prepare a polyolefin film;
step three: polishing the polyolefin film, then washing the polyolefin film with deionized water for 7min, washing the polyolefin film with ethanol for 8min, and drying the polyolefin film at 80 ℃; the polyolefin film was then laminated to methyl methacrylate: glycidyl methacrylate: 2-hydroxyethyl acrylate: the mass ratio of the acrylic acid is 2:3:2:1, soaking the mixture in the mixed liquid for 200min; introducing chlorine with the flow rate of 4mmol/min under the environment of an ultraviolet lamp, and reacting for 4.5 hours at the temperature of 95 ℃; washing the product with acetone after the reaction is finished, and drying at 80 ℃ to prepare a pretreatment film;
step four: polyethylene glycol: polyglutamic acid: the mass ratio of the polyalanine is 1:2:2 adding the modifier into cyclohexane solvent, stirring fully to obtain mixed solution, immersing the pretreated film into the mixed solution, reacting at 24 ℃ for 26 hours, washing at 70 ℃ for 26 hours after the reaction is finished, and drying at 26 ℃ for 48 hours to obtain the finished product.
Comparative example 2: in step three, methyl methacrylate: glycidyl methacrylate: 2-hydroxyethyl acrylate: the mass ratio of acrylic acid becomes 2:2:2:1, the rest is the same as in example 1, the specific steps are as follows: step one: mixing 32 parts of polyethylene, 48 parts of polypropylene, 10 parts of polyester type thermoplastic elastomer, 1.0 part of composite stabilizer and 5 parts of ethylene-methyl acrylate copolymer, and stirring for 40min at a rotating speed of 2500r/min to prepare a polyolefin mixture;
step two: extruding and blow molding the polyolefin mixture at the extrusion temperature of 175 ℃ and the extrusion speed of 150m/min under the condition of blowing pressure of 0.6MPa to prepare a polyolefin film;
step three: polishing the polyolefin film, then washing the polyolefin film with deionized water for 7min, washing the polyolefin film with ethanol for 8min, and drying the polyolefin film at 80 ℃; the polyolefin film was then laminated to methyl methacrylate: glycidyl methacrylate: 2-hydroxyethyl acrylate: the mass ratio of the acrylic acid is 2:2:2:1, soaking the mixture in the mixed liquid for 200min; introducing chlorine with the flow rate of 4mmol/min under the environment of an ultraviolet lamp, and reacting for 4.5 hours at the temperature of 95 ℃; washing the product with acetone after the reaction is finished, and drying at 80 ℃ to prepare a pretreatment film;
step four: polyethylene glycol: polyglutamic acid: the mass ratio of the polyalanine is 1:2:2 adding the modifier into cyclohexane solvent, stirring fully to obtain mixed solution, immersing the pretreated film into the mixed solution, reacting at 24 ℃ for 26 hours, washing at 70 ℃ for 26 hours after the reaction is finished, and drying at 26 ℃ for 48 hours to obtain the finished product.
Comparative example 3: in the third step, the chlorine flow was changed to 2mmol/min, and the other steps were the same as in example 1, and were as follows: step one: mixing 32 parts of polyethylene, 48 parts of polypropylene, 10 parts of polyester type thermoplastic elastomer, 1.0 part of composite stabilizer and 5 parts of ethylene-methyl acrylate copolymer, and stirring for 40min at a rotating speed of 2500r/min to prepare a polyolefin mixture;
step two: extruding and blow molding the polyolefin mixture at the extrusion temperature of 175 ℃ and the extrusion speed of 150m/min under the condition of blowing pressure of 0.6MPa to prepare a polyolefin film;
step three: polishing the polyolefin film, then washing the polyolefin film with deionized water for 7min, washing the polyolefin film with ethanol for 8min, and drying the polyolefin film at 80 ℃; the polyolefin film was then laminated to methyl methacrylate: glycidyl methacrylate: 2-hydroxyethyl acrylate: the mass ratio of the acrylic acid is 2:3:2:1, soaking the mixture in the mixed liquid for 200min; introducing chlorine with the flow rate of 2mmol/min under the environment of an ultraviolet lamp, and reacting for 4.5 hours at the temperature of 95 ℃; washing the product with acetone after the reaction is finished, and drying at 80 ℃ to prepare a pretreatment film;
step four: polyethylene glycol: polyglutamic acid: the mass ratio of the polyalanine is 1:2:2 adding the modifier into cyclohexane solvent, stirring fully to obtain mixed solution, immersing the pretreated film into the mixed solution, reacting at 24 ℃ for 26 hours, washing at 70 ℃ for 26 hours after the reaction is finished, and drying at 26 ℃ for 48 hours to obtain the finished product.
Comparative example 4: the third and fourth steps were removed, and the rest was the same as in example 1, and the specific steps were as follows: step one: mixing 32 parts of polyethylene, 48 parts of polypropylene, 10 parts of polyester type thermoplastic elastomer, 1.0 part of composite stabilizer and 5 parts of ethylene-methyl acrylate copolymer, and stirring for 40min at a rotating speed of 2500r/min to prepare a polyolefin mixture;
step two: and (3) carrying out extrusion blow molding on the polyolefin mixture under the conditions of extrusion temperature of 175 ℃, extrusion speed of 150m/min and blowing pressure of 0.6MPa to prepare the polyolefin film.
Detection test:
tensile strength at break test: the method is carried out according to GB/T1040-1992 'method for testing tensile properties of plastics', the size of a sample is 115 multiplied by 25 multiplied by 2mm, the experimental speed is 50mm/min +/-10%, three points are measured for each sample, an arithmetic average value is taken, and finally the tensile strength at break is calculated through a formula.
Elongation at break test: according to GB/T1040-1992, the method is implemented by a plastic tensile property test method, the size of a sample is 115 multiplied by 25 multiplied by 2mm, the test speed is 50mm/min +/-10%, three points are measured by each sample, an arithmetic average value is taken, and the elongation at break is calculated through a formula;
water contact angle measurement: the prepared sample was subjected to a water contact angle test according to GB/T30693-2014, cut into rectangular shapes, kept dry before the test, and then measured for water contact angle using a water contact angle meter from DataPhysics, germany. The results are shown in the following table;
| tensile Strength at break/Mpa | Elongation at break/% | Water contact angle/° | |
| Example 1 | 39 | 850 | 48 |
| Example 2 | 39 | 848 | 47 |
| Example 3 | 39 | 848 | 47 |
| Example 4 | 38 | 847 | 46 |
| Example 5 | 38 | 847 | 46 |
| Comparative example 1 | 33 | 787 | 47 |
| Comparative example 2 | 36 | 819 | 47 |
| Comparative example 3 | 37 | 837 | 46 |
| Comparative example 4 | 35 | 797 | 107 |
Conclusion: the amounts of examples 1 to 5 were unchanged, and only part of the reaction parameters were modified. From experimental data, the properties of the spun polyolefin film do not change significantly. Comparative example 1: in the first step, the mass ratio of polyethylene to polypropylene is changed to 1:1, the rest is the same as in example 1, and it is found from the experimental data that the tensile strength at break is reduced to 33Mpa and the elongation at break is 787% compared with example 1, and the analysis is because: when the blending ratio of polyethylene and polypropylene is less than 1:1.5 to 2.5, the strength and toughness of the polyolefin film prepared may be low, and thus the tensile strength at break and elongation at break may be reduced.
Comparative example 2: in step three, methyl methacrylate: glycidyl methacrylate: 2-hydroxyethyl acrylate: the mass ratio of acrylic acid becomes 2:2:2:1, the rest is the same as in example 1, and it is found from the experimental data that the tensile strength at break is reduced to 36Mpa and the elongation at break is 819% compared with example 1, because: when the mass ratio of the mixed liquid is less than 2:3-5:2:1, the toughness of the polyolefin film is deteriorated.
Comparative example 3: in the third step, the flow rate of chlorine gas was changed to 2mmol/min, and the rest was the same as in example 1, and it was found from the experimental data that the tensile strength at break was reduced to 37MPa and the elongation at break was changed to 837% as compared with example 1, and the analysis was performed because: when the amount of chlorine used as an initiator is reduced, the efficiency of the grafting reaction is deteriorated, and thus the toughness of the polyolefin film is deteriorated.
Comparative example 4: the test data shows that the tensile strength at break is reduced to 35Mpa, the elongation at break is 797%, and the water contact angle is 107 ° as compared with example 1, and the results are: after the third step and the fourth step are removed, the breaking tensile strength and breaking elongation of the polyolefin film are reduced, and the hydrophobicity of the polyolefin film is stronger.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation process of a high-toughness tensile polyolefin film is characterized by comprising the following steps: the method comprises the following steps:
step one: mixing polyolefin, polyester type thermoplastic elastomer, composite stabilizer and compatilizer, and fully stirring to prepare polyolefin mixture;
step two: extruding and blow molding the polyolefin mixture to prepare a polyolefin film;
step three: polishing the polyolefin film, cleaning and drying; then, the polyolefin film is soaked in mixed liquid composed of methyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate and acrylic acid, and the mass ratio is 2: (3-5): 2:1, a step of; then, in the environment of chlorine and ultraviolet lamp, the polyolefin film undergoes chlorination in-situ grafting reaction; washing the product with acetone after the reaction is finished, and drying to prepare a pretreatment film;
step four: polyethylene glycol, polyglutamic acid and polyalanine are mixed according to the following ratio (0.5-1.5): 2:2, mixing and adding the mixture into cyclohexane solvent, fully stirring to obtain mixed solution, immersing the pretreatment film into the mixed solution for reaction, and washing and drying after the reaction is finished to obtain the finished product.
2. The process for preparing a high-toughness tensile polyolefin film according to claim 1, wherein: in the first step, the rotating speed is 2000-2500r/min and the time is 20-40min when the stirring is carried out fully.
3. The process for preparing a high-toughness tensile polyolefin film according to claim 1, wherein: in the first step, the polyolefin mixture comprises the following components: 80-90 parts of polyolefin, 10-20 parts of polyester thermoplastic elastomer, 0.5-1.5 parts of composite stabilizer and 5-8 parts of compatilizer.
4. A process for preparing a high toughness tensile polyolefin film according to claim 3, characterized in that: the polyolefin is a mixture of polyethylene and polypropylene, and the mass ratio is 1: (1.5-2.5); the composite stabilizer is a mixture of dodecyl hydroxyphenoxymethyl ketone and triphenyl phosphate in a mass ratio of 1:1; the compatilizer is ethylene-methyl acrylate copolymer.
5. The process for preparing a high-toughness tensile polyolefin film according to claim 1, wherein: in the second step, the extrusion blow molding process parameters are as follows: extrusion temperature: 165-175 ℃, extrusion speed: 30-150m/min, and blowing pressure: 0.3-0.6MPa.
6. The process for preparing a high-toughness tensile polyolefin film according to claim 1, wherein: in the third step, during cleaning, deionized water is firstly used for cleaning for 3-7min, and then ethanol is used for cleaning for 4-8min; the drying temperature is 60-80 ℃; the soaking time is 100-200min; the chlorine flow is 3-6mmol/min, the reaction temperature is 85-95 ℃ and the reaction time is 3.5-4.5h.
7. The process for preparing a high-toughness tensile polyolefin film according to claim 1, wherein: in the fourth step, the reaction conditions are as follows: the reaction temperature is 20-26 ℃ and the reaction time is 20-26h; cleaning conditions: the cleaning temperature is 50-70 ℃ and the cleaning time is 20-26h; drying conditions: the drying temperature is 20-26 ℃, and the drying time is 24-48h.
8. A high toughness tensile polyolefin film prepared according to the preparation process of any one of claims 1 to 7.
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| JP2010100700A (en) * | 2008-10-22 | 2010-05-06 | Tosoh Corp | Unsaturated carboxylic acid grafted polyolefin and method for producing the same |
| CN105820365A (en) * | 2016-04-25 | 2016-08-03 | 中国科学院化学研究所 | Directly coated polyolefin film and preparation method thereof |
| CN108297511A (en) * | 2018-01-30 | 2018-07-20 | 江苏光辉包装材料有限公司 | One kind is for casting and stretching thermal contractive label film and preparation method thereof |
| CN112194811A (en) * | 2020-09-30 | 2021-01-08 | 谢婉雯 | Preparation method of PE film |
| CN114058123A (en) * | 2021-12-20 | 2022-02-18 | 苏州度辰新材料有限公司 | Master batch for polyolefin film, preparation method, polyolefin film and BOPP film |
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| JP2010100700A (en) * | 2008-10-22 | 2010-05-06 | Tosoh Corp | Unsaturated carboxylic acid grafted polyolefin and method for producing the same |
| CN105820365A (en) * | 2016-04-25 | 2016-08-03 | 中国科学院化学研究所 | Directly coated polyolefin film and preparation method thereof |
| CN108297511A (en) * | 2018-01-30 | 2018-07-20 | 江苏光辉包装材料有限公司 | One kind is for casting and stretching thermal contractive label film and preparation method thereof |
| CN112194811A (en) * | 2020-09-30 | 2021-01-08 | 谢婉雯 | Preparation method of PE film |
| CN114058123A (en) * | 2021-12-20 | 2022-02-18 | 苏州度辰新材料有限公司 | Master batch for polyolefin film, preparation method, polyolefin film and BOPP film |
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