CN113354928A - Biological plastic for manufacturing degradable film and preparation method thereof - Google Patents
Biological plastic for manufacturing degradable film and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of biodegradable plastic application, and provides a biodegradable plastic for manufacturing a degradable film and a preparation method thereof, wherein the technical scheme is as follows: the precursor liquid raw material of the PBAT is adsorbed in micropores of the porous inorganic filler for esterification and polycondensation, so that a PBAT interface is formed in the gap and on the surface of the porous inorganic filler, and the porous inorganic filler carries epoxy groups, so that the inorganic filler is added in a high amount in the PBAT to prepare the bioplastic, the obtained bioplastic is low in cost, can be directly used for preparing a degradable film by blow molding, is free from obvious reduction in strength, is stable in film preparation by blow molding, and is suitable for various packaging bags.
Description
Technical Field
The invention belongs to the field of functional plastics, particularly relates to the technical field of application of biodegradable plastics, and particularly relates to a biodegradable plastic for manufacturing a degradable film and a preparation method thereof.
Background
Plastic products are now a necessity in production, life and industry, and especially the instant plastic packaging bags for shopping and packaging are used in a great amount. The plastic film products are different from durable plastic products, and various shopping bags and packaging bags of the plastic film products can be discarded after being used, and are difficult to recycle. Since the plastic film product is difficult to naturally decompose after use, it becomes white and polluted, and it becomes a factor affecting the environment. At present, plastic bags are basically buried together with garbage, and are easy to cause lasting pollution. In order to effectively solve the problem of environmental pollution caused by plastics, biodegradable plastics are beginning to be popularized and used on a large scale.
Due to the increase of technical development investment, the types of the existing biodegradable plastics are more, and the biodegradable plastics can be divided into two types of bio-based plastics and petrochemical-based plastics according to the source of raw materials. The bio-based degradable plastics include polylactic acid (PLA), polyhydroxyalkanoate Polymers (PHAs), full starch, cellulose and the like; the petrochemical-based bioplastic comprises polybutylene succinate (PBS), polybutylene adipate-terephthalate (PBAT), carbon dioxide copolymer (PPC), Polycaprolactone (PCL) and the like.
However, due to the influence of technical maturity, stable supply of raw materials and the like, the bio-plastics which can be produced and supplied on a large scale are mainly polylactic acid (PLA) and polybutylene adipate terephthalate (PBAT). And the two bioplastics still have the problems of high cost, poor processing stability, poor service performance of the obtained plastic product and the like. Compared with the existing traditional plastics (PE and PP), the composite material has a larger gap and also becomes an obstacle for influencing the popularization and the application of the bioplastic.
The degradable film is formed by extruding, melting and blowing the biological plastic by a screw, so that the biological plastic is required to have good melt strength, film forming property and proper softness. Film products are also the most demanding raw material of all plastic products. However, the film forming processability of the existing bioplastics polylactic acid (PLA) and polybutylene adipate terephthalate (PBAT) still has more problems.
Polylactic acid (PLA) is polymerized from fermented lactic acid, is separated from the traditional petroleum raw materials, has good biocompatibility and higher strength and modulus, but is hard and poor in toughness, lacks flexibility and elasticity, is difficult to prepare into a film, and is mainly used for injection molding products at present.
The poly (butylene adipate terephthalate) (PBAT) is prepared by taking 1, 4-Butanediol (BDO), Adipic Acid (AA), terephthalic acid (PTA) or terephthalic acid glycol ester (DMT) as raw materials through a direct esterification or ester exchange method, has better ductility and elongation at break, ensures that a molecular chain has good flexibility due to the flexible fatty chain segment, and is a good material for film forming processing. Currently, polybutylene adipate terephthalate (PBAT) has become the mainstream raw material for degradation of membranes. However, the film products processed from pure PBAT resin in the current market have no use value, and the main reason is that the film processed from pure PBAT resin by blowing is too soft, the rigidity is poor, the stability of the blown film is poor, and the processed film packaging bag products have poor openness, softness, poor use experience and high cost.
Aiming at solving the problems of over-softness and high cost of a film prepared from polybutylene adipate terephthalate (PBAT), the prior art has targeted improvement. The problem of too soft PBAT film is improved by blending PBAT with polylactic acid (PLA) with rigidity and the like; the problem of excessive softness of the PBAT film is improved by adding inorganic filler, starch and the like.
Chinese patent CN109825048A discloses a PLA/PBAT composite material and a preparation method thereof. The problem of poor adhesion of two-phase interfaces is solved by using EGMA, a PLA-EGMA-PBAT continuous phase is formed, hydrogen bonds are formed between OMMT and PLA or PBAT, the function of a physical crosslinking point is achieved, the strength of the material is further improved, the prepared product has the high strength of PLA and the toughness of PBAT, and the prepared product can be used for agricultural films and packaging products.
Chinese patent CN110105727A discloses a full-biodegradable mulch film material for crops in irrigation areas and a preparation method and application thereof, the raw materials adopt poly (terephthalic acid) -butylene glycol ester, poly (ethylene furan dicarboxylate), aliphatic carboxylic acid zinc compounds, a compatibilizer, a filler, an antioxidant and an ultraviolet absorbent, and PEF (polyethylene furan dicarboxylate) with strong rigidity is used for carrying out rigidity-enhancing modification on PBAT under the action of the compatibilizer, so that the rigidity of the PBAT is improved, and the rigidity balance of the PBAT is improved.
The Chinese invention patent CN111647183A discloses a preparation method of an inorganic micropowder/PBAT fully-degradable composite film, wherein inorganic fillers of calcium carbonate, silica micropowder, talcum powder, mica powder, gypsum powder, montmorillonite powder, hydromica powder and other inorganic micropowder are added into PBAT to prepare a degradable film, so that the stiffness of the film is improved, and the preparation method is favorable for PBAT film blowing bag making.
Chinese patent CN 103013065B discloses a composite material for poly (butylene succinate) degradable films and a preparation method thereof, wherein poly (butylene succinate), poly (butylene adipate-terephthalate), a filler and a lubricant are directly extruded and granulated, the filler is micron calcium carbonate or corn starch, the cost is reduced, the rigidity of the films is improved, and the preparation is stable.
The blending modification of PBAT is the simplest method for effectively reducing the cost and improving the processing performance of PBAT. However, when polylactic acid is used for hardening modification of PBAT, the compatibility of the polylactic acid and the PBAT is poor, more compatilizers need to be added, the usage amount of the polylactic acid is not too high, and the compatibility is seriously affected by too high usage amount of the polylactic acid, so that the film forming by blow molding is difficult. In addition, polylactic acid is expensive, and the cost is further increased by increasing the amount of polylactic acid used. The inorganic filler, starch and the like are used for modifying the PBAT, the advantage of reducing the PBAT cost is obvious, the rigidity of the film is moderately increased, and the method is also an effective means for reducing the PBAT cost and improving the rigidity of the film in the current market. However, the compatibility of the inorganic filler with PBAT is inferior, and if the problem of compatibility cannot be solved well, the amount of PBAT to be added is limited. According to the feedback of the current market, the addition amount of the inorganic filler for modifying PBAT is within 15 percent, and once the addition amount is increased, the strength of the film is reduced, and the use value is lost.
Therefore, how to solve the problem of maintaining good compatibility with PBAT and stable strength at high inorganic filler contents is very necessary to advance the use of PBAT.
Disclosure of Invention
At present, the inorganic filler is used for improving the PBAT, so that the cost is reduced, and the rigidity of the film is improved, but the inorganic filler has low addition amount due to poor compatibility with the PBAT, if the addition amount of the inorganic filler is further improved, the strength of the film is accelerated to be reduced, the stability of the blown film is even influenced, and the blown film is very easy to break.
In view of the above technical problems, the present invention provides a bio-plastic for producing a degradable film, and further provides a preparation method of the bio-plastic.
One of the technical schemes of the invention is realized by the following technical measures: the biological plastic for manufacturing the degradable film is characterized by comprising the following specific preparation methods:
(1) 1, 4-butanediol, adipic acid and terephthalic acid are mixed according to a molar ratio of 8: 2.2: 1.8 weighing for later use as a premixed material A;
(2) adding the premixed material A obtained in the step (1) into a reaction kettle, adding a catalyst, and uniformly stirring; then adding porous inorganic filler with the particle size of less than 5 mu m, stirring at a low speed, starting a vacuum pump, stabilizing a vacuum pressure gauge at-0.08 MPa, treating for 10-15min, closing the vacuum pump, and reacting in a reaction kettle at 180 ℃ for 120-150 min; heating to 240 ℃, adjusting the temperature and the reaction pressure to be 20-50Pa, performing polycondensation for 80-100min, and discharging to obtain a material B;
(3) cooling and crushing the material B obtained in the step (2), and grinding and dispersing the material B, epoxy resin and a dispersing agent in a grinder to obtain a material C;
(4) putting 40-50 parts by weight of the material C obtained in the step (3), 50-70 parts by weight of poly (butylene adipate-terephthalate) and 1-2 parts by weight of a lubricant into a high-speed mixer, controlling the temperature at 80-100 ℃, and dispersing for 10-15min at the rotating speed of 400-700 rpm; then conveying the mixture to a double-screw extruder, extruding at the temperature of 130-150 ℃, air-cooling, drawing strips, and pelletizing to obtain the bioplastic for manufacturing the degradable film.
In the invention, the catalyst in the step (2) is one of tetrabutyl titanate and stannous chloride; the dosage of the catalyst is 1 to 1.5 percent of the mass of the material A.
In the invention, the mixing mass ratio of the mixed material A and the porous inorganic filler in the step (2) is 1: 3-5.
In the invention, the porous inorganic filler in the step (2) is at least one of zeolite powder, diatomite and hollow glass microspheres. Further preferably, the porous inorganic filler is hollow glass microspheres; the hollow glass beads, except for gaps and surface load PBAT, are used as fillers for the PBAT, have excellent filling compatibility, low density and obvious effect of reducing the density of the PBAT; especially, the hollow glass beads have a ball effect, the use of a lubricant is reduced, heat can be dissipated in time to prevent excessive thermal shear degradation of PBAT, and the prepared degradation film has few surface smoothness defects.
The material A is adsorbed in the micropores for polycondensation by selecting the porous inorganic filler, so that the poly (butylene adipate-terephthalate) is formed in the gaps and on the surface of the porous inorganic filler, the interface compatibility of the inorganic filler is greatly improved when the inorganic filler is added in the poly (butylene adipate-terephthalate), and a compatilizer is not required to be added.
The basic process adopted in the step (2) is esterification and polycondensation to prepare PBAT, and the aim is to form a PBAT interface on the micropores and the surface of the porous inorganic filler so as to conveniently fill the PBAT in a later period without compatibility treatment.
In the invention, the material B, the epoxy resin and the dispersing agent in the step (3) are mixed according to the mass ratio of 100: 2-2.5:1-1.5 grinding and dispersing; the epoxy resin is one of epoxy resin E51 and epoxy resin E44; the dispersing agent is polyethylene wax. The porous inorganic filler is further provided with epoxy groups by grinding the material B and the epoxy resin, and when the porous inorganic filler is used for poly (butylene adipate-terephthalate) (PBAT), the epoxy groups are easy to extend chain with carboxyl groups of the PBAT, so that the strength is improved in an auxiliary mode, and the thermal degradation in blow molding processing is prevented.
In the invention, the grinding in the step (3) adopts conventional grinding, preferably ball milling, and the material B, the epoxy resin and the dispersant are uniformly dispersed; and (3) preventing the poly (butylene adipate-terephthalate) attached with the porous inorganic filler from being degraded due to over-grinding, and preferably performing ball milling for 10-15 min.
In the invention, the polybutylene adipate-terephthalate in the step (4) selects a film grade PBAT with a melt index of 5-7g/10min (190 ℃, the pressure of 2.16 kg); the lubricant is selected from one of paraffin, stearic acid and glyceryl monostearate.
The invention also provides the bioplastic for manufacturing the degradable film, which is prepared by the method. In order to ensure that the compatibility of the inorganic filler for PBAT is good, reduce the influence on the strength and ensure that a film can be stably blown without breaking holes when the inorganic filler is highly filled, the invention selects a porous inorganic material, and adsorbs a precursor liquid raw material (material A) of PBAT in micropores of the porous inorganic filler for polycondensation so as to form polybutylene adipate-terephthalate (PBAT) in the gaps and on the surface of the porous inorganic filler, the modification treatment is different from common coupling modification and interface compatibility modification, the modification treatment of the invention ensures that the inorganic filler has a good PBAT interface, the interface is stable and cannot fall off due to grinding, shearing and the like, and the obvious advantages are that the interface compatibility is greatly improved when the inorganic filler is added into the polybutylene adipate-terephthalate, and no compatilizer is required to be added, so that more filler can be added into the polybutylene adipate-terephthalate without breaking the strength, The processing stability is influenced, and holes are not easy to appear in the blow molding film preparation; the epoxy resin-modified polypropylene composite material has the more excellent effect that the epoxy resin-modified polypropylene composite material is ground with epoxy resin, so that the porous inorganic filler further carries epoxy groups, and when the epoxy group is used for poly (butylene adipate-terephthalate) (PBAT), the epoxy groups are easy to extend chain with carboxyl groups of the PBAT, thereby assisting in improving the strength and preventing thermal degradation in blow molding processing.
Compared with the prior art, the bioplastic for manufacturing the degradable film and the preparation method thereof have the positive effects that:
1. according to the invention, the porous inorganic material is utilized, and the precursor liquid raw material (material A) of the PBAT is adsorbed in the micropores of the porous inorganic filler for polycondensation, so that a PBAT interface is formed in the gaps and on the surface of the porous inorganic filler, the inorganic filler is added in a high amount in the PBAT for preparing the bioplastic, the cost is low, the strength is not obviously reduced, and the blow molding membrane preparation is stable.
2. According to the invention, the porous inorganic filler is enabled to carry the epoxy group, when the porous inorganic filler is used for polybutylene adipate-terephthalate (PBAT), the epoxy group is easy to extend chain with the carboxyl group of the PBAT, so that the strength is improved in an auxiliary manner and the thermal degradation in blow molding processing is prevented.
3. The preparation process is easy to control, the raw materials are easy to obtain, and the preparation method is suitable for stable large-scale production, and the prepared bioplastic can be directly used for preparing degradable films by blow molding and is suitable for various packaging bags.
Drawings
The technical scheme of the invention is further explained by combining the accompanying drawings as follows:
FIG. 1 is a diagram showing the effect of the bio-plastic film blowing obtained by the embodiment of example 1.
FIG. 2 is a graph showing the effect of the bio-plastic film blowing obtained by the embodiment of comparative example 1.
Detailed Description
In order to make the technical solution of the present invention better understood, the technical solution of the present invention will be clearly and completely described below with reference to the embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments obtained by a person skilled in the art without any inventive step based on the technical idea of the present invention shall fall within the scope of protection of the present invention.
Example 1
(1) 1, 4-butanediol, adipic acid and terephthalic acid are mixed according to a molar ratio of 8: 2.2: 1.8 weighing for later use as a premixed material A;
(2) weighing 2kg of the premixed material A obtained in the step (1), adding into a reaction kettle, weighing 20g of catalyst tetrabutyl titanate, and uniformly stirring; then adding 6kg of zeolite powder with the particle size of less than 5 mu m and the porosity of more than 50 percent, starting a stirring paddle of the reaction kettle, stirring at a low speed of 40rpm, starting a vacuum pump, processing for 15min at-0.08 MPa by a stable vacuum pressure gauge, closing the vacuum pump, maintaining the low speed stirring at 40rpm, and reacting for 150min at 180 ℃ in the reaction kettle; heating to 240 ℃, adjusting the temperature and the reaction pressure to 50Pa, performing polycondensation for 80min, and discharging to obtain a material B;
(3) cooling and crushing the material B obtained in the step (2), weighing 5kg, weighing epoxy resin E510.1kg and polyethylene wax 0.05kg, adding into a ball mill, ball-milling for 10min by taking zirconia balls as grinding media, and grinding and dispersing to obtain a material C;
(4) 5kg of the material C obtained in the step (3), 7kg of film-grade PBAT with the melt index of 5g/10min and 0.1kg of glycerin monostearate are put into a high-speed mixer according to the parts by weight, the temperature is controlled at 100 ℃, and the dispersion is carried out for 15min at the rotating speed of 400 rpm; and then conveying the mixture to a parallel co-rotating twin-screw extruder for extrusion and granulation, wherein the temperature control process from a feed inlet to a discharge outlet is T1 ═ 130 ℃, T2 ═ 135 ℃, T3 ═ 140 ℃, T4 ═ 150 ℃, T5 ═ 135 ℃, air cooling and stretching, and granulating to obtain the bioplastic for manufacturing the degradable film, wherein the inorganic filler is more than 30%. .
Example 2
(1) 1, 4-butanediol, adipic acid and terephthalic acid are mixed according to a molar ratio of 8: 2.2: 1.8 weighing for later use as a premixed material A;
(2) weighing 2kg of the premixed material A obtained in the step (1), adding the premixed material A into a reaction kettle, weighing 30g of catalyst tetrabutyl titanate, and uniformly stirring; then adding 7kg of diatomite with the particle size of less than 5 mu m and the porosity of more than 50 percent, starting a stirring paddle of the reaction kettle, stirring at a low speed of 40rpm, starting a vacuum pump, stabilizing a vacuum pressure gauge at-0.08 MPa, treating for 15min, closing the vacuum pump, maintaining the low speed stirring at 40rpm, and reacting the reaction kettle at 165 ℃ for 150 min; heating to 240 ℃, adjusting the temperature and the reaction pressure to 40Pa, performing polycondensation for 80min, and discharging to obtain a material B;
(3) cooling and crushing the material B obtained in the step (2), weighing 5kg, weighing epoxy resin E440.125kg and polyethylene wax 0.075kg, adding into a ball mill, ball-milling for 10min by taking zirconia balls as grinding media, and grinding and dispersing to obtain a material C;
(4) putting 4kg of the material C obtained in the step (3), 6kg of film-grade PBAT with the melt index of 5g/10min and 0.1kg of paraffin into a high-speed mixer according to the parts by weight, controlling the temperature at 100 ℃, and dispersing for 15min at the rotating speed of 700 rpm; and then conveying the mixture to a parallel co-rotating twin-screw extruder for extrusion and granulation, wherein the temperature control process from a feed inlet to a discharge outlet is T1 ═ 130 ℃, T2 ═ 135 ℃, T3 ═ 140 ℃, T4 ═ 150 ℃, T5 ═ 135 ℃, air cooling and stretching, and granulating to obtain the bioplastic for manufacturing the degradable film, wherein the inorganic filler is more than 30%.
Example 3
(1) 1, 4-butanediol, adipic acid and terephthalic acid are mixed according to a molar ratio of 8: 2.2: 1.8 weighing for later use as a premixed material A;
(2) weighing 2kg of the premixed material A obtained in the step (1), adding the premixed material A into a reaction kettle, weighing 30g of catalyst tetrabutyl titanate, and uniformly stirring; then adding 6kg of hollow glass microspheres with the particle size of less than 5 microns and the porosity of more than 35 percent, starting a stirring paddle of the reaction kettle, stirring at a low speed of 40rpm, starting a vacuum pump, stabilizing a vacuum pressure gauge at-0.08 MPa for processing for 10min, closing the vacuum pump, maintaining the low speed stirring at 40rpm, and reacting the reaction kettle at 170 ℃ for 120 min; heating to 240 ℃, adjusting the temperature and the reaction pressure to 50Pa, performing polycondensation for 100min, and discharging to obtain a material B;
(3) cooling and crushing the material B obtained in the step (2), weighing 5kg, weighing epoxy resin E440.1kg and polyethylene wax 0.075kg, adding into a ball mill, ball-milling for 12min by taking zirconia balls as grinding media, and grinding and dispersing to obtain a material C;
(4) 5kg of the material C obtained in the step (3), 7kg of film grade PBAT with the melt index of 5g/10min and 0.1kg of stearic acid are put into a high-speed mixer according to the parts by weight, the temperature is controlled at 80 ℃, and the dispersion is carried out for 15min at the rotating speed of 400 rpm; and then conveying the mixture to a parallel co-rotating twin-screw extruder for extrusion and granulation, wherein the temperature control process from a feed inlet to a discharge outlet is T1 ═ 130 ℃, T2 ═ 135 ℃, T3 ═ 140 ℃, T4 ═ 150 ℃, T5 ═ 135 ℃, air cooling and stretching, and granulating to obtain the bioplastic for manufacturing the degradable film, wherein the inorganic filler is more than 30%.
Comparative example 1
(1) 1, 4-butanediol, adipic acid and terephthalic acid are mixed according to a molar ratio of 8: 2.2: 1.8 weighing for later use as a premixed material A;
(2) weighing 2kg of the premixed material A obtained in the step (1), adding into a reaction kettle, weighing 20g of catalyst tetrabutyl titanate, and uniformly stirring; then adding 6kg of calcium carbonate with the particle size of less than 5 mu m, starting a stirring paddle of the reaction kettle, stirring at a low speed of 40rpm, starting a vacuum pump, treating for 15min at-0.08 MPa by using a stable vacuum pressure gauge, closing the vacuum pump, maintaining the low speed stirring at 40rpm, and reacting for 150min at 180 ℃ by using the reaction kettle; heating to 240 ℃, adjusting the temperature and the reaction pressure to 50Pa, performing polycondensation for 80min, and discharging to obtain a material B;
(3) cooling and crushing the material B obtained in the step (2), weighing 5kg, weighing epoxy resin E510.1kg and polyethylene wax 0.05kg, adding into a ball mill, ball-milling for 10min by taking zirconia balls as grinding media, and grinding and dispersing to obtain a material C;
(4) 5kg of the material C obtained in the step (3), 7kg of film-grade PBAT with the melt index of 5g/10min and 0.1kg of glycerin monostearate are put into a high-speed mixer according to the parts by weight, the temperature is controlled at 100 ℃, and the dispersion is carried out for 15min at the rotating speed of 400 rpm; and then conveying the mixture to a parallel co-rotating twin-screw extruder for extrusion and granulation, wherein the temperature control process from a feed inlet to a discharge outlet is T1 ═ 130 ℃, T2 ═ 135 ℃, T3 ═ 140 ℃, T4 ═ 150 ℃, T5 ═ 135 ℃, air cooling, stretching, and pelletizing to obtain the bioplastic for preparing the degradable film.
Comparative example 2
(1) 1, 4-butanediol, adipic acid and terephthalic acid are mixed according to a molar ratio of 8: 2.2: 1.8 weighing for later use as a premixed material A;
(2) weighing 2kg of the premixed material A obtained in the step (1), adding into a reaction kettle, weighing 20g of catalyst tetrabutyl titanate, and uniformly stirring; then adding 6kg of zeolite powder with the particle size of less than 5 mu m and the porosity of more than 50 percent, starting a stirring paddle of the reaction kettle, stirring at a low speed of 40rpm, starting a vacuum pump, processing for 15min at-0.08 MPa by a stable vacuum pressure gauge, closing the vacuum pump, maintaining the low speed stirring at 40rpm, and reacting for 150min at 180 ℃ in the reaction kettle; heating to 240 ℃, adjusting the temperature and the reaction pressure to 50Pa, performing polycondensation for 80min, and discharging to obtain a material B;
(3) cooling and crushing the material B obtained in the step (2), weighing 5kg, weighing 0.05kg of polyethylene wax, adding into a ball mill, carrying out ball milling for 10min by taking zirconia balls as grinding media, and grinding and dispersing to obtain a material C;
(4) 5kg of the material C obtained in the step (3), 7kg of film-grade PBAT with the melt index of 5g/10min and 0.1kg of glycerin monostearate are put into a high-speed mixer according to the parts by weight, the temperature is controlled at 100 ℃, and the dispersion is carried out for 15min at the rotating speed of 400 rpm; and then conveying the mixture to a parallel co-rotating twin-screw extruder for extrusion and granulation, wherein the temperature control process from a feed inlet to a discharge outlet is T1 ═ 130 ℃, T2 ═ 135 ℃, T3 ═ 140 ℃, T4 ═ 150 ℃, T5 ═ 135 ℃, air cooling, stretching, and pelletizing to obtain the bioplastic for preparing the degradable film.
Comparative example 3
(1) Weighing 3kg of zeolite powder with the particle size of less than 5 mu m and the porosity of more than 50 percent, 7kg of film-grade PBAT with the melt index of 5g/10min, 0.5kg of silane coupling agent and 0.1kg of glycerin monostearate, putting into a high-speed mixer, controlling the temperature at 100 ℃, and dispersing for 15min at the rotating speed of 400 rpm;
(2) and (3) conveying the mixture to a parallel co-rotating twin-screw extruder for extrusion and granulation, wherein the temperature control process from a feed inlet to a discharge outlet is T1 ═ 130 ℃, T2 ═ 135 ℃, T3 ═ 140 ℃, T4 ═ 150 ℃, T5 ═ 135 ℃, air cooling, stretching, and pelletizing to obtain the bioplastic for manufacturing the degradable film.
And (3) testing the film blowing stability:
the bio-plastics obtained in the experiments of examples 1-3 and comparative examples 1-3 and PBAT without filler are subjected to film blowing in a film blowing machine, wherein the temperatures of five sections of the film blowing machine are respectively as follows: 120 ℃, 145 ℃, 165 ℃, 160 ℃ and 140 ℃; the bio-plastic obtained in examples 1-3 and comparative example 2 has stable blown film, smooth surface and no film breaking and breaking; as shown in attached figure 1, the blown film of the bio-plastic blown film in the example 1 is stable and uniform in film surface. The surface roughness of the film when the bioplastic of comparative example 1 is blown into the film is shown in the attached figure 2; the bioplastic in the comparative example 3 has rough film surface and is easy to break holes when being blown into a film, and the film can not be blown continuously. Pure PBAT is extremely unstable but can form a good film.
And (3) mechanical property comparison test:
the tensile strength of the blown film samples was tested at a test speed of 50mm/min, according to the test of GB/T1040 "test methods for tensile Properties of plastics", the test results being shown in Table 1.
Table 1:
through tests, the bioplastic prepared by the technology still keeps good processing stability when the filler content is more than 30%, and the strength loss of the film is small, so that the requirement on strength of a packaging bag product is met.
Comparative example 1 in the implementation process of using non-porous conventional inorganic filler calcium carbonate instead of porous zeolite powder, because calcium carbonate has no void, PBAT has no ability to be condensed in the void of inorganic filler, only surface condensation, the interface modified calcium carbonate interface obtained is poor in effect, the binding force of the interface between PBAT interface and calcium carbonate surface is weak, so the compatibility of filling in PBAT can be affected, the surface of the film is rough when the film is blown by the prepared biological plastic under high filling amount, and the strength of the obtained film is low.
Comparative example 2 no epoxy treatment was applied to material B during the implementation, and the fillers did not extend the carboxyl groups of PBAT well when filled in PBAT, thus the blown film strength was slightly poor.
Comparative example 3 in the application process, the zeolite powder is not subjected to adsorption polycondensation PBAT treatment in advance, but the traditional coupling treatment is adopted, the PBAT can not be subjected to polycondensation in the pores of the zeolite powder, the obtained interface coupling modification has poor effect, the binding force of the PBAT interface and the interface of the zeolite powder surface is weak, so the compatibility of filling in the PBAT can be influenced, and the prepared bioplastic has rough film surface, is easy to break and can not blow the film when the film is blown; the obtained film has low strength.
Claims (8)
1. A preparation method of a biological plastic for manufacturing a degradable film is characterized by comprising the following steps:
(1) 1, 4-butanediol, adipic acid and terephthalic acid are mixed according to a molar ratio of 8: 2.2: 1.8 weighing for later use as a premixed material A;
(2) adding the premixed material A obtained in the step (1) into a reaction kettle, adding a catalyst, and uniformly stirring; then adding porous inorganic filler with the particle size of less than 5 mu m, stirring at a low speed, starting a vacuum pump, stabilizing a vacuum pressure gauge at-0.08 MPa, treating for 10-15min, closing the vacuum pump, and reacting in a reaction kettle at 180 ℃ for 120-150 min; heating to 240 ℃, adjusting the temperature and the reaction pressure to be 20-50Pa, performing polycondensation for 80-100min, and discharging to obtain a material B;
(3) cooling and crushing the material B obtained in the step (2), and grinding and dispersing the material B, epoxy resin and a dispersing agent in a grinder to obtain a material C;
(4) putting 40-50 parts by weight of the material C obtained in the step (3), 50-70 parts by weight of poly (butylene adipate-terephthalate) and 1-2 parts by weight of a lubricant into a high-speed mixer, controlling the temperature at 80-100 ℃, and dispersing for 10-15min at the rotating speed of 400-700 rpm; then conveying the mixture to a double-screw extruder, extruding at the temperature of 130-150 ℃, air-cooling, drawing strips, and pelletizing to obtain the bioplastic for manufacturing the degradable film.
2. The method for preparing a bio-plastic for making a degradable film according to claim 1, wherein the method comprises the following steps: the catalyst in the step (2) is one of tetrabutyl titanate and stannous chloride; the dosage of the catalyst is 1 to 1.5 percent of the mass of the material A.
3. The method for preparing a bio-plastic for making a degradable film according to claim 1, wherein the method comprises the following steps: the mixing mass ratio of the mixed material A and the porous inorganic filler in the step (2) is 1: 3-5; the porous inorganic filler is at least one of zeolite powder, diatomite and hollow glass microspheres.
4. The method for preparing a bio-plastic for making a degradable film according to claim 1, wherein the method comprises the following steps: and (3) mixing the material B, the epoxy resin and the dispersing agent according to the mass ratio of 100: 2-2.5:1-1.5 grinding and dispersing; the epoxy resin is one of epoxy resin E51 and epoxy resin E44; the dispersing agent is polyethylene wax.
5. The method for preparing a bio-plastic for making a degradable film according to claim 1, wherein the method comprises the following steps: and (4) ball milling is adopted in the grinding in the step (3), and the ball milling time is 10-15 min.
6. The method for preparing a bio-plastic for making a degradable film according to claim 1, wherein the method comprises the following steps: the polybutylene adipate-terephthalate in the step (4) is selected from a film grade PBAT with a melt index of 5-7g/10min (190 ℃ and 2.16kg of pressure).
7. The method for preparing a bio-plastic for making a degradable film according to claim 1, wherein the method comprises the following steps: and (4) selecting one of paraffin, stearic acid and glyceryl monostearate as the lubricant.
8. A bioplastic for use in the manufacture of a degradable film, characterised by being produced by the method of any one of claims 1 to 7.
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| CN202110728987.9A CN113354928B (en) | 2021-06-29 | 2021-06-29 | Biological plastic for manufacturing degradable film and preparation method thereof |
| PCT/CN2021/103465 WO2023272569A1 (en) | 2021-06-29 | 2021-06-30 | Bioplastic for manufacturing degradable film, and preparation method therefor |
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