CN111234279A - Water vapor barrier biodegradable polymer film and preparation and application thereof - Google Patents
Water vapor barrier biodegradable polymer film and preparation and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of biodegradable materials, and discloses a water vapor barrier biodegradable polymer film and preparation and application thereof. The invention improves the whole process design of the preparation method, and modifies the biodegradable polymer film by using a biaxial tension process and an electron beam irradiation technology, so that the problem of poor water vapor barrier property of the biodegradable polymer film can be effectively solved, and the invention can be widely applied to a plurality of fields such as agricultural mulching films, food and daily necessities packaging, electronic product packaging and the like.
Description
Technical Field
The invention belongs to the field of biodegradable materials, and particularly relates to a water vapor barrier biodegradable polymer film, and preparation and application thereof.
Background
The poly (butylene adipate/terephthalate) and the blend of the poly (butylene adipate/terephthalate) and other biodegradable polymers have the characteristics of complete biodegradation, good mechanical property and processing property, and can be widely used for agricultural covering films and packaging films. But the water vapor transmission capacity of the poly adipic acid/butylene terephthalate and the biodegradable blend film thereof is higher, the water vapor transmission capacity of the pure poly adipic acid/butylene terephthalate film is more than twice of that of the polyethylene film with the same thickness, and the production cost of the pure poly adipic acid/butylene terephthalate film is 2-3 times of that of the polyethylene film with the same thickness, so that the popularization and application of the poly adipic acid/butylene terephthalate and the biodegradable blend film thereof are greatly limited.
In order to solve the problem of poor water vapor barrier property of the poly (adipic acid)/butylene terephthalate and biodegradable blend films thereof, an effective method is to add inorganic platy fillers, particularly oriented nano layered fillers. The addition of inorganic fillers also brings new problems or difficulties: how to improve the compatibility of the filler and the polymer matrix, prevent the aggregation of the filler, ensure the good light transmission of the film, prevent the filler from becoming a stress concentration point to damage the mechanical property of the film and the like. On the other hand, in order to reduce the cost of the poly (adipic acid)/butylene terephthalate and biodegradable blend film thereof, besides reducing the raw material cost and improving the equipment and process to reduce the energy consumption of production and processing, reducing the film thickness is also a simple and effective means. It is difficult to effectively reduce the film thickness by molding or tape casting. Reducing die gap, increasing draw ratio or blow-up ratio is a common method of reducing the thickness of polymer films during blow molding. However, these measures are liable to cause the fracture of the biodegradable polymer melt or the defect of the film product, and affect the mechanical properties and the water and gas barrier capability of the film. The thickness of the film can also be reduced by stretching the polymer film in two directions, and the obtained film has ideal mechanical property, water-gas barrier property and optical property and can be widely applied to non-degradable polymer films of polyolefin (such as polypropylene and the like). The biaxial stretching process has high requirements on the uniformity and material toughness of the polymer film, for example, the carbon dioxide-propylene oxide copolymer is difficult to use in the biaxial stretching process, and whether the biaxial stretching can be carried out on most biodegradable polymer films is not clear. On the other hand, the electron beam irradiation technology is adopted to improve the mechanical properties such as tensile strength, elongation at break and the like of the poly (adipic acid)/butylene terephthalate) film, and the problem of mechanical property reduction caused by thinning of the biodegradable polymer film is solved (Chinese patent invention CN106883566A), but the improvement effect of the mechanical properties still needs to be further enhanced, and the influence of the electron beam irradiation post-treatment on the water vapor barrier property of the biodegradable polymer film in the prior art is not clear.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention aims to provide a water vapor barrier biodegradable polymer film and preparation and application thereof, the whole process design of the preparation method is improved, a biaxial tension process and an electron beam irradiation post-treatment technology are used for modifying the biodegradable polymer film, the molecular chains of the polymer are oriented in the transverse direction and the longitudinal direction by biaxial tension to form ordered arrangement, and heat setting is carried out in a tension state to fix the oriented macromolecular structure; meanwhile, the biodegradable polymer film is crosslinked to form a three-dimensional crosslinked network through electron beam irradiation treatment, and the water vapor barrier property and the mechanical property of the biodegradable polymer film can be improved through the cooperation effect of the two.
To achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a water vapor barrier biodegradable polymer film, comprising the steps of:
(1) blending biodegradable polymer and cross-linking agent to obtain a biodegradable polymer film special material; wherein the biodegradable polymer comprises at least a poly (butylene adipate terephthalate);
(2) forming and processing the special material for the biodegradable polymer film obtained in the step (1) into a biodegradable polymer thick film, wherein the thickness of the thick film is not less than 0.02 mm;
(3) performing biaxial tension on the biodegradable polymer thick film obtained in the step (2) to obtain a biaxial orientation film;
(4) and (4) performing electron beam irradiation on the bidirectional oriented film obtained in the step (3) to obtain the water vapor barrier biodegradable polymer film, so that the water vapor barrier property of the biodegradable polymer film is improved.
As a further preferred of the present invention, in the step (1), the biodegradable polymer is specifically poly (butylene adipate/terephthalate), or a blend of poly (butylene adipate/terephthalate) and other degradable polymers, wherein the other degradable polymers are one of polylactic acid, thermoplastic starch, carbon dioxide-propylene oxide copolymer, poly (butylene succinate), polycaprolactone and polyhydroxybutyrate; in the blend of the poly-adipic acid/terephthalic acid-butanediol ester and other degradable polymers, the proportion of the poly-adipic acid/terephthalic acid-butanediol ester is not less than 70 wt%.
As a further preferred aspect of the present invention, said step (1) further comprises a processing aid, and correspondingly, said biodegradable polymer film special material also comprises a processing aid, wherein said processing aid is not more than 10 wt% of said biodegradable polymer.
In a further preferred embodiment of the present invention, in the step (1), the crosslinking agent is one of triallyl isocyanurate, triallyl cyanurate, trimethylolpropane trimethacrylate and trimethylolpropane triacrylate, and the amount of the crosslinking agent added is 0.5 to 10 wt% of the biodegradable polymer.
As a further preferred aspect of the present invention, in the step (2), the molding process is specifically one of compression molding, blow molding, and casting; the thickness of the biodegradable polymer thick film is 0.02 mm-1 mm.
In a further preferable mode of the present invention, in the step (3), the biaxial stretching is performed at 60 to 90 ℃, and both the transverse stretching and the longitudinal stretching are performed at a stretching speed of 20 to 100mm/s and a stretching ratio of 1.5 to 7;
preferably, in the step (3), the biaxial stretching is simultaneous biaxial stretching.
As a further preferable mode of the present invention, in the step (4), the irradiation dose of the electron beam irradiation is not more than 200 kGy;
the electron beam irradiation is performed in a nitrogen atmosphere, a vacuum atmosphere, or an air atmosphere.
According to another aspect of the present invention, the present invention provides a water vapor barrier biodegradable polymer film prepared by the above-mentioned preparation method.
According to still another aspect of the present invention, the present invention provides the use of the above-mentioned water vapor barrier biodegradable polymer film as an agricultural mulching film or a packaging material.
Compared with the prior art, the technical scheme of the invention firstly adopts the biaxial stretching to obtain the biaxially oriented biodegradable polymer film by the poly (adipic acid)/butylene terephthalate and the biodegradable blend film thereof prepared by the traditional thermoforming processing mode, and then places the biaxially oriented film in an electron beam irradiation generating device to be irradiated by a certain dose of electron beams, thereby obtaining the film product with good mechanical property and water vapor barrier property. The stretching orientation makes the molecular chain of the polymer arranged in an oriented way and the molecular arrangement more compact, thereby improving the mechanical property and the water vapor barrier capability of the polymer.
The invention adopts the poly-adipic acid/terephthalic acid-butanediol ester as the biodegradable polymer, which can be pure poly-adipic acid/terephthalic acid-butanediol ester, or the blend of the poly-adipic acid/terephthalic acid-butanediol ester and other degradable polymers (other degradable polymers are one of polylactic acid, thermoplastic starch, carbon dioxide-propylene oxide copolymer, poly-succinic acid-butanediol ester, polycaprolactone and polyhydroxybutyrate, and the proportion of the poly-adipic acid/terephthalic acid-butanediol ester in the blend is not less than 70 wt%, so as to ensure that the prepared thick film has good toughness). The flexibility of the polymer molecular chain, the compatibility of the polymer blend, the structure of the cross-linking agent and other factors can influence the optimal stretching ratio and stretching speed of stretching orientation, the flexibility of different biodegradable polymer molecular chains and the compatibility of the blends thereof have larger difference, and the difference between the flexibility of different biodegradable polymer molecular chains and the compatibility of the blends thereof is obvious and the difference between the flexibility of different biodegradable polymer molecular chains and the compatibility of the blends thereof is excellent. The invention particularly controls the stretching ratio and the stretching speed preferably, controls the stretching speeds of transverse stretching and longitudinal stretching to be 20-100 mm/s and controls the stretching ratio to be 1.5-7, and ensures good comprehensive performance of the polymer. The draw ratio is too small, and the orientation of the polymer is not perfect; too high a draw ratio tends to cause defects in the polymer; the effect of the draw rate on the structure and properties of the polymer is similar to the draw ratio; in addition, the temperature of the biaxial stretching is preferably controlled to be 60-90 ℃, so that the proper stretching orientation temperature can be obtained.
The invention can further ensure the comprehensive performance of the polymer film by further preferably controlling the type and the dosage of the cross-linking agent, the irradiation dose of the electron beam and the like. Besides the conventional requirement that the cross-linking agent is uniformly dispersed in the polymer and the blend thereof to avoid the formation of stress concentration points in the polymer product and the deterioration of the product performance of the polymer, the chemical structure and the addition amount of the cross-linking agent also influence the dispersibility of the cross-linking agent in the polymer. The present invention can ensure the action and effect of the crosslinking agent by preferably controlling the specific type and amount of the crosslinking agent. The electron beam irradiation has double functions, on one hand, polymer molecules and a cross-linking agent are subjected to cross-linking reaction to form a three-dimensional polymer network, and the tensile strength of the polymer and the water vapor barrier capability of a film product of the polymer are improved by matching with the biaxial tension effect; excessive crosslinking can also form defects in the polymer film, affecting the properties of the article. On the other hand, electron beam irradiation degrades polymer molecular chains, can improve the impact resistance of the polymer to a certain degree, but can lose the tensile strength and the water vapor barrier property of the polymer product. The invention also controls the irradiation dose of the electron beam to be not more than 200kGy by preferably controlling the irradiation dose of the electron beam and matching with the components and the structure of the biodegradable polymer and the type and the dosage of the cross-linking agent, thereby avoiding the adverse effects of excessive cross-linking of the cross-linking agent, degradation of a molecular chain of a degraded polymer and the like caused by overhigh irradiation dose of the electron beam and ensuring the performance of a prepared polymer product.
Specifically, the present invention can achieve the following advantageous effects:
(1) the molecular chains of the poly (adipic acid)/butylene terephthalate and the biodegradable blend thereof are simultaneously oriented in the transverse direction and the longitudinal direction by biaxial stretching to form a more closely arranged ordered structure, thereby improving the water vapor barrier property and the mechanical property of the polymer film. And, in particular, simultaneous biaxial stretching can be used to optimize the properties (in which case the molecular chains of the polymer will be oriented in both the transverse and longitudinal directions to form an ordered arrangement).
(2) The invention preferably controls the dose of electron beam irradiation to ensure that the molecular chain of the poly adipic acid/butylene terephthalate generates micro-crosslinking, thereby further improving the water vapor barrier capability and the mechanical property of the biodegradable polymer film.
(3) The electron beam generated by the electron accelerator is used as a radiation source to modify the biodegradable film, and the radiation process has no pollution, simple process and low processing cost.
(4) The molecular chain micro-crosslinking structure of the poly (adipic acid)/butylene terephthalate and the biodegradable blend thereof treated by biaxial stretching and electron beam irradiation does not influence the biodegradation characteristics of the film product.
(5) The biodegradable polymer film with good light transmittance, excellent mechanical property and excellent water vapor barrier property and very thin thickness can be obtained by biaxial stretching and electron beam irradiation treatment, and the cost of the film product per unit area can be effectively reduced. The invention utilizes the cooperation of biaxial tension treatment and electron beam irradiation, and the mechanical property of the obtained film is far higher than that of the film obtained by single electron beam irradiation treatment in the prior art.
(6) The water vapor barrier biodegradable polymer film obtained by biaxial stretching and electron beam irradiation treatment can be used in a plurality of fields such as agricultural mulching films, food and daily necessities packaging, electronic product packaging and the like.
In conclusion, the biodegradable polymer film is modified by using the biaxial stretching process and the electron beam irradiation technology, so that the problem of poor water vapor barrier property of the biodegradable polymer film can be effectively solved, and the biodegradable polymer film can be widely applied to various fields such as agricultural mulching films, food and daily necessities packaging, electronic product packaging and the like.
Drawings
FIG. 1 is a moisture permeation coefficient-electron beam irradiation dose curve of the biodegradable polymer film obtained in example 1.
Fig. 2 is a moisture permeation coefficient-electron beam irradiation dose curve and a tensile strength-electron beam irradiation dose curve of the biodegradable polymer film obtained in example 2, wherein a in fig. 2 is the moisture permeation coefficient-electron beam irradiation dose curve and b in fig. 2 is the tensile strength-electron beam irradiation dose curve.
Fig. 3 is a graph of the relationship between moisture permeation coefficient and biaxial stretching ratio and the relationship between tensile strength and biaxial stretching ratio of biaxially oriented biodegradable polymer films of different stretching ratios, wherein a in fig. 3 is a graph of the relationship between moisture permeation coefficient and biaxial stretching ratio, and b in fig. 3 is a graph of the relationship between tensile strength and biaxial stretching ratio.
FIG. 4 is a comparison graph of moisture permeability coefficients of water vapor barrier biodegradable polymer films obtained with different biaxial stretching ratios under different electron beam irradiation doses.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The preparation method of the water vapor barrier biodegradable polymer film comprises the following steps:
(1) the biodegradable polymer, the cross-linking agent and the processing aid (such as an opening agent, titanium dioxide, calcium carbonate and the like) are blended to obtain the special material for the biodegradable polymer film. The biodegradable polymer is poly adipic acid/butylene terephthalate or a blend of poly adipic acid/butylene terephthalate and other degradable polymers, and the other degradable polymers are one of polylactic acid, thermoplastic starch, carbon dioxide-propylene oxide copolymer, polybutylene succinate, polycaprolactone and polyhydroxybutyrate. The biodegradable polymer film speciality may or may not contain a processing aid. The crosslinking agent is one of triallyl isocyanurate, triallyl cyanurate, trimethylolpropane trimethacrylate and trimethylolpropane triacrylate, and the addition amount of the crosslinking agent is 0.5-10 wt% of the biodegradable polymer. In the blend of the poly-butylene adipate/terephthalate and other degradable polymers, the proportion of the poly-butylene adipate/terephthalate is not less than 70%. Wherein the processing aid is optional or optional and wherein different processing means comprise different processing aids, typically not more than 10 wt% of the biodegradable polymer.
(2) And (2) forming and processing the special material for the biodegradable polymer film in the step (1) into a biodegradable polymer thick film. The molding processing is one of compression molding, blow molding and tape casting; the thickness of the biodegradable polymer thick film is 0.02 mm-1 mm.
(3) And (3) performing biaxial tension on the biodegradable polymer thick film obtained in the step (2) to obtain a biaxially oriented film. The biaxial stretching is carried out at the temperature of 60-90 ℃, the stretching speed is 20-100 mm/s, and the stretching ratio is 1.5-7.
(4) And (4) irradiating the bidirectional oriented film obtained in the step (3) by adopting an electron beam to obtain the water vapor barrier biodegradable polymer film. The electron beam irradiation is performed in a nitrogen atmosphere, a vacuum atmosphere, or an air atmosphere. The irradiation dose of the electron beam irradiation is not higher than 200 kGy.
The water vapor barrier biodegradable polymer film obtained by the preparation method can be used in a plurality of fields such as agricultural mulching films, food and daily necessities packaging, electronic product packaging and the like.
The following are specific examples and comparative examples:
comparative example 1:
a biodegradable polymer thick film was prepared as follows for comparative sample:
drying the poly (adipic acid)/butylene terephthalate in a forced air drying oven at 50-80 ℃ for 12-24 h, and then cooling with cold air to room temperature. And (2) banburying the dried poly (adipic acid)/butylene terephthalate resin and triallyl isocyanurate (the dosage is 2 wt% of the poly (adipic acid)/butylene terephthalate) in a banbury mixer at the temperature of 130 ℃ for 13min to obtain the special material for the biodegradable polymer film. Then hot-pressed into a 0.2mm thick biodegradable polymer film by a flat vulcanizing press.
Measuring the thickness of the prepared biodegradable polymer thick film according to the GB/T20220-2006 standard; the water vapor barrier property is characterized by adopting a W3/60 type water vapor transmission rate test system according to GB/T16928 and GB1037-70 standards, and the area of the test film is 33cm2The water vapor transmission of a 0.2mm thick poly (butylene adipate/terephthalate) film was measured at an ambient relative humidity of 90% RH and a temperature of 38 ℃ and was further calculated to give a moisture permeability coefficient of 4.06 x 10 independent of the sample thickness-11g.m.m-2.pa-1.s-1. The tensile strength of the film was measured at a tensile rate of 50mm/min in accordance with GBT1040-1992 standard and was 25.3 MPa.
Comparative example 2:
biaxially oriented biodegradable polymer films were prepared as comparative samples according to the following procedure:
(1) drying the poly (adipic acid)/butylene terephthalate in a forced air drying oven at 50-80 ℃ for 12-24 h, and then cooling with cold air to room temperature. Banburying and blending the dried poly (adipic acid)/butylene terephthalate resin and triallyl isocyanurate (the dosage is 2 wt% of the poly (adipic acid)/butylene terephthalate) in a banbury mixer, wherein the banburying temperature is 130 ℃, and the banburying time is 13min, so as to obtain the special material for the biodegradable polymer film;
(2) hot-pressing the special material for the biodegradable polymer film obtained in the step (1) into a biodegradable polymer thick film with the thickness of 0.2mm by a flat vulcanizing machine;
(3) synchronously and bidirectionally stretching the biodegradable polymer thick film obtained in the step (2) at 80 ℃ to obtain a bidirectionally oriented film; the drawing speed was 100mm/s and the drawing ratio was 1.5.
Measuring the thickness of the prepared bidirectional oriented biodegradable polymer film according to GB/T20220-2006 standard; the water vapor barrier property is characterized by adopting a W3/60 type water vapor transmission rate test system according to GB/T16928 and GB1037-70 standards, and the area of the test film is 33cm2The ambient relative humidity was 90% RH and the temperature was 38 ℃. The water vapor transmission of a 1.5 draw ratio poly (adipic acid)/butylene terephthalate) film was measured and further calculated to give a moisture permeability coefficient of 3.57 x 10 independent of the sample thickness-11g.m.m-2.pa-1.s-1. The tensile strength of the film was measured at a tensile rate of 50mm/min in accordance with GBT1040-1992 standard and was 30 MPa.
Example 1:
several water vapor barrier biodegradable polymer films were prepared as follows:
(1) drying the poly (adipic acid)/butylene terephthalate in a forced air drying oven at 50-80 ℃ for 12-24 h, and then cooling with cold air to room temperature. And (2) banburying and blending the dried poly (adipic acid)/butylene terephthalate resin and triallyl isocyanurate (the dosage is 2 wt% of the poly (adipic acid)/butylene terephthalate) in a banbury mixer, wherein the banburying temperature is 130 ℃, and the banburying time is 13min, so as to obtain the special material for the biodegradable polymer film.
(2) And (2) hot-pressing the special material for the biodegradable polymer film obtained in the step (1) into a biodegradable polymer thick film with the thickness of 0.2mm by adopting a flat vulcanizing machine.
(3) Synchronously and bidirectionally stretching the biodegradable polymer thick film obtained in the step (2) at 80 ℃ to obtain a bidirectionally oriented film; the drawing speed was 100mm/s and the drawing ratio was 3.
(4) And (4) placing the bidirectional oriented film obtained in the step (3) under an electron accelerator in a vacuum seal manner, and performing electron beam irradiation at room temperature to obtain the water vapor barrier biodegradable polymer film. The irradiation doses used were 25kGy, 50kGy, 75kGy, 100kGy, 125kGy and 150kGy, respectively.
The water vapor barrier biodegradable polymer film can be applied to the fields of agricultural mulching films, food and daily necessities packaging and electronic product packaging.
Measuring the thickness of the prepared water vapor barrier biodegradable polymer film according to the GB/T20220-2006 standard; the water vapor barrier property is standardized according to GB/T16928 and GB1037-70 by adopting a W3/60 type water vapor transmission rate testing system, and the area of a testing film is 33cm2The ambient relative humidity was 90% RH and the temperature was 38 ℃. The water vapor transmission amount is measured, and the moisture permeability coefficient independent of the thickness of the sample is further calculated. The biaxially oriented film obtained in the above step (3) without electron beam irradiation was also used as a comparative sample A, and the moisture permeability coefficient thereof was measured.
The water vapor permeability coefficient of the above-mentioned water vapor-barrier biodegradable polymer film was plotted against the irradiation dose of electron beam, and the result is shown in fig. 1, and the water vapor permeability coefficient of comparative sample a is also plotted in fig. 1 (point where the irradiation dose was 0 kGy). As can be seen from fig. 1, all the samples had a lower water vapor permeability coefficient than the sample of comparative example 1 (4.06 × 10)-11g.m.m-2.pa-1.s-1) Namely, the water vapor barrier property of the biodegradable polymer film can be obviously improved by biaxial stretching and electron beam irradiation. And the influence of the electron beam irradiation dose on the water vapor barrier property of the biodegradable polymer film is large, and the optimal water vapor barrier property can be ensured by matching with a preparation method through optimally controlling the electron beam irradiation dose.
Example 2:
several water vapor barrier biodegradable polymer films were prepared as follows:
(1) drying the poly (adipic acid)/butylene terephthalate in a forced air drying oven at 50-80 ℃ for 12-24 h, and then cooling with cold air to room temperature. And (2) banburying and blending the dried poly (adipic acid)/butylene terephthalate resin and triallyl isocyanurate (the dosage is 2 wt% of the poly (adipic acid)/butylene terephthalate) in a banbury mixer, wherein the banburying temperature is 130 ℃, and the banburying time is 13min, so as to obtain the special material for the biodegradable polymer film.
(2) And (2) hot-pressing the special material for the biodegradable polymer film obtained in the step (1) into a biodegradable polymer thick film with the thickness of 0.2mm by adopting a flat vulcanizing machine.
(3) Synchronously and bidirectionally stretching the biodegradable polymer thick film obtained in the step (2) at 80 ℃ to obtain a bidirectionally oriented film; the drawing speed was 100mm/s and the drawing ratio was 3.5.
(4) And (4) placing the bidirectional oriented film obtained in the step (3) under an electron accelerator in a vacuum seal manner, and performing electron beam irradiation at room temperature to obtain the water vapor barrier biodegradable polymer film. The irradiation doses used were 25kGy, 50kGy, 75kGy, 100kGy, 125kGy and 150kGy, respectively.
The water vapor barrier biodegradable polymer film can be applied to the fields of agricultural mulching films, food and daily necessities packaging and electronic product packaging.
Measuring the thickness of the prepared water vapor barrier biodegradable polymer film according to the GB/T20220-2006 standard; the water vapor barrier property is standardized according to GB/T16928 and GB1037-70 by adopting a W3/60 type water vapor transmission rate testing system, and the area of a testing film is 33cm2The ambient relative humidity was 90% RH and the temperature was 38 ℃. The water vapor transmission amount is measured, and the moisture permeability coefficient independent of the thickness of the sample is further calculated. The biaxially oriented film obtained in the above step (3) without electron beam irradiation was also used as a comparative sample B, and the moisture permeability coefficient thereof was measured. The tensile strength of the film was measured at a stretching rate of 50mm/min in accordance with GBT1040-1992 standard.
Making the above-mentioned water vapour barrier materialThe moisture vapor permeability coefficient of the biodegradable polymer film was plotted against the electron beam irradiation amount, and the result is shown as a in fig. 2, and the moisture permeability coefficient of comparative sample B is also plotted as a in fig. 2 (point where the irradiation dose was 0 kGy). Meanwhile, the tensile strength of the water vapor barrier biodegradable polymer film and the comparative experiment B is plotted against the electron beam irradiation amount, and the result is shown as B in FIG. 2. As can be seen from a in FIG. 2, all the samples had a lower water vapor permeability coefficient than the sample of comparative example 1 (4.06 x 10)-11g.m.m-2.pa-1.s-1) Namely, the water vapor barrier property of the biodegradable polymer film can be obviously improved by biaxial stretching and electron beam irradiation. As can be seen from b in fig. 2, the electron beam irradiation post-treatment can significantly improve the tensile strength of the biaxially oriented film. And the influence of the irradiation dose of the electron beam on the water vapor barrier property and the tensile strength of the biodegradable polymer film is larger, and the optimal water vapor barrier property and the optimal mechanical strength can be ensured by optimally controlling the irradiation dose of the electron beam and matching with a preparation method.
The moisture permeation coefficient and tensile strength of the biodegradable polymer films prepared in comparative example 1, comparative example 2, comparative sample a in example 1, and comparative sample B in example 2 were plotted against the biaxial stretching ratio, respectively, and the results are shown in fig. 3. It can be seen that: the moisture barrier properties and tensile strength of the biodegradable polymer film were also improved by biaxial orientation alone without electron beam irradiation treatment (the moisture permeability coefficient of all the stretch-oriented samples was lower than 4.06 x 10 of the sample of comparative example 1-11g.m.m-2.pa-1.s-1A value; tensile strength of the tensile-oriented sample is higher than 25.3MPa of the sample of comparative example 1), and the moisture barrier property and tensile strength of the biodegradable polymer film are improved as the tensile ratio is increased within a certain range of the tensile ratio.
The moisture permeability coefficients of the water vapor barrier biodegradable polymer films (samples prepared in example 1 and example 2, respectively) obtained at different biaxial stretching ratios were compared at different electron beam irradiation doses, and the results are shown in fig. 4. It can be seen that the moisture barrier properties of the biodegradable polymer film increase with increasing stretch ratio at all electron beam irradiation doses used over a range of stretch ratios.
Example 3:
a water vapor barrier biodegradable polymer film is prepared by the following steps:
(1) mixing the dried poly (butylene adipate/terephthalate), polylactic acid, triallyl cyanurate and calcium carbonate in a high-speed mixer, and melting and blending in a double-screw extruder to obtain the biodegradable polymer particles. The mass ratio of the poly adipic acid to the poly butylene terephthalate to the polylactic acid is 70: 30; the addition amounts of triallyl cyanurate and calcium carbonate are both 0.5 wt% of the total amount of the polyadipic acid/butylene terephthalate and polylactic acid.
(2) And (2) drying the biodegradable polymer particles prepared in the step (1) and then preparing the biodegradable polymer thick film with the thickness of 0.02mm by adopting a blow molding process.
(3) Synchronously and bidirectionally stretching the biodegradable polymer thick film obtained in the step (2) at 70 ℃ to obtain a bidirectionally oriented film; the drawing speed is 20mm/s and the drawing ratio is 1.5;
(4) and (4) sealing the bidirectional oriented film obtained in the step (3) by using nitrogen, placing the film under an electron accelerator at room temperature, and performing electron beam irradiation with the irradiation dose of 100kGy to obtain the water vapor barrier biodegradable polymer film.
The water vapor barrier biodegradable polymer film obtained by the preparation method can be used in a plurality of fields such as agricultural mulching films, food and daily necessities packaging, electronic product packaging and the like.
Example 4:
a water vapor barrier biodegradable polymer film is prepared by the following steps:
(1) mixing the poly (adipic acid)/butylene terephthalate, the carbon dioxide-propylene oxide copolymer, the triallyl isocyanurate and the opening agent in a high-speed mixer, and melting and blending in a double-screw extruder to prepare the biodegradable polymer particles. The mass ratio of the poly (adipic acid)/butylene terephthalate to the carbon dioxide-propylene oxide copolymer is 80; 20; the amount of triallyl isocyanurate added was 1.0 wt% based on the total amount of the polyadipic acid/butylene terephthalate and carbon dioxide-propylene oxide copolymer; the amount of the opening agent added was 5.0 wt% of the total amount of the polyadipic acid/butylene terephthalate and carbon dioxide-propylene oxide copolymer.
(2) And (2) drying the biodegradable polymer particles prepared in the step (1) and then preparing the biodegradable polymer thick film with the thickness of 0.05mm by adopting a blow molding process.
(3) Synchronously and bidirectionally stretching the biodegradable polymer thick film obtained in the step (2) at 60 ℃ to obtain a bidirectionally oriented film; the drawing speed was 50mm/s and the drawing ratio was 5.0.
(4) And (4) sealing the bidirectional oriented film obtained in the step (3) by using nitrogen, placing the film under an electron accelerator at room temperature, and performing electron beam irradiation with the irradiation dose of 150kGy to obtain the water vapor barrier biodegradable polymer film.
The water vapor barrier biodegradable polymer film obtained by the preparation method can be used in a plurality of fields such as agricultural mulching films, food and daily necessities packaging, electronic product packaging and the like.
Example 5:
a water vapor barrier biodegradable polymer film is prepared by the following steps:
(1) mixing the poly (adipic acid)/butylene terephthalate, the thermoplastic starch and the triallyl isocyanurate in a high-speed mixer, and melting and blending in a double-screw extruder to prepare the biodegradable polymer particles. The mass ratio of the adipic acid/butylene terephthalate to the thermoplastic starch is 85: 15; the triallyl isocyanurate was added in an amount of 5.0 wt% based on the total amount of the polyadipic acid/butylene terephthalate and the thermoplastic starch.
(2) And (2) hot-pressing the biodegradable polymer film particles obtained in the step (1) into a biodegradable polymer thick film with the thickness of 1.0mm by adopting a flat vulcanizing machine.
(3) Synchronously and bidirectionally stretching the biodegradable polymer thick film obtained in the step (2) at 90 ℃ to obtain a bidirectionally oriented film; the drawing speed was 50mm/s and the drawing ratio was 7.0.
(4) And (4) sealing the bidirectional oriented film obtained in the step (3) in vacuum, placing the film at room temperature under an electron accelerator, and performing electron beam irradiation with the irradiation dose of 50kGy to obtain the water vapor barrier biodegradable polymer film.
The water vapor barrier biodegradable polymer film obtained by the preparation method can be used in a plurality of fields such as agricultural mulching films, food and daily necessities packaging, electronic product packaging and the like.
Example 6:
a water vapor barrier biodegradable polymer film is prepared by the following steps:
(1) mixing poly (butylene adipate/terephthalate), poly (butylene succinate), trimethylolpropane trimethacrylate and an opening agent in a high-speed mixer, and melting and blending in a double-screw extruder to prepare the biodegradable polymer particles. The mass ratio of the poly (adipic acid)/butylene terephthalate to the poly (butylene succinate) is 70: 30; the addition amount of the trimethylolpropane trimethacrylate is 3.0 wt% of the total amount of the poly (adipic acid)/butylene terephthalate and the poly (butylene succinate); the addition amount of the opening agent was 2.0 wt% of the total amount of the polyadipic acid/butylene terephthalate and polybutylene succinate.
(2) And (2) hot-pressing the biodegradable polymer film particles obtained in the step (1) into a biodegradable polymer thick film with the thickness of 0.5mm by adopting a flat vulcanizing machine.
(3) Synchronously and bidirectionally stretching the biodegradable polymer thick film obtained in the step (2) at 70 ℃ to obtain a bidirectionally oriented film; the drawing speed was 50mm/s and the drawing ratio was 5.0.
(4) And (4) sealing the bidirectional oriented film obtained in the step (3) in vacuum, placing the film at room temperature under an electron accelerator, and performing electron beam irradiation with the irradiation dose of 125kGy to obtain the water vapor barrier biodegradable polymer film.
The water vapor barrier biodegradable polymer film obtained by the preparation method can be used in a plurality of fields such as agricultural mulching films, food and daily necessities packaging, electronic product packaging and the like.
Example 7:
a water vapor barrier biodegradable polymer film is prepared by the following steps:
(1) mixing the poly (butylene adipate/terephthalate), polycaprolactone, organic montmorillonite and trimethylolpropane triacrylate in a high-speed mixer, and melting and blending in a double-screw extruder to obtain the biodegradable polymer particles. The mass ratio of the poly (adipic acid)/butylene terephthalate to the polycaprolactone is 90: 10; the addition amount of the trimethylolpropane triacrylate is 3.0wt percent of the total amount of the poly (adipic acid)/butylene terephthalate and the polycaprolactone; the addition amount of the organic montmorillonite is 10 wt% of the total amount of the poly adipic acid/butylene terephthalate and polycaprolactone.
(2) And (2) preparing the biodegradable polymer film particles obtained in the step (1) into a biodegradable polymer thick film with the thickness of 0.05mm by adopting a tape casting method.
(3) Synchronously and bidirectionally stretching the biodegradable polymer thick film obtained in the step (2) at 80 ℃ to obtain a bidirectionally oriented film; the drawing speed was 100mm/s and the drawing ratio was 4.0.
(4) And (4) placing the bidirectional oriented film obtained in the step (3) under an air atmosphere and at room temperature under an electron accelerator, and performing electron beam irradiation with the irradiation dose of 200kGy to obtain the water vapor barrier biodegradable polymer film.
The water vapor barrier biodegradable polymer film obtained by the preparation method can be used in a plurality of fields such as agricultural mulching films, food and daily necessities packaging, electronic product packaging and the like.
Example 8:
a water vapor barrier biodegradable polymer film is prepared by the following steps:
(1) mixing the dried poly (butylene adipate/terephthalate), polyhydroxybutyrate and triallyl isocyanurate in a high-speed mixer, and carrying out melt blending in a double-screw extruder to obtain the biodegradable polymer particles. The mass ratio of the poly (adipic acid)/butylene terephthalate and polyhydroxybutyrate is 80: 20; triallyl isocyanurate was added in an amount of 10% by weight of the total amount of the polyadipic acid/butylene terephthalate and polyhydroxybutyrate.
(2) And (2) preparing the biodegradable polymer film particles obtained in the step (1) into a biodegradable polymer thick film with the thickness of 0.10mm by adopting a tape casting method.
Synchronously and bidirectionally stretching the biodegradable polymer thick film obtained in the step (2) at 80 ℃ to obtain a bidirectionally oriented film; the drawing speed was 100mm/s and the drawing ratio was 5.0.
(4) And (4) placing the bidirectional oriented film obtained in the step (3) under an air atmosphere and at room temperature under an electron accelerator, and performing electron beam irradiation with the irradiation dose of 200kGy to obtain the water vapor barrier biodegradable polymer film.
The water vapor barrier biodegradable polymer film obtained by the preparation method can be used in a plurality of fields such as agricultural mulching films, food and daily necessities packaging, electronic product packaging and the like.
The raw materials used in the invention can be commercial products directly, for example, the poly adipic acid/terephthalic acid-butanediol ester can be commercial poly adipic acid/terephthalic acid-butanediol ester directly (of course, adipic acid, terephthalic acid and butanediol can also be used as preparation raw materials, and the three preparation raw materials are polymerized together to prepare the poly adipic acid/terephthalic acid-butanediol ester by self, and the proportion of the adipic acid and the terephthalic acid in the preparation raw materials can be adjusted flexibly).
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of a water vapor barrier biodegradable polymer film is characterized by comprising the following steps:
(1) blending biodegradable polymer and cross-linking agent to obtain a biodegradable polymer film special material; wherein the biodegradable polymer comprises at least a poly (butylene adipate terephthalate);
(2) forming and processing the special material for the biodegradable polymer film obtained in the step (1) into a biodegradable polymer thick film, wherein the thickness of the thick film is not less than 0.02 mm;
(3) performing biaxial tension on the biodegradable polymer thick film obtained in the step (2) to obtain a biaxial orientation film;
(4) and (4) performing electron beam irradiation on the bidirectional oriented film obtained in the step (3) to obtain the water vapor barrier biodegradable polymer film, so that the water vapor barrier property of the biodegradable polymer film is improved.
2. The method of claim 1, wherein in the step (1), the biodegradable polymer is poly (butylene adipate/terephthalate), or a blend of poly (adipate/terephthalate) and other degradable polymers, and the other degradable polymers are one of poly (lactic acid), thermoplastic starch, carbon dioxide-propylene oxide copolymer, poly (butylene succinate), polycaprolactone, and polyhydroxybutyrate; in the blend of the poly-adipic acid/terephthalic acid-butanediol ester and other degradable polymers, the proportion of the poly-adipic acid/terephthalic acid-butanediol ester is not less than 70 wt%.
3. The method of claim 1, wherein a processing aid is further used in step (1), and accordingly, the biodegradable polymer film material further comprises a processing aid, wherein the processing aid is not more than 10 wt% of the biodegradable polymer.
4. The method of claim 1, wherein in the step (1), the crosslinking agent is one of triallyl isocyanurate, triallyl cyanurate, trimethylolpropane trimethacrylate, and trimethylolpropane triacrylate, and the amount of the crosslinking agent added is 0.5 wt% to 10 wt% of the biodegradable polymer.
5. The method for preparing the water vapor barrier biodegradable polymer film according to claim 1, wherein in the step (2), the forming process is one of compression molding, blow molding and tape casting; the thickness of the biodegradable polymer thick film is 0.02 mm-1 mm.
6. The method for preparing the water vapor barrier biodegradable polymer film according to claim 1, wherein in the step (3), the biaxial stretching is performed at 60 to 90 ℃, and both the transverse stretching and the longitudinal stretching are performed at a stretching speed of 20 to 100mm/s and a stretching ratio of 1.5 to 7;
preferably, in the step (3), the biaxial stretching is simultaneous biaxial stretching.
7. The method for producing a water vapor-barrier biodegradable polymer film according to claim 1, wherein in the step (4), the irradiation dose of the electron beam irradiation is not more than 200 kGy;
the electron beam irradiation is performed in a nitrogen atmosphere, a vacuum atmosphere, or an air atmosphere.
8. The water vapor barrier biodegradable polymer film produced by the production method according to any one of claims 1 to 7.
9. Use of the water vapor barrier biodegradable polymer film of claim 8 as an agricultural mulching film or a packaging material.
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