CN114163788A - Preparation method of high-strength high-barrier biodegradable film - Google Patents
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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Abstract
The invention utilizes electron beam irradiation to realize surface activation and graft modification of nano-cellulose, effectively improves the dispersibility and compatibility of the nano-cellulose in a polymer matrix, prepares a film after blending processing is finished, and then adopts electron beam irradiation to crosslink the film to form a three-dimensional crosslinking network taking the nano-cellulose as a crosslinking point.
Description
Technical Field
The invention belongs to the field of biodegradable materials, and particularly relates to a preparation method of a high-strength high-barrier biodegradable film.
Background
Under the background of promoting green economy and carbon cycle, people's attention to materials gradually turns to properties such as non-toxicity and biodegradability, and more typically, polybutylene adipate terephthalate and polylactic acid are popular materials which are attracted attention in recent years and applied to the fields of packaging, agriculture and the like.
The poly terephthalic acid-adipic acid-butanediol ester (PBAT) is aliphatic aromatic copolyester prepared from petroleum-based resources, and has degradability of the aliphatic polyester and better mechanical property of the aromatic polyester.
The polylactic acid (PLA) is a biological polymer material prepared by fermenting, purifying, polymerizing and other production processes by using crops such as cassava, sorghum, corn, straw and the like as raw materials, and the energy consumption for production is 30-50% lower than that of synthetic polymers produced by using petroleum products as raw materials.
However, most films on the market are made of polyethylene and polypropylene, and due to the fact that the film is produced in the older times, the performance research and the preparation process are more mature. In contrast, films produced from fully biodegradable plastics have, therefore, more or less certain disadvantages, such as:
1. the strength and the barrier property of the full-biodegradable film have a large difference from those of the traditional polyethylene film, in order to improve the barrier property of the film, a lamellar nano filler is usually required to be added, and the compatibility of the fillers and a polymer substrate is poor, so the filler usually reduces the mechanical strength of the film remarkably and reduces the transparency of the film, for example, a biodegradable compostable high-barrier composite film material disclosed in CN214395794U realizes the high barrier property of the film by virtue of an aluminized PBAT layer, the composite process is complex, light-proof and difficult to be applied to a single-layer film or an application occasion with a transparency requirement, and a PBAT-based biodegradable composite material with high water vapor barrier property provided in CN106957514B has good water vapor barrier property, wherein although the barrier property is improved by the mode of bridging the inorganic material, no chemical bond effect exists between the inorganic material and the polymer substrate, the molecular chain of the polymer is easy to crystallize, so that the transparency of the film is poor;
2. the preparation method comprises the preparation process of a degradable material and the processing process of a thin film, for example, CN111234279B adopts a trifunctional cross-linking agent to be blended with the degradable polymer and then processed into a polymer thick film, the polymer thick film is biaxially stretched to obtain a biaxially oriented thin film, and then the electron beam irradiation cross-linking is adopted to obtain the thin film material.
In general, the complexity of the process and the high processing cost remain the main factors restricting the biodegradation of the film. From the aspect of processing technology, the method mainly comprises several processes such as stretching (unidirectional stretching or bidirectional stretching), blow molding, compression molding, casting and the like, generally speaking, the mechanical property and the optical property of the film obtained by bidirectional stretching are ideal, but the equipment price of the stretching process is high, so that the obtained product is higher in price; the blow molding process is low in cost, but causes the melt of the biodegradable polymer to crack or the defects of a film product; it is difficult to obtain a thin film by molding or tape casting.
In view of this, the invention provides a method for preparing biodegradable film with high quality, simple process and low cost.
Disclosure of Invention
The invention provides a preparation method of a high-strength high-barrier biodegradable film, and aims to solve the problems of high production cost and complex process of the existing high-strength high-barrier high-transparency biodegradable film.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a high-strength high-barrier biodegradable film is characterized by comprising the following steps: the method comprises the following steps:
step one, preparing modified nano-cellulose:
adding the nano-cellulose powder and the liquid cross-linking agent into a high-speed mixer, fully and uniformly stirring at the rotating speed of 1500rpm plus 1000 ℃, standing for 2-4h, then irradiating the nano-cellulose powder fully soaked in the liquid cross-linking agent by using an electron accelerator, exciting the nano-cellulose to generate free radicals and initiating the liquid cross-linking agent to be grafted onto the nano-cellulose, wherein the irradiation dose is 2-20kGy to obtain the modified nano-cellulose,
wherein the liquid crosslinking agent is one or a composition of more of triallyl isocyanurate, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate, and the mass ratio of the nano cellulose powder to the liquid crosslinking agent is 90-99.5: 0.5-10;
step two, preparing a film:
fully stirring and uniformly mixing 80-95 parts by mass of base material, 3-15 parts by mass of modified nano cellulose, 0.5-1.5 parts by mass of antistatic agent, 0.1-0.3 part by mass of opening agent and 0.1-0.3 part by mass of lubricant, granulating by a double-screw extruder to obtain blended plastic particles, preparing a film by adopting a film blowing, tape casting or unidirectional stretching process to obtain a primary film with the thickness of 20-60 mu m, irradiating the primary film by using an electron accelerator with the irradiation dose of 50-200kGy, and finally obtaining the high-strength high-barrier biodegradable film;
the base material contains 60-100 wt% of polybutylene adipate terephthalate and 0-40 wt% of degradable polymer, and the degradable polymer is one of polylactic acid, thermoplastic starch and polycaprolactone;
the antistatic agent is polyoxyethylene ether;
the opening agent is one or a mixture of more of oleamide, erucamide, silicon dioxide, talcum powder and diatomite;
the lubricant is one or a mixture of more of stearic acid amide, methylene bis stearamide, ethylene bis stearamide, hydroxystearic acid, calcium stearate or zinc stearate;
preferably, the twin-screw extruder has a length to diameter ratio of greater than or equal to 40.
Preferably, the temperature of the twin-screw extruder is set at 140-160 ℃.
The design principle and the effect of the invention are as follows:
1. in the technical scheme of the invention, electron beam irradiation is used twice: the surface activation grafting modification of the nano-cellulose is realized by electron beam irradiation, so that the nano-modified filler with the crosslinking function is obtained, the dispersibility and compatibility of the nano-cellulose in a base material are effectively improved, and a film is prepared after blending processing is completed; and secondly, performing electron beam irradiation crosslinking on the film to form a three-dimensional crosslinking network taking the nano-cellulose as crosslinking points, so that the strength and the transparency of the film can be remarkably improved.
2. According to the technical scheme, the nanocellulose is modified, the mechanical property of the film is enhanced, so that the film has blown film orientation, and the film is not easy to crack when the thickness of the film is reduced by reducing the die gap and increasing the traction ratio or the blow-up ratio.
3. According to the technical scheme, the mechanical effect (expensive equipment of the biaxial stretching process) which can be achieved by biaxial stretching is realized by changing the material formula and the process route, and the production cost is indirectly and greatly reduced on the premise of ensuring the good performance of the film.
4. The film prepared by the technical scheme of the invention has good mechanical properties, and keeps high transparency and high barrier property.
5. In general, the technical scheme of the invention utilizes the synergistic effect of electron beam irradiation crosslinking and modified nanocellulose to greatly improve the strength, barrier property and transparency of the film, so as to obtain the high-strength and high-barrier transparent film material.
Detailed Description
The invention is further described below in connection with examples 1-3 and comparative examples 1-3:
example 1:
firstly, preparing modified nano cellulose, adding 95 parts of nano cellulose powder and 5 parts of TMPTMA (trimethylolpropane trimethacrylate) into a high-speed mixer, stirring at 1000rpm for 5min, and standing for 2 h. Irradiating the infiltrated nano-cellulose by using an electron accelerator, wherein the irradiation dose is 10 kGy;
then, as shown in the formula of example 1 in table 1, the base material, the modified nanocellulose, the polyoxyethylene ether, the oleamide, the silicon dioxide and the stearic acid amide are fully mixed, and are granulated at 150 ℃ by a double-screw extruder with the length-diameter ratio of 40 to obtain blended plastic particles;
a film blowing machine is adopted to prepare the film, the blow-up ratio is 3, and the thickness of the film is controlled to be 30 mu m. The film was then irradiated at a dose of 100kGy under a 0.5MeV electron accelerator.
Example 2:
firstly, preparing modified nano-cellulose, adding 98 parts of nano-cellulose powder and 2 parts of TMPTMA (trimethylolpropane trimethacrylate) into a high-speed mixer, stirring at 1000rpm for 8min, and standing for 3 h. Irradiating the soaked nano-cellulose by using an electron accelerator, wherein the irradiation dose is 15 kGy;
then, as shown in the formula of example 2 in table 1, the base material, the modified nano-cellulose, the polyoxyethylene ether, the erucamide, the talcum powder and the calcium stearate are fully mixed, and are granulated at 140 ℃ by a double-screw extruder with the length-diameter ratio of 40 to obtain blended plastic particles;
a film blowing machine is adopted to prepare the film, the blow-up ratio is 3, and the thickness of the film is controlled to be 30 mu m. The film was then irradiated at a dose of 80kGy under a 0.5MeV electron accelerator.
Example 3:
firstly, preparing modified nano-cellulose, adding 99.5 parts of nano-cellulose powder and 0.5 part of TMPTMA (trimethylolpropane trimethacrylate) into a high-speed mixer, stirring at 1200rpm for 5min, and standing for 2 h. Irradiating the infiltrated nano-cellulose by using an electron accelerator, wherein the irradiation dose is 8 kGy;
then, as shown in the formula of example 3 in table 1, the base material, the modified nanocellulose, the polyoxyethylene ether, the oleamide, the silicon dioxide and the zinc stearate are fully mixed, and are granulated at 150 ℃ by a double-screw extruder with the length-diameter ratio of 40 to obtain blended plastic particles;
a film blowing machine is adopted to prepare the film, the blow-up ratio is 2.8, and the thickness of the film is controlled to be 40 mu m. The film was then irradiated at a dose of 150kGy under a 1MeV electron accelerator.
Comparative example 1:
according to the formula shown in comparative example 1 in table 1, base material, nano cellulose, polyoxyethylene ether, oleamide, silicon dioxide and stearic acid amide are fully mixed, and are granulated at 150 ℃ by a double-screw extruder with the length-diameter ratio of 40 to obtain blended plastic particles;
a film blowing machine is adopted to prepare the film, the blow-up ratio is 3, and the thickness of the film is controlled to be 30 mu m. The film was then irradiated at a dose of 100kGy under a 0.5MeV electron accelerator.
Comparative example 2:
firstly, preparing modified nano-cellulose, adding 98 parts of nano-cellulose powder and 2 parts of TMPTMA into a high-speed mixer, stirring at 1000rpm for 8min, and standing for 3 h. Irradiating the soaked nano-cellulose by using an electron accelerator, wherein the irradiation dose is 15 kGy;
then, as shown in a formula of a comparative example 2 in the table 1, fully mixing the base material, the modified nano-cellulose, the polyoxyethylene ether, the erucamide, the talcum powder and the calcium stearate, and granulating at 140 ℃ by using a double-screw extruder with the length-diameter ratio of 40 to obtain blended plastic particles;
a film blowing machine is adopted to prepare the film, the blow-up ratio is 3, and the thickness of the film is controlled to be 30 mu m. The film was then irradiated at a dose of 80kGy under a 0.5MeV electron accelerator.
Comparative example 3:
firstly, preparing modified nano-cellulose, adding 99.5 parts of nano-cellulose powder and 0.5 part of TMPTMA into a high-speed mixer, stirring at 1200rpm for 5min, and standing for 2 h. Irradiating the infiltrated nano-cellulose by using an electron accelerator, wherein the irradiation dose is 8 kGy;
then, as shown in a formula of a comparative example 3 in table 1, fully mixing the base material, the modified nano-cellulose, polyoxyethylene ether, oleamide, silicon dioxide and zinc stearate, and granulating at 150 ℃ by using a double-screw extruder with a length-diameter ratio of 40 to obtain blended plastic particles;
a film blowing machine is adopted to prepare the film, the blow-up ratio is 2.8, and the thickness of the film is controlled to be 40 mu m.
TABLE 1 biodegradable film Material formulations and Processes
TABLE 2 comparison of the Properties of biodegradable film materials
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (3)
1. A preparation method of a high-strength high-barrier biodegradable film is characterized by comprising the following steps: the method comprises the following steps:
step one, preparing modified nano-cellulose:
adding the nano-cellulose powder and the liquid cross-linking agent into a high-speed mixer, fully and uniformly stirring at the rotating speed of 1500rpm plus 1000 ℃, standing for 2-4h, then irradiating the nano-cellulose powder fully soaked in the liquid cross-linking agent by using an electron accelerator, exciting the nano-cellulose to generate free radicals and initiating the liquid cross-linking agent to be grafted onto the nano-cellulose, wherein the irradiation dose is 2-20kGy to obtain the modified nano-cellulose,
wherein the liquid crosslinking agent is one or a composition of more of triallyl isocyanurate, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate, and the mass ratio of the nano cellulose powder to the liquid crosslinking agent is 90-99.5: 0.5-10;
step two, preparing a film:
fully stirring and uniformly mixing 80-95 parts by mass of base material, 3-15 parts by mass of modified nano cellulose, 0.5-1.5 parts by mass of antistatic agent, 0.1-0.3 part by mass of opening agent and 0.1-0.3 part by mass of lubricant, granulating by a double-screw extruder to obtain blended plastic particles, preparing a film by adopting a film blowing, tape casting or unidirectional stretching process to obtain a primary film with the thickness of 20-60 mu m, irradiating the primary film by using an electron accelerator with the irradiation dose of 50-200kGy, and finally obtaining the high-strength high-barrier biodegradable film;
the base material contains 60-100 wt% of polybutylene adipate terephthalate and 0-40 wt% of degradable polymer, and the degradable polymer is one of polylactic acid, thermoplastic starch and polycaprolactone;
the antistatic agent is polyoxyethylene ether;
the opening agent is one or a mixture of more of oleamide, erucamide, silicon dioxide, talcum powder and diatomite;
the lubricant is one or a mixture of more of stearic acid amide, methylene bis stearamide, ethylene bis stearamide, hydroxystearic acid, calcium stearate or zinc stearate.
2. The method of claim 1, wherein: the double screw extruder has a length to diameter ratio of greater than or equal to 40.
3. The method of claim 1, wherein: the temperature of the twin-screw extruder was set at 140-160 ℃.
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