CN117683331A - Biodegradable clip chain self-sealing bag and preparation method thereof - Google Patents
Biodegradable clip chain self-sealing bag and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000011256 inorganic filler Substances 0.000 claims abstract description 73
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 73
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 54
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 49
- 239000002131 composite material Substances 0.000 claims abstract description 47
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- 238000010096 film blowing Methods 0.000 claims abstract description 16
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- 239000000203 mixture Substances 0.000 claims description 22
- 235000021355 Stearic acid Nutrition 0.000 claims description 18
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 18
- 239000007822 coupling agent Substances 0.000 claims description 18
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 18
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 18
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- 238000001035 drying Methods 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 13
- 239000008116 calcium stearate Substances 0.000 claims description 13
- 235000013539 calcium stearate Nutrition 0.000 claims description 13
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical group CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 13
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 10
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 5
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- 239000004698 Polyethylene Substances 0.000 description 1
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- 239000004840 adhesive resin Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a biodegradable clip chain self-sealing bag and a preparation method thereof. The self-sealing bag comprises the following raw materials in parts by weight: 100 parts of PBAT, 5-35 parts of PLA, 4-8 parts of hyperbranched polyester, 1-5 parts of compatibilizer resin, 5-30 parts of inorganic filler, 0.1-1 part of chain extender and 0.1-0.6 part of auxiliary agent. The self-sealing bag is prepared by matching PLA, hyperbranched polyester and PBAT, and simultaneously matching a chain extender and PBAT compatibilizer resin with inorganic filler and auxiliary agent for reaction. In the film blowing forming process, the melt strength of the composite modified granules is guaranteed at low temperature, the bonding degree of the rib buckle and the barrel film is higher, and the interface bonding property is effectively improved, so that the surface of the rib buckle primary-secondary tooth of the self-sealing bag is flat and smooth, has high stiffness, has excellent repeated opening performance and sealing property, is easy for industrial production, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a biodegradable clip chain self-sealing bag and a preparation method thereof.
Background
The self-sealing bag with the clamping chain is a packaging bag which can be sealed by pressing, is commonly provided with a keel bag, a zipper bag and the like, and is widely applied to product packaging in various fields. The main component of the self-sealing bags on the market at present is polyolefin, and low-density polyethylene and high-voltage line type polyethylene are generally selected to be compounded, formed by film blowing and hot cut into bags. However, since polyolefin cannot be degraded, most of self-sealing bags can be reused for multiple times, but as the demand of consumer goods in various society continues to rise, the consumption of plastic packages increases, and the use amount of the self-sealing bags with clip chains also rises sharply, so the development of biodegradable self-sealing bags with clip chains is also the key point of development and research of plastic packaging materials.
The existing biodegradable clip chain self-sealing bag is prepared by taking biodegradable polyesters such as polybutylene terephthalate/adipate (PBAT), polylactic acid (PLA), polypropylene carbonate (PPC), polycaprolactone (PCL) and the like as matrixes, melting and blending, then performing film blowing molding, and hot cutting to prepare the common self-sealing bag. However, the existing biodegradable self-sealing bag has the defects of insufficient rib-buckle engagement force, low opening tension and the like of the self-sealing strip on the bag body, so that the biodegradable self-sealing strip is developed and researched by Chinese patent application CN 109627703A, PLA and PBAT are melt-blended and extruded through a specific die orifice to be rapidly cooled and rolled up by water, the biodegradable self-sealing strip is further prepared, the self-sealing strip is attached to a packaging bag by secondary processing, and the zipper bag meeting the use requirement can be prepared, but the self-sealing bag prepared by the method still has certain limitation and the bonding strength difference between the self-sealing strip and the packaging bag is easy to break away; the Chinese patent application CN 115216126A selects PLA, PPC and PBAT and matches with specific auxiliary agents to prepare a composite material, and then the composite material is prepared into a biodegradable self-sealing bag through a film blowing one-step molding process, the matching of the Wake auxiliary agents and the chain extender improves the melt strength of the composite material, the compatibility of a base material is improved, the primary and secondary teeth formability of the rib buckle is improved, however, although the selected component resins have similar processing temperature intervals, the melt needs to have certain stiffness before the rib buckle is cooled and molded due to poor matching of the melting temperature between the resins in the process of the film blowing and the rib buckle, so that the poor bonding strength between the rib buckle and the film bag is easily caused, the finished product of the clamp chain self-sealing bag is poor in sealing and poor in usability. Therefore, the performance and the preparation process of the biodegradable clip chain self-sealing bag are still to be further improved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a biodegradable clip chain self-sealing bag and a preparation method thereof. The biodegradable clip chain self-sealing bag provided by the invention has the advantages of flat and smooth surface, high stiffness, excellent repeated opening performance and sealing performance, simple preparation method, easiness in industrial production and good application prospect.
The technical scheme of the invention is as follows:
the biodegradable clip chain self-sealing bag comprises the following raw materials in parts by weight: 100 parts of PBAT, 5-35 parts of PLA, 4-8 parts of hyperbranched polyester, 1-5 parts of compatibilizer resin, 5-30 parts of inorganic filler, 0.1-1 part of chain extender and 0.1-0.6 part of auxiliary agent.
PLA and adhesive resin hyperbranched polyester are matched with PBAT, chain extender with active functional groups and corresponding compatibilizer of the PBAT are selected, and inorganic filler and auxiliary agent are matched for reactive melt blending extrusion to prepare the composite modified granules. In the film blowing molding process for preparing the biodegradable plastic self-sealing bag by adopting the composite modified granules, the melt strength of the composite modified granules can be effectively ensured at low temperature, the bonding degree of the rib buckle and the barrel film is higher under the action of hyperbranched polyester, and the interfacial adhesion is effectively improved, so that the surface of the rib buckle primary tooth of the biodegradable plastic self-sealing bag is flat and smooth, the stiffness is high, and the biodegradable plastic self-sealing bag has excellent repeated opening performance and sealing performance.
Further, the melting temperature of the PLA is in the range of 125-140 ℃; melt flow rate: at 190℃and 2.16kg, the value is 4-8g/10min.
The PLA with low melting point and higher fluidity is selected, chain end grafting reaction is more easily generated between the PLA and the hyperbranched polyester as well as between the PLA and the PBAT, and finally the melt strength of the polymer is effectively improved under the combined action of the PLA, the epoxy chain extender, the hyperbranched polyester and the like. In addition, in the melt stretching process of film blowing molding, PLA is easier to form a fibrous structure, and the melt strength of the composite modified granules can be effectively ensured at a lower temperature.
Further, the hyperbranched polyester is a carboxyl-terminated hyperbranched polyester. Among them, aromatic carboxyl-terminated hyperbranched polyesters are preferred. Because the carboxyl-terminated hyperbranched polyester contains aromatic functional groups, the structure of the carboxyl-terminated hyperbranched polyester is similar to that of PBAT, and the carboxyl-terminated hyperbranched polyester is easier to undergo grafting reaction with the carboxyl-terminated hyperbranched polyester under the action of the compatibilizer resin.
Further, the compatibilizing resin is resin grafted with PBAT by active groups; preferably one or more of PBAT-g-MA and PBAT-g-GMA.
Further, the chain extender is an epoxy oligomer chain extender; the inorganic filler is an inorganic filler with a sheet-shaped structure.
Further, the PLA is dall LX930 or LX975;
the hyperbranched polyester is Hyper C302;
the chain extender is KLE-4370B;
the auxiliary agent comprises a lubricant and a slipping agent, wherein the lubricant is calcium stearate; the slipping agent is erucamide;
the inorganic filler is one of mica, talcum powder and montmorillonite with a platy structure, and the particle size range is 2000-6000 meshes; preferably 3000 mesh.
Further, the inorganic filler is activated inorganic filler; the activation process of the inorganic filler comprises the following steps: drying inorganic filler until the water content is lower than 2000ppm, then adding aluminum-titanium composite coupling agent and stearic acid into the inorganic filler, mixing to obtain activated inorganic filler, and sealing and preserving; wherein, the weight portions of the raw materials are respectively 100 portions of inorganic filler, 0.1 to 1 portion of aluminum-titanium composite coupling agent and 0.1 to 1 portion of stearic acid.
The invention also provides a preparation method of the biodegradable clip chain self-sealing bag, which comprises the following steps:
step S1: raw material pretreatment and blending
Firstly, drying and activating inorganic filler, secondly, carrying out dehumidification and drying pretreatment on PLA, PBAT and hyperbranched polyester, and then blending the PBAT, PLA, hyperbranched polyester, compatibilizer resin, inorganic filler, chain extender and auxiliary agent in a high-speed mixer to obtain a blend;
step S2: extrusion granulation of blend materials
Adding the blend obtained in the step S1 into a double-screw extruder for extrusion granulation, and carrying out dehumidification and drying treatment to obtain composite modified granules;
step S3: shaping processing of composite modified granules
And (3) blowing the composite modified granules obtained in the step (S2) by using a self-sealing bag film blowing machine to form a film, rolling the film into a barrel film, and then hot-cutting the rolled barrel film into the self-sealing bag with a clamping chain by using a bag making machine.
Further, the preparation method of the biodegradable clip chain self-sealing bag comprises the following steps:
step S1: raw material pretreatment and blending
Firstly, the inorganic filler is dried and activated, specifically: adding inorganic filler into a high-speed mixer with temperature control, fully drying at the rotation speed of 1000rpm and the temperature of 80 ℃ to ensure that the water content of the inorganic filler is lower than 2000ppm, then adding an aluminum-titanium composite coupling agent and stearic acid into the inorganic filler, continuously mixing for 5min, taking out the activated inorganic filler, and sealing and preserving;
secondly, carrying out dehumidification drying pretreatment on PLA, PBAT and hyperbranched polyester, and then weighing the following materials according to the weight ratio: adding PBAT, PLA, hyperbranched polyester, a compatibilizer, an inorganic filler, a chain extender and an auxiliary agent into a high-speed mixer for blending again to obtain a blend;
step S2: extrusion granulation of blend materials
Adding the blend obtained in the step S1 into a double-screw extruder for extrusion and granulation, setting the temperature interval of the extruder to be 100-150 ℃, setting the rotating speed of the extruder to be 100-300rpm, and setting the feeding speed of the extruder to be 15-30kg/h to obtain composite modified granules and carrying out dehumidification and drying treatment;
step S3: shaping processing of composite modified granules
And (3) blowing the composite modified granules dried in the step (S2) by using a self-sealing bag film blowing machine to form and rolling the composite modified granules into barrel films, wherein the self-sealing bag film blowing machine consists of two single-screw extruders and a co-extrusion die head, the temperature interval of the single-screw extruders and the die head is set to be 130-150 ℃, the rotating speed of the extruders is 40-60rpm, the feeding frequency is 20-40hz, the traction frequency is 10-30hz, the blowing expansion ratio is 2.5-4 times, and then the rolled barrel films are thermally cut into the clip chain self-sealing bags by using a bag making machine.
Compared with the prior art, the biodegradable clip chain self-sealing bag and the preparation method thereof provided by the invention have the following advantages:
the invention selects specific PLA and carboxyl-terminated hyperbranched polyester to match with PBAT, and selects epoxy chain extender with active functional groups, PBAT compatibilizer resin, inorganic filler and auxiliary agent to perform reactive melt blending extrusion to obtain composite modified granules, thereby preparing the biodegradable chain-clamping self-sealing bag. Because the carboxyl-terminated hyperbranched polyester contains aromatic functional groups, the structure of the carboxyl-terminated hyperbranched polyester is similar to that of PBAT, so that the carboxyl-terminated hyperbranched polyester is easier to have grafting reaction with the carboxyl-terminated hyperbranched polyester under the action of the compatibilizer resin; and PLA is easier to undergo chain end grafting reaction with hyperbranched polyester and PBAT under the action of the epoxy chain extender, and finally the melt strength of the polymer is effectively improved under the action of the epoxy chain extender and the hyperbranched polyester.
As can be seen from the attached figure 1 of the invention, because the PLA with lower melting temperature and higher fluidity is selected, the PLA is easier to form a fibrous structure in the melt stretching process of film blowing molding, so that the melt strength of the composite modified granules can be effectively ensured at lower temperature. Furthermore, the sheet inorganic filler not only can ensure the stiffness of the melt and further reduce the shrinkage rate, but also can promote the stiffness of the rib buckle, and after the sheet inorganic filler is combined with hyperbranched polyester, the bonding degree of the rib buckle and a barrel film is higher, the interfacial adhesion is effectively improved, the surface of the finally prepared rib buckle primary and secondary tooth is flat and smooth, the stiffness is high, the opening and closing repetition rate is high, and the sealing usability of the self-sealing bag is also ensured. The biodegradable clip chain self-sealing bag prepared by the method has excellent repeated opening performance, simple preparation process and good application prospect, and is easy for industrial production.
Drawings
Fig. 1 is a schematic diagram of the synergistic effect of the components in the process of blowing the film of the composite modified pellet of the invention (the right side diagram in fig. 1 is a schematic diagram of the enlarged part of the rib buckle).
Detailed Description
The invention is further illustrated by the following description of specific embodiments, which are not intended to be limiting, and various modifications or improvements can be made by those skilled in the art in light of the basic idea of the invention, but are within the scope of the invention as long as they do not depart from the basic idea of the invention.
In the following examples and comparative examples, the reagents not specifically described are conventional reagents, and can be purchased from conventional reagent manufacturing and selling companies.
A preparation method of a biodegradable clip chain self-sealing bag comprises the following steps:
step S1: raw material pretreatment and blending
Firstly, the inorganic filler is dried and activated, specifically: adding inorganic filler into a high-speed mixer with temperature control, fully drying at the rotation speed of 1000rpm and the temperature of 80 ℃ to ensure that the water content of the inorganic filler is lower than 2000ppm, then adding an aluminum-titanium composite coupling agent and stearic acid into the inorganic filler, continuously mixing for 5min, taking out the activated inorganic filler, and sealing and preserving;
secondly, carrying out dehumidification drying pretreatment on PLA, PBAT and hyperbranched polyester, and then weighing the following materials according to the weight ratio: adding PBAT, PLA, hyperbranched polyester, a compatibilizer, an inorganic filler, a chain extender and an auxiliary agent into a high-speed mixer for blending again to obtain a blend;
step S2: extrusion granulation of blend materials
Adding the blend obtained in the step S1 into a double-screw extruder for extrusion and granulation, setting the temperature interval of the extruder to be 100-150 ℃, setting the rotating speed of the extruder to be 270rpm, and setting the feeding speed of the extruder to be 20kg/h to obtain composite modified granules and carrying out dehumidification and drying treatment;
step S3: shaping processing of composite modified granules
And (3) blowing the composite modified granules dried in the step (S2) by using a self-sealing bag film blowing machine to form and rolling the composite modified granules into a barrel film, wherein the self-sealing bag film blowing machine consists of two single-screw extruders and a co-extrusion die head, the temperature interval of the single-screw extruders and the die head is set to 140-150 ℃, the rotating speed of the extruders is 50rpm, the feeding frequency is 30hz, the traction frequency is 10hz, the blowing ratio is 2.5 times, the film thickness is 80 mu m, and then the rolled barrel film is thermally cut into a clip chain self-sealing bag by using a bag making machine.
Comparative example 1:
100 parts of inorganic filler spherical calcium carbonate with 3000 meshes is dried according to the step S1, then 0.5 part of aluminum-titanium composite coupling agent and 0.8 part of stearic acid are selected for mixing and activating, and 100 parts of PBAT, 30 parts of PLA, 4 parts of compatibilizer resin (PBAT-g-GMA), 20 parts of inorganic filler (activated calcium carbonate) and 0.2 part of lubricant (calcium stearate), 0.3 part of chain extender (KLE-4370B) and 0.1 part of slipping agent (erucamide) are selected for blending in a high-speed mixer to obtain a blend.
Wherein PLA is selected from Fengyuan PLA FY601, the melt flow rate measured under the same condition is 9g/10min, and the melting temperature is 175 ℃.
Comparative example 2:
100 parts of inorganic filler talcum powder with 1000 meshes is dried according to the step S1, then 0.3 part of aluminum-titanium composite coupling agent and 0.4 part of stearic acid are selected for mixed activation, and 100 parts of PBAT, 20 parts of PLA (dadel LX 930), 4 parts of compatibilizer resin (PBAT-g-GMA), 20 parts of inorganic filler (activated talcum powder) and 0.1 part of lubricant (calcium stearate) are selected, and 0.5 part of chain extender (KLE-4370B) and 0.1 part of slipping agent (erucamide) are added into a high-speed mixer for blending to obtain a blend.
The melting temperature of the PLA is 130 ℃; melt flow rate: at 190℃under 2.16kg, the value was 8g/10min.
Comparative example 3
100 parts of 8000 meshes of inorganic filler talcum powder is dried according to the step S1, then 0.3 part of aluminum-titanium composite coupling agent and 0.4 part of stearic acid are selected for mixed activation, and 100 parts of PBAT, 20 parts of PLA (dadel LX 930), 4 parts of compatibilizer resin (PBAT-g-GMA), 20 parts of inorganic filler (activated talcum powder) and 0.1 part of lubricant (calcium stearate) are selected, and 0.5 part of chain extender (KLE-4370B) and 0.1 part of slipping agent (erucamide) are added into a high-speed mixer for blending to obtain a blend.
The melting temperature of the PLA is 130 ℃; melt flow rate: at 190℃under 2.16kg, the value was 8g/10min.
Comparative example 4
According to the step S1, 100 parts of inorganic filler talcum powder of 2000 meshes is dried, then 0.5 part of aluminum-titanium composite coupling agent and 0.5 part of stearic acid are selected for mixing and activating, and 100 parts of PBAT, 5 parts of PLA (dadel LX 930), 6 parts of hyperbranched polyester (aliphatic hydroxyl-terminated hyperbranched polyester Hyper H102), 4 parts of compatibilizer resin (PBAT-g-GMA), 25 parts of inorganic filler (activated talcum powder), 0.1 part of lubricant (calcium stearate), 0.5 part of chain extender (KLE-4370B) and 0.1 part of slipping agent (erucamide) are added into a high-speed mixer for blending to obtain a blend.
The melting temperature of the PLA is 130 ℃; melt flow rate: at 190℃under 2.16kg, the value was 8g/10min.
Comparative example 5
According to the step S1, 100 parts of inorganic filler mica with 2000 meshes is dried, then 0.5 part of aluminum-titanium composite coupling agent and 0.5 part of stearic acid are selected for mixed activation, and 100 parts of PBAT, 10 parts of PLA (Fengyuan PLA FY 601), 4 parts of compatibilizer resin (PBAT-g-GMA), 25 parts of inorganic filler (activated mica) and 0.1 part of lubricant (calcium stearate), 0.5 part of chain extender (KLE-4370B) and 0.1 part of slipping agent (erucamide) are added into a high-speed mixer for blending to obtain a blend.
Example 1:
according to the step S1, 100 parts of inorganic filler talcum powder of 2000 meshes is dried, then 0.5 part of aluminum-titanium composite coupling agent and 0.5 part of stearic acid are selected for mixing and activating, and 100 parts of PBAT, 5 parts of PLA (dadel LX 930), 6 parts of hyperbranched polyester (long-chain aromatic carboxyl-terminated hyperbranched polyester Hyper C302), 4 parts of compatibilizer resin (PBAT-g-GMA), 25 parts of inorganic filler (activated talcum powder), 0.1 part of lubricant (calcium stearate), 0.5 part of chain extender (KLE-4370B) and 0.1 part of slipping agent (erucamide) are added into a high-speed mixer for blending to obtain a blend.
The melting temperature of the PLA is 130 ℃; melt flow rate: at 190℃under 2.16kg, the value was 8g/10min.
Example 2:
according to the step S1, 100 parts of 6000 meshes of inorganic filler mica are dried, then 0.8 part of aluminum-titanium composite coupling agent and 0.9 part of stearic acid are selected for mixing and activating, and 100 parts of PBAT, 25 parts of PLA (dadel LX 975), 8 parts of hyperbranched polyester (long-chain aromatic carboxyl-terminated hyperbranched polyester Hyper C302), 4 parts of compatibilizer resin (PBAT-g-GMA), 18 parts of inorganic filler (activated mica), 0.3 part of lubricant (calcium stearate), 0.6 part of chain extender (KLE-4370B) and 0.15 part of slipping agent (erucamide) are added into a high-speed mixer for blending to obtain a blend.
The melting temperature of the PLA is 130 ℃; melt flow rate: at 190℃under 2.16kg, the value was 4g/10min.
Example 3:
according to the step S1, 100 parts of inorganic filler montmorillonite with 3000 meshes is dried, then 0.8 part of aluminum-titanium composite coupling agent and 0.9 part of stearic acid are selected for mixing and activating, and 100 parts of PBAT, 20 parts of PLA (dadel LX 930), 4 parts of hyperbranched polyester (long-chain aromatic carboxyl-terminated hyperbranched polyester Hyper C302), 2 parts of compatibilizer resin (PBAT-g-MA), 30 parts of inorganic filler (activated montmorillonite), 0.3 part of lubricant (calcium stearate), 0.6 part of chain extender (KLE-4370B) and 0.2 part of slipping agent (erucamide) are added into a high-speed mixer for blending.
The melting temperature of the PLA is 130 ℃; melt flow rate: at 190℃under 2.16kg, the value was 8g/10min.
Example 4:
according to the step S1, 100 parts of 5000 meshes of inorganic filler mica are dried, then 0.6 part of aluminum-titanium composite coupling agent and 0.9 part of stearic acid are selected for mixed activation, and 100 parts of PBAT, 35 parts of PLA (dadel LX 930), 8 parts of hyperbranched polyester (long-chain aromatic carboxyl-terminated hyperbranched polyester Hyper C302), 2 parts of compatibilizer resin (PBAT-g-GMA, 2 parts of PBAT-g-MA), 30 parts of inorganic filler (activated mica), 0.3 part of lubricant (calcium stearate), 0.6 part of chain extender (KLE-4370B) and 0.2 part of slipping agent (erucamide) are added into a high-speed mixer for blending.
The melting temperature of the PLA is 130 ℃; melt flow rate: at 190℃under 2.16kg, the value was 8g/10min.
Example 5:
according to the step S1, 100 parts of inorganic filler talcum powder with 3000 meshes is dried, then 0.8 part of aluminum-titanium composite coupling agent and 0.9 part of stearic acid are selected for mixed activation, and 100 parts of PBAT, 30 parts of PLA (dadel LX 975), 8 parts of hyperbranched polyester (long-chain aromatic carboxyl-terminated hyperbranched polyester Hyper C302), 3 parts of compatibilizer resin (PBAT-g-MA), 30 parts of inorganic filler (activated talcum powder), 0.3 part of lubricant (calcium stearate), 0.6 part of chain extender (KLE-4370B) and 0.2 part of slipping agent (erucamide) are added into a high-speed mixer for blending.
The melting temperature of the PLA is 130 ℃; melt flow rate: at 190℃under 2.16kg, the value was 4g/10min.
Example 6:
according to the step S1, 100 parts of inorganic filler montmorillonite with 3000 meshes is dried, then 0.6 part of aluminum-titanium composite coupling agent and 0.5 part of stearic acid are selected for mixed activation, and 100 parts of PBAT, 15 parts of PLA (dadel LX 975), 8 parts of hyperbranched polyester (long-chain aromatic carboxyl-terminated hyperbranched polyester Hyper C302), 3 parts of compatibilizer resin (PBAT-g-MA), 5 parts of inorganic filler (activated montmorillonite), 0.3 part of lubricant (calcium stearate), 0.6 part of chain extender (KLE-4370B) and 0.3 part of slipping agent (erucamide) are added into a high-speed mixer for blending.
The melting temperature of the PLA is 130 ℃; melt flow rate: at 190℃under 2.16kg, the value was 4g/10min.
Test example:
the products of the examples and comparative examples of the present invention were tested in part according to BB/T0014-2011, and the test results are shown in the following table.
Table 1: the performance test of the biodegradable clip chain self-sealing bag obtained in the embodiment of the invention and the comparative example
As can be seen from the performance test results of the comparative examples and the examples, under the form and the particle size of the inorganic filler, the opening tension of the rib buckle in the film bag is effectively improved, and the heat sealing strength of the film and the rib buckle can be further improved by using specific polylactic acid and hyperbranched polyester, so that the phenomena of low heat sealing strength and detachment of the rib buckle and the film surface caused by insufficient interfacial adhesion force are avoided.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. The biodegradable clip chain self-sealing bag is characterized by comprising the following raw materials in parts by weight: 100 parts of PBAT, 5-35 parts of PLA, 4-8 parts of hyperbranched polyester, 1-5 parts of compatibilizer resin, 5-30 parts of inorganic filler, 0.1-1 part of chain extender and 0.1-0.6 part of auxiliary agent.
2. The biodegradable clip-on self-sealing bag according to claim 1, characterized in that said PLA has a melting temperature ranging from 125 to 140 ℃; melt flow rate: at 190℃and 2.16kg, the value is 4-8g/10min.
3. The biodegradable bag of claim 1, wherein said hyperbranched polyester is a carboxyl-terminated hyperbranched polyester.
4. The biodegradable bag of claim 3, wherein said hyperbranched polyester is an aromatic carboxyl-terminated hyperbranched polyester.
5. The biodegradable, clip-on self-sealing bag according to claim 1, wherein said compatibilizer is a resin of a reactive group grafted PBAT.
6. The biodegradable, clip-on self-sealing bag according to claim 1, wherein said chain extender is an epoxy oligomer chain extender; the inorganic filler is an inorganic filler with a sheet-shaped structure.
7. The biodegradable clip-on self-sealing bag according to claim 1, wherein said PLA is dayer LX930 or dayer LX975;
the hyperbranched polyester is Hyper C302;
the compatibilizer resin is one or more of PBAT-g-MA and PBAT-g-GMA;
the chain extender is KLE-4370B;
the auxiliary agent comprises a lubricant and a slipping agent, wherein the lubricant is calcium stearate; the slipping agent is erucamide;
the inorganic filler is one of mica, talcum powder and montmorillonite with a platy structure, and the particle size range is 2000-6000 meshes.
8. The biodegradable clip-on self-sealing bag according to claim 1, characterized in that said inorganic filler is an activated inorganic filler; the activation process of the inorganic filler comprises the following steps: drying inorganic filler until the water content is lower than 2000ppm, then adding aluminum-titanium composite coupling agent and stearic acid into the inorganic filler, mixing to obtain activated inorganic filler, and sealing and preserving; wherein, the weight portions of the raw materials are respectively 100 portions of inorganic filler, 0.1 to 1 portion of aluminum-titanium composite coupling agent and 0.1 to 1 portion of stearic acid.
9. A method of making a biodegradable clip-on self-sealing bag according to any one of claims 1-8, comprising the steps of:
step S1: raw material pretreatment and blending
Firstly, drying and activating inorganic filler, secondly, carrying out dehumidification and drying pretreatment on PLA, PBAT and hyperbranched polyester, and then blending the PBAT, PLA, hyperbranched polyester, compatibilizer resin, inorganic filler, chain extender and auxiliary agent in a high-speed mixer to obtain a blend;
step S2: extrusion granulation of blend materials
Adding the blend obtained in the step S1 into a double-screw extruder for extrusion granulation, and carrying out dehumidification and drying treatment to obtain composite modified granules;
step S3: shaping processing of composite modified granules
And (3) blowing the composite modified granules obtained in the step (S2) by using a self-sealing bag film blowing machine to form a film, rolling the film into a barrel film, and then hot-cutting the rolled barrel film into the self-sealing bag with a clamping chain by using a bag making machine.
10. The method of making a biodegradable clip-on self-sealing bag according to claim 9, comprising the steps of:
step S1: raw material pretreatment and blending
Firstly, the inorganic filler is dried and activated, specifically: adding inorganic filler into a high-speed mixer with temperature control, fully drying at the rotation speed of 1000rpm and the temperature of 80 ℃ to ensure that the water content of the inorganic filler is lower than 2000ppm, then adding an aluminum-titanium composite coupling agent and stearic acid into the inorganic filler, continuously mixing for 5min, taking out the activated inorganic filler, and sealing and preserving;
secondly, carrying out dehumidification drying pretreatment on PLA, PBAT and hyperbranched polyester, and then weighing the following materials according to the weight ratio: adding PBAT, PLA, hyperbranched polyester, a compatibilizer, an inorganic filler, a chain extender and an auxiliary agent into a high-speed mixer for blending again to obtain a blend;
step S2: extrusion granulation of blend materials
Adding the blend obtained in the step S1 into a double-screw extruder for extrusion and granulation, setting the temperature interval of the extruder to be 100-150 ℃, setting the rotating speed of the extruder to be 100-300rpm, and setting the feeding speed of the extruder to be 15-30kg/h to obtain composite modified granules and carrying out dehumidification and drying treatment;
step S3: shaping processing of composite modified granules
And (3) blowing the composite modified granules dried in the step (S2) by using a self-sealing bag film blowing machine to form and rolling the composite modified granules into barrel films, wherein the self-sealing bag film blowing machine consists of two single-screw extruders and a co-extrusion die head, the temperature interval of the single-screw extruders and the die head is set to be 130-150 ℃, the rotating speed of the extruders is 40-60rpm, the feeding frequency is 20-40hz, the traction frequency is 10-30hz, the blowing expansion ratio is 2.5-4 times, and then the rolled barrel films are thermally cut into the clip chain self-sealing bags by using a bag making machine.
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