Polyglycolic acid composite material, and preparation method and application thereof

Abstract

The application discloses a kind of polyglycolic acid composite material and its preparation method and application, the polyglycolic acid composite material, including PGA, PBC, PLA, talcum powder and additive;Wherein, PGA, PBC and PLA structural unit degree of polymerization n are all greater than 300;With the total mass of PGA, PBC and PLA as benchmark, the mass content of PGA is 5~90%, the mass content of PBC is 5~90%, the mass content of PLA is 5~90%.The composite material provided by the application is prepared by blending modification to obtain a kind of high toughness, the whole biodegradable composite material of blow film processing, with the advantages of high toughness, good blow film processability, good opening, excellent performance, simple method, subsequent industrialization difficulty is low.

Description

Technical Field

[0001] This invention belongs to the field of polyglycolic acid composite materials, and relates to a polyglycolic acid composite material, its preparation method and application, and particularly to a polyglycolic acid / polybutylene carbonate / polylactic acid composite material with excellent comprehensive properties, its preparation method and application. Background Technology

[0002] Polyglycolic acid (PGA) is a biodegradable, highly crystalline aliphatic polyester. Due to its outstanding crystallinity and segmental structure, it possesses excellent mechanical properties, gas barrier properties, and biocompatibility, making it widely used in biomedical and ecological fields. However, PGA also has drawbacks, such as poor toughness, low melt strength making blown film difficult, and short shelf life, which limit its large-scale production and application. These issues require further research and solutions.

[0003] Polybutylene carbonate (PBC) is also an important biodegradable polymer material, characterized by moderate biodegradation rate, excellent toughness, and good biocompatibility. Furthermore, its structure is tunable, the product has good color, requires less catalyst, and the polymerization process is simple, showing promising industrialization prospects. Aliphatic polycarbonates and PGA have naturally complementary thermodynamic and mechanical properties, and blending PGA with aliphatic polycarbonates is an effective way to address the aforementioned problems of PGA. However, the slow crystallization rate of PBC leads to easy adhesion and difficulty in opening during blown film production, limiting its convenience in large-scale blown film production. However, the improvement in the crystallization rate of PBC using nucleating agents or opening agents is insufficient to meet the opening requirements during blown film production; therefore, this is also a problem that needs to be studied and solved.

[0004] Polylactic acid (PLA) is a novel biodegradable material made from starch derived from renewable plant resources (such as corn), and is recognized as an environmentally friendly material. It possesses excellent mechanical and physical properties. PLA is suitable for various processing methods such as blow molding and thermoplasticizing, making it easy to process and widely applicable. PLA exhibits a faster crystallization rate and good compatibility with polyvinyl chloride (PBC), thus it can be used as a modifier to improve the opening performance of PGA / PBC composite blown films. Summary of the Invention

[0005] To address the problems existing in the prior art, the present invention aims to provide a polyglycolic acid composite material, its preparation method and application, so as to improve the high toughness and blown film processability of the polyglycolic acid composite material.

[0006] To achieve one aspect of the above-mentioned objective, the polyglycolic acid composite material provided by the present invention adopts the following technical solution:

[0007] A polyglycolic acid composite material, comprising PGA, PBC, PLA, talc and additives;

[0008] The structures of PGA, PBC, and PLA are shown in Equation I, Equation II, and Equation III, respectively:

[0009]

[0010] Among them, the degree of polymerization n of PGA, PBC and PLA structural units is greater than 300;

[0011] Based on the total mass of PGA, PBC, and PLA, the mass content of PGA is 5-90%, the mass content of PBC is 5-90%, and the mass content of PLA is 5-90%.

[0012] To achieve another aspect of the above-mentioned objective, the method for preparing the polyglycolic acid composite material as described above provided by the present invention includes the following steps:

[0013] S1: Mix PGA, PBC, PLA, talc and additives to obtain a mixture;

[0014] S2: The mixture is melted and extruded into granules to obtain the polyglycolic acid composite material.

[0015] To achieve another aspect of the above-mentioned objectives, the present invention provides the application of the polyglycolic acid composite material as described above as a film material and an injection molding material.

[0016] In this invention, unless otherwise specified, all proportions or percentages mentioned are mass ratios or mass percentages.

[0017] Compared with the prior art, the present invention has the following advantages:

[0018] The composite material provided by this invention improves the toughness and processability of PGA by blending and modifying it with PBC, and regulates its degradation rate, enabling continuous blown film processing. Furthermore, addressing the problem of poor opening properties in blends where nucleating agents or opening agents cannot effectively solve the issue, PLA is added. Its rapid crystallization rate and good compatibility with PBC resolve the problem of poor PGA / PBC opening properties caused by the slow crystallization rate of PBC. This results in a high-toughness, blown film-processable, fully biodegradable composite material. The blend prepared using the method described in this invention has advantages such as high toughness, good blown film processability, good opening properties, excellent performance, and a simple method with low difficulty in subsequent industrialization. Detailed Implementation

[0019] To enable those skilled in the art to better understand the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.

[0020] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and should be understood to include values ​​close to these ranges or values, such as values ​​±10% of the endpoint values. For numerical ranges, endpoint values ​​of various ranges, endpoint values ​​of various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. Without conflict, the embodiments and features described in this application can be combined with each other.

[0021] It should be noted that the terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion, for example, a process, method, system, product, or device that includes a series of steps or units is not necessarily limited to those steps or units that are explicitly listed, but may include other steps or units that are not explicitly listed or that are inherent to such process, method, product, or device.

[0022] The polyglycolic acid composite material of the present invention includes polyglycolic acid (PGA), polybutylene carbonate (PBC), polylactic acid (PLA), talc, and additives; the additives include heat stabilizers, antioxidants, opening agents, and chain extenders.

[0023] The structures of PGA, PBC, and PLA are shown in Equation I, Equation II, and Equation III, respectively:

[0024]

[0025] Among them, the degree of polymerization n of PGA, PBC and PLA structural units is greater than 300;

[0026] Based on the total mass of PGA, PBC, and PLA, the mass content of PGA is 5-90%, the mass content of PBC is 5-90%, and the mass content of PLA is 5-90%.

[0027] In one embodiment, the amount of talc added is 2-30% of the total mass of PGA, PBC and PLA, for example 2%, 5%, 8%, 11%, 14%, 17%, 20%, 23%, 26%, 30%, preferably 2-10%.

[0028] In this invention, based on the total mass of PGA, PBC, and PLA, the mass content of PGA can be 5% to 90%, for example 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, preferably 10% to 40%.

[0029] In one embodiment, the melt flow index of PGA is less than 40 g / 10 min (230°C, 2.16 kg), preferably less than or equal to 20 g / 10 min (230°C, 2.16 kg). The melt flow index of PGA can be 10–20 g / 10 min, for example 10 g / 10 min, 12 g / 10 min, 15 g / 10 min, 16 g / 10 min, 18 g / 10 min, and 20 g / 10 min.

[0030] In this invention, the degree of polymerization of the repeating units of PGA is greater than 300, preferably 300-600, such as 400 or 500.

[0031] In this invention, based on the total mass of PGA, PBC, and PLA, the mass content of PBC can be 5% to 90%, for example 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, preferably 10-80%.

[0032] In one embodiment, the melt flow index of the PBC is less than 20 g / 10 min (150 °C, 2.16 kg), preferably less than 10 g / 10 min (150 °C, 2.16 kg). The melt flow index of the PBC can be 0.7 to 6 g / 10 min. For example, 0.7 g / 10 min, 1.5 g / 10 min, 1.8 g / 10 min, 2 g / 10 min, 3 g / 10 min, 4 g / 10 min, 5 g / 10 min, and 6 g / 10 min.

[0033] In this invention, the degree of polymerization of the repeating units of PBC is greater than 300, preferably 300-600, such as 400 or 500.

[0034] In this invention, based on the total mass of PGA, PBC, and PLA, the mass content of PLA can be 5% to 90%, for example 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, preferably 10% to 60%.

[0035] In one embodiment, the melt index of PLA is less than 20 g / 10 min (190°C, 2.16 kg), preferably less than 10 g / 10 min (190°C, 2.16 kg). The melt index of PLA can be 0.7 to 6 g / 10 min. For example, 0.7 g / 10 min, 1.5 g / 10 min, 1.8 g / 10 min, 2 g / 10 min, 3 g / 10 min, 4 g / 10 min, 5 g / 10 min, and 6 g / 10 min.

[0036] In this invention, the degree of polymerization of the repeating units of PLA is greater than 300, preferably 300-600, such as 400 or 500.

[0037] In one embodiment, the additive includes one, two, or more of a heat stabilizer, antioxidant, opening agent, and chain extender.

[0038] In one embodiment, based on the total mass of PGA, PBC, and PLA, the mass content of the heat stabilizer can be 0.01% to 3%, for example, 0.05%, 0.08%, 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.5%, 2%, or 2.5%; preferably, the mass content of the heat stabilizer can be 0.05% to 1%.

[0039] In one embodiment, based on the total mass of PGA, PBC, and PLA, the mass content of the antioxidant can be 0.01% to 3%, for example, 0.05%, 0.08%, 0.1%, 0.15%, 0.2%, 0.5%, 0.8%, 1%, 1.5%, 2%, or 2.5%; preferably, the mass content of the antioxidant can be 0.05% to 1%.

[0040] In one embodiment, based on the total mass of PGA, PBC, and PLA, the mass content of the opening agent can be 0.01% to 3%, for example, 0.05%, 0.08%, 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.5%, 2%, or 2.5%; preferably, the mass content of the opening agent can be 0.05% to 1%.

[0041] In one embodiment, based on the total mass of PGA, PBC, and PLA, the mass content of the chain extender can be 0.01% to 5%, for example, 0.05%, 0.08%, 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, or 4.5%; preferably, the mass content of the chain extender can be 0.1% to 2%.

[0042] In one embodiment, the heat stabilizer may be at least one of phosphite heat stabilizers, preferably one or more of triphenyl phosphite, trimethyl phosphite, and ethyl phosphite.

[0043] In one embodiment, the antioxidant may be a hindered phenolic antioxidant, such as pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N-1,6-hexylene-di-[3,5-di-tert-butyl-4-hydroxyphenylpropionamide], or N,N-bis[β(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine.

[0044] In one embodiment, the opening agent may be oleamide and / or erucamide.

[0045] In one embodiment, the chain extender may be one or more of diepoxides, dioximidazoles, diisocyanates, polycarbodiimides, bisphthalimides, carboxylic anhydrides, bicyclic imides, organosilazanes, peroxides, and diacylbislactams; preferably, the chain extender may be N,N-diepoxypropylbenzamide, hexamethylene diisocyanate, 1,2,4,5-benzenetetracarboxylic dianhydride, phthalic anhydride, succinic anhydride, hexaphenyltrisilazane, and N,N-oxalylbiscaprolactam, toluene diisocyanate, diphenylmethane diisocyanate. The following are one or more of the following: ester, polydiphenylmethane diisocyanate, methylene bis(4-cyclohexyl isocyanate), dicyclohexylmethane-4-4-diisocyanate, 2,2,4-trimethylhexane diisocyanate, bis(phthalimide), benzoyl peroxide, dicumyl peroxide, dibutyl peroxide, α,α-bis(tert-butylperoxy)diisopropylbenzene, 1,2,4,5-benzenetetracarboxylic acid dianhydride, bis(dioxazolone) or bis(benzoxazine), octamethylcyclotetrasilazane, hexaphenyltrisilazane 2,2-bis(2-dioxazoline).

[0046] The present invention also provides a method for preparing the above-mentioned PGA / PBC / PLA material, comprising the following steps:

[0047] S1: Mix PGA, PBC, PLA, talc and additives to obtain a mixture;

[0048] S2: The mixture is melted and extruded into granules to obtain PGA / PBC / PLA material.

[0049] In one embodiment, in step S2, the mixture can be melt-blended and extruded using a twin-screw extruder.

[0050] In one embodiment, the temperature of the twin-screw extruder can be 190–250°C, preferably 210–240°C, for example 230°C; the rotational speed can be 30–500 r / min, preferably 70–200 r / min, for example 90 r / min, 100 r / min, 120 r / min, 150 r / min, 160 r / min, 180 r / min, or 190 r / min.

[0051] This invention utilizes a blending modification method to prepare a toughened and biodegradable PGA / PBC / PLA blend composite material, overcoming the shortcomings of PGA such as poor toughness, low melt strength making it difficult to blown film, and short shelf life of the finished product; it also solves the problem of poor opening properties after blown film processing of the blend. The blend prepared by the method described in this invention has advantages such as good toughness, good processability, good opening properties, and simple operation, showing potential application prospects in green packaging, biomaterials, consumer products, and building materials.

[0052] The following describes, with reference to embodiments, a PGA / PBC / PLA material of the present invention and its preparation thereof. The performance parameters in each embodiment and comparative example were measured according to the following method:

[0053] 1. Melt Flow Index

[0054] Place 5g of the PGA / PBC / PLA composition into the chamber of the melt flow index tester and measure the melt flow index at 230℃ and 2.16kg temperature and pressure according to the test standard GB / T3682-2000.

[0055] 2. Degradation rate

[0056] Add 10 ml of water and 2 g of the sample film to be tested to a sealed container, and place it in a constant temperature and humidity chamber at 37℃ for 30 days; dry and weigh to obtain the undegraded mass. Degradation rate = (2 - undegraded mass) / 2 * 100%.

[0057] 3. Elongation at break

[0058] The sample was tested according to standard ISO 527 (2012) on a universal testing machine (Instron 1122, UK). The sample size was 80×4×2mm. During the test, the movement speed of the fixture beam was 20mm / min.

[0059] Unless otherwise specified, all reagents used in the following examples / comparative examples are of analytical grade.

[0060] Example 1

[0061] S1: Mix 10 kg PGA (melt index 19 g / 10 min (230℃, 2.16 kg)), 80 kg PBC (melt index 4 g / 10 min (150℃, 2.16 kg)), 10 kg PLA (melt index 4 g / 10 min (190℃, 2.16 kg)), 0.2 kg pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.1 kg trimethyl phosphite, 0.2 kg oleamide, 0.4 kg diphenylmethane diisocyanate, and 5 kg talc powder evenly to obtain a blend.

[0062] S2: The uniformly mixed blend was added to a twin-screw extruder. The extruder temperature was set to 232℃ and the speed to 80 r / min. The blend was extruded and granulated to obtain PGA / PBC / PLA material, which was then subjected to blown film processing. The PGA / PBC / PLA material was characterized according to the aforementioned method. Its melt index was 14 g / 10 min (230℃, 2.16 kg), its elongation at break was 349%, and its degradation rate was 28%. This formulation can be continuously blown into film and has excellent opening performance.

[0063] Example 2

[0064] S1: Mix 10 kg PGA (melt index 19 g / 10 min (230℃, 2.16 kg)), 70 kg PBC (melt index 4 g / 10 min (150℃, 2.16 kg)), 20 kg PLA (melt index 5 g / 10 min (190℃, 2.16 kg)), 0.1 kg pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.2 kg triphenyl phosphite, 0.1 kg erucamide, 1 kg succinic anhydride, and 8 kg talc powder evenly to obtain a blend.

[0065] S2: The uniformly mixed blend was added to a twin-screw extruder. The extruder temperature was set to 228℃ and the speed to 90 r / min. The blend was extruded and granulated to obtain PGA / PBC / PLA material, which was then subjected to blown film processing. The PGA / PBC / PLA material was characterized according to the aforementioned method. Its melt index was 15 g / 10 min (230℃, 2.16 kg), its elongation at break was 285%, and its degradation rate was 36%. This formulation can be continuously blown into film and has excellent opening performance.

[0066] Example 3

[0067] S1: Mix 10 kg PGA (melt index 17 g / 10 min (230℃, 2.16 kg)), 60 kg PBC (melt index 5 g / 10 min (150℃, 2.16 kg)), 30 kg PLA (melt index 3 g / 10 min (190℃, 2.16 kg)), 0.15 kg N,N-1,6-hexylene-di-[3,5-di-tert-butyl-4-hydroxyphenylpropionamide], 0.15 kg triphenyl phosphite, 0.3 kg erucamide, 1.4 kg toluene diisocyanate, and 6 kg talc powder evenly to obtain a blend.

[0068] S2: The uniformly mixed blend was added to a twin-screw extruder. The extruder temperature was set to 238℃ and the speed to 110 r / min. The blend was extruded and granulated to obtain PGA / PBC / PLA material, which was then subjected to blown film processing. The PGA / PBC / PLA material was characterized according to the aforementioned method. Its melt index was 15 g / 10 min (230℃, 2.16 kg), its elongation at break was 208%, and its degradation rate was 47%. This formulation can be continuously blown into film and has excellent opening performance.

[0069] Example 4

[0070] S1: Mix 40 kg PGA (melt index 18 g / 10 min (230℃, 2.16 kg)), 50 kg PBC (melt index 3 g / 10 min (150℃, 2.16 kg)), 10 kg PLA (melt index 4 g / 10 min (190℃, 2.16 kg)), 0.1 kg N,N-1,6-hexylene-di-[3,5-di-tert-butyl-4-hydroxyphenylpropionamide], 0.2 kg triethyl phosphite, 0.14 kg oleamide, 1.4 kg 1,2,4,5-benzenetetracarboxylic acid dianhydride, and 7 kg talc powder evenly to obtain a blend.

[0071] S2: The uniformly mixed blend was added to a twin-screw extruder. The extruder temperature was set to 232℃ and the speed to 80 r / min. The blend was extruded and granulated to obtain PGA / PBC / PLA material, which was then subjected to blown film processing. The PGA / PBC / PLA material was characterized according to the aforementioned method. Its melt index was 17 g / 10 min (230℃, 2.16 kg), its elongation at break was 170%, and its degradation rate was 51%. This formulation can be continuously blown into film and has excellent opening performance.

[0072] Example 5

[0073] S1: Mix 30 kg PGA (melt index 17 g / 10 min (230℃, 2.16 kg)), 40 kg PBC (melt index 2 g / 10 min (150℃, 2.16 kg)), 30 kg PLA (melt index 4 g / 10 min (190℃, 2.16 kg)), 0.15 kg N,N-1,6-hexylene-di-[3,5-di-tert-butyl-4-hydroxyphenylpropionamide], 0.2 kg triphenyl phosphite, 0.3 kg oleamide, 1 kg dioxazolone, and 3 kg talc evenly to obtain a blend.

[0074] S2: The uniformly mixed blend was added to a twin-screw extruder. The extruder temperature was set to 234℃ and the speed to 95 r / min. The blend was extruded and granulated to obtain PGA / PBC / PLA material, which was then subjected to blown film processing. The PGA / PBC / PLA material was characterized according to the aforementioned method. Its melt index was 13 g / 10 min (230℃, 2.16 kg), its elongation at break was 150%, and its degradation rate was 60%. This formulation can be continuously blown into film and has excellent opening performance.

[0075] Example 6

[0076] S1: Mix 20 kg PGA (melt index 17 g / 10 min (230℃, 2.16 kg)), 30 kg PBC (melt index 1 g / 10 min (150℃, 2.16 kg)), 50 kg PLA (melt index 2 g / 10 min (190℃, 2.16 kg)), 0.14 kg N,N-bis[β(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 0.22 kg triphenyl phosphite, 0.1 kg erucamide, 1 kg octamethylcyclotetrasilazane, and 4 kg talc powder evenly to obtain a blend.

[0077] S2: The uniformly mixed blend was added to a twin-screw extruder. The extruder temperature was set to 227℃ and the speed to 80 r / min. The blend was extruded and granulated to obtain PGA / PBC / PLA material, which was then subjected to blown film processing. The PGA / PBC / PLA material was characterized according to the aforementioned method. Its melt index was 12 g / 10 min (230℃, 2.16 kg), its elongation at break was 147%, and its degradation rate was 63%. This formulation can be continuously blown into film and has excellent opening performance.

[0078] Example 7

[0079] S1: Mix 30 kg PGA (melt index 14 g / 10 min (230℃, 2.16 kg)), 20 kg PBC (melt index 4 g / 10 min (150℃, 2.16 kg)), 50 kg PLA (melt index 4 g / 10 min (190℃, 2.16 kg)), 0.3 kg N,N-1,6-hexylene-di-[3,5-di-tert-butyl-4-hydroxyphenylpropionamide], 0.12 kg triphenyl phosphite, 0.2 kg oleamide, 1.5 kg α,α-bis(tert-butylperoxy)diisopropylbenzene, and 9 kg talc powder evenly to obtain a blend.

[0080] S2: The uniformly mixed blend is added to a twin-screw extruder. The extruder temperature is set to 235℃ and the speed to 100 r / min. The blend is extruded and granulated to form PGA / PBC / PLA material, which is then blown into a film. The PGA / PBC / PLA material is characterized according to the aforementioned method. Its melt index is 14 g / 10 min (230℃, 2.16 kg), elongation at break is 123%, and degradation rate is 67%. This formulation can be continuously blown into a film and has excellent opening performance.

[0081] Example 8

[0082] S1: Mix 30 kg PGA (melt index 13 g / 10 min (230℃, 2.16 kg)), 10 kg PBC (melt index 1.7 g / 10 min (150℃, 2.16 kg)), 60 g PLA (melt index 4 g / 10 min (190℃, 2.16 kg)), 0.15 kg N,N-1,6-hexylene-di-[3,5-di-tert-butyl-4-hydroxyphenylpropionamide], 0.13 kg trimethyl phosphite, 0.3 kg erucamide, 0.9 kg hexamethylene diisocyanate, and 6 kg talc powder evenly to obtain a blend.

[0083] S2: The uniformly mixed blend was added to a twin-screw extruder. The extruder temperature was set to 237℃ and the speed to 150 r / min. The blend was extruded and granulated to obtain PGA / PBC / PLA material, which was then subjected to blown film processing. The PGA / PBC / PLA material was characterized according to the aforementioned method. Its melt index was 11 g / 10 min (230℃, 2.16 kg), its elongation at break was 108%, and its degradation rate was 74%. This formulation can be continuously blown into film and has excellent opening performance.

[0084] Comparative Example 1

[0085] S1: Mix 100kg PGA, 0.2kg N,N-1,6-hexyl-bis-[3,5-di-tert-butyl-4-hydroxyphenylpropionamide], 0.12kg trimethyl phosphite, 0.3kg erucamide, 0.8kg hexamethylene diisocyanate, and 6kg talc to obtain a blend.

[0086] S2: The uniformly mixed blend was added to a twin-screw extruder. The extruder temperature was set to 235℃ and the speed to 150 r / min. The blend was extruded and granulated, and then blown into film. The PGA sample was characterized according to the aforementioned method. Its melt index was 17 g / 10 min (230℃, 2.16 kg), elongation at break was 4%, and the degradation rate was 100%. The sample could not be continuously blown into film.

[0087] Comparative Example 2

[0088] S1: Mix 100 kg PBC, 0.1 kg N,N-1,6-hexylene-bis-[3,5-di-tert-butyl-4-hydroxyphenylpropionamide], 0.15 kg triphenyl phosphite, 0.14 kg oleamide, 1.2 kg α,α-bis(tert-butylperoxy)diisopropylbenzene, and 9 kg talc powder evenly to obtain a blend.

[0089] S2: The uniformly mixed blend was added to a twin-screw extruder. The extruder temperature was set to 235℃ and the speed to 90 r / min. The blend was extruded and granulated. The PBC sample was characterized according to the aforementioned method. Its melt index was 2 g / 10 min (150℃, 2.16 kg), its elongation at break was 395%, and its degradation rate was 10%. The sample could not be continuously blown into film.

[0090] Comparative Example 3

[0091] S1: Mix 100kg PLA, 0.1kg N,N-1,6-hexylene-bis-[3,5-di-tert-butyl-4-hydroxyphenylpropionamide], 0.15kg triphenyl phosphite, 0.14kg oleamide, 1.2kg α,α-bis(tert-butylperoxy)diisopropylbenzene, and 9kg talc powder evenly to obtain a blend.

[0092] S2: The uniformly mixed blend was added to a twin-screw extruder. The extruder temperature was set to 235℃ and the speed to 90 r / min. The blend was extruded and granulated. The PLA sample was characterized according to the aforementioned method. Its melt index was 4 g / 10 min (190℃, 2.16 kg), its elongation at break was 395%, and its degradation rate was 10%. The sample could not be continuously blown into film.

[0093] Comparative Example 4

[0094] S1: Mix 50 kg PGA, 50 kg PBC, 0.1 kg N,N-1,6-hexylene-bis-[3,5-di-tert-butyl-4-hydroxyphenylpropionamide], 0.15 kg triphenyl phosphite, 0.14 kg oleamide, 1.2 kg α,α-bis(tert-butylperoxy)diisopropylbenzene, and 9 kg talc powder evenly to obtain a blend.

[0095] S2: The uniformly mixed blend was added to a twin-screw extruder. The extruder temperature was set to 235℃ and the speed to 90 r / min. The blend was extruded and granulated. The PGA / PBC sample was characterized according to the aforementioned method. Its melt index was 5 g / 10 min (190℃, 2.16 kg), elongation at break was 160%, and degradation rate was 55%. The sample could be continuously blown into film, but the sample could not be opened.

[0096] Comparative Example 5

[0097] S1: Mix 50 kg PGA, 50 kg PLA, 0.1 kg N,N-1,6-hexylene-bis-[3,5-di-tert-butyl-4-hydroxyphenylpropionamide], 0.15 kg triphenyl phosphite, 0.14 kg oleamide, 1.2 kg α,α-bis(tert-butylperoxy)diisopropylbenzene, and 9 kg talc powder evenly to obtain a blend.

[0098] S2: The uniformly mixed blend was added to a twin-screw extruder. The extruder temperature was set to 235℃ and the speed to 90 r / min. The blend was extruded and granulated. The PGA / PLA sample was characterized according to the aforementioned method. Its melt index was 3.5 g / 10 min (190℃, 2.16 kg), elongation at break was 6%, and the degradation rate was 70%. The sample could not be continuously blown into film.

[0099] Table 1 Performance test results of materials in each embodiment and comparative example

[0100]

[0101]

[0102]

[0103] Based on the above description and the results in Table 1, the elongation at break of the material in Comparative Example 1 was 4%, the melt index of the material in Comparative Example 2 was 2 g / 10 min, and the elongation at break of the material in Comparative Example 3 was 8%, both of which showed significant deficiencies. However, the materials in Examples 1-8 exhibited significantly improved elongation at break and melt index compared to the materials in Comparative Examples 1 and 2. This indicates that blending PGA with PBC can solve the problem of PGA's low toughness hindering blown film processing, and the introduction of PLA solves the problem of slow PBC crystallization causing the film to fail to open. Furthermore, as the PBC content in the examples increased, the elongation at break increased accordingly, while the degradation rate decreased within the same time period, thus improving the material's degradation rate and toughness.

[0104] Unless otherwise specified, the terms used in this invention have the meanings commonly understood by those skilled in the art.

[0105] Obviously, the present invention is not limited to the above embodiments, and many variations are possible. All variations that can be directly derived or conceived by those skilled in the art from the content disclosed in this invention should be considered within the scope of protection of this invention.

Claims

1. A polyglycolic acid composite material, comprising PGA, PBC, PLA, talc, and additives; in, The structures of PGA, PBC, and PLA are shown in Equation I, Equation II, and Equation III, respectively: (Formula I); (Formula II); (Formula III) Among them, the degree of polymerization n of PGA, PBC and PLA structural units is greater than 300; Based on the total mass of PGA, PBC, and PLA, the mass content of PGA is 5-90%, the mass content of PBC is 5-90%, and the mass content of PLA is 5-90%.

2. The polyglycolic acid composite material according to claim 1, characterized in that, The amount of talc added is 2-30% of the total mass of PGA, PBC and PLA.

3. The polyglycolic acid composite material according to claim 2, characterized in that, The amount of talc added is 2-10% of the total mass of PGA, PBC and PLA.

4. The polyglycolic acid composite material according to claim 1, characterized in that, Based on the total mass of PGA, PBC, and PLA, the mass content of PGA is 10-40%, the mass content of PBC is 10-80%, and the mass content of PLA is 10-60%.

5. The polyglycolic acid composite material according to claim 1, characterized in that, Under the conditions of a test temperature of 230℃ and an applied load weight of 2.16kg, the melt index of PGA is less than 40g / 10min; The degree of polymerization of repeating units in PGA is 300-600.

6. The polyglycolic acid composite material according to claim 5, characterized in that, The melt flow index of PGA is 10-20 g / 10 min.

7. The polyglycolic acid composite material according to claim 1, characterized in that, Under the conditions of a test temperature of 150℃ and an applied load weight of 2.16kg, the melt index of PBC is less than 20g / 10min; The degree of polymerization of repeating units in PBC is 300-600.

8. The polyglycolic acid composite material according to claim 7, characterized in that, The melt flow index of PBC is 0.7–6 g / 10 min.

9. The polyglycolic acid composite material according to claim 1, characterized in that, Under the conditions of a test temperature of 190℃ and an applied load of 2.16kg, the melt index of PLA is less than 20g / 10min; The degree of aggregation of repeating units in PLA is 300-600.

10. The polyglycolic acid composite material according to claim 9, characterized in that, The melt flow index of PLA is 0.7–6 g / 10 min.

11. The polyglycolic acid composite material according to claim 1, characterized in that, The additives include one, two or more of the following: heat stabilizers, antioxidants, opening agents, and chain extenders.

12. The polyglycolic acid composite material according to claim 11, characterized in that, The heat stabilizer is a phosphite-based heat stabilizer; Based on the total mass of PGA, PBC, and PLA, the mass content of the heat stabilizer is 0.01% to 3%.

13. The polyglycolic acid composite material according to claim 12, characterized in that, The heat stabilizer is one or more of triphenyl phosphite, trimethyl phosphite, and ethyl phosphite; Based on the total mass of PGA, PBC, and PLA, the mass content of the heat stabilizer is 0.05% to 1%.

14. The polyglycolic acid composite material according to claim 11, characterized in that, The antioxidant is a hindered phenolic antioxidant; Based on the total mass of PGA, PBC, and PLA, the antioxidant content is 0.01% to 3% by mass.

15. The polyglycolic acid composite material according to claim 14, characterized in that, The antioxidant is one or more of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N-1,6-hexene-di-[3,5-di-tert-butyl-4-hydroxyphenylpropionamide], and N,N-bis[β(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine; Based on the total mass of PGA, PBC, and PLA, the antioxidant content is 0.05% to 1% by mass.

16. The polyglycolic acid composite material according to claim 11, characterized in that, The opening agent is oleamide and / or erucamide; Based on the total mass of PGA, PBC and PLA, the mass content of the opening agent is 0.01-3%.

17. The polyglycolic acid composite material according to claim 16, characterized in that, Based on the total mass of PGA, PBC, and PLA, the mass content of the opening agent is 0.05% to 1%.

18. The polyglycolic acid composite material according to claim 11, characterized in that, The chain extender is one or more selected from the following: diepoxide, dioximidazole, diisocyanate, polycarbodiimide, bisphthalimide, carboxylic anhydride, bicyclic imide, organosilazane, peroxide, and diacylbislactam. Based on the total mass of PGA, PBC, and PLA, the mass content of the chain extender is 0.01–5%.

19. The polyglycolic acid composite material according to claim 18, characterized in that, The chain extender is one or more of N,N-diepoxypropylbenzamide, hexamethylene diisocyanate, 1,2,4,5-benzenetetracarboxylic acid dianhydride, phthalic anhydride, succinic anhydride, hexaphenyltrisilazane, and N,N-oxalylbiscaprolactam, toluene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, methylene bis(4-cyclohexyl isocyanate), dicyclohexylmethane-4-4-diisocyanate, 2,2,4-trimethylhexane diisocyanate, bis(phthalimide), benzoyl peroxide, dicumyl peroxide, dibutyl peroxide, α,α-bis(tert-butylperoxy)diisopropylbenzene, 1,2,4,5-benzenetetracarboxylic acid dianhydride, bis(dioxazolone) or bis(benzoxazine), octamethylcyclotetrasilazane, hexaphenyltrisilazane, and 2,2-bis(2-dioxazoline). Based on the total mass of PGA, PBC, and PLA, the mass content of the chain extender is 0.1% to 2%.

20. A method for preparing the polyglycolic acid composite material according to any one of claims 1-19, comprising the following steps: S1: Mix PGA, PBC, PLA, talc and additives to obtain a mixture; S2: The mixture is melted and extruded into granules to obtain the polyglycolic acid composite material.

21. The preparation method according to claim 20, characterized in that, In step S2, the mixture is melt-blended and extruded using a twin-screw extruder.

22. The preparation method according to claim 21, characterized in that, The temperature of the twin-screw extruder is 190–250℃; the rotation speed is 30–500 r / min.

23. The preparation method according to claim 22, characterized in that, The temperature of the twin-screw extruder is 210–240℃; the rotation speed is 70–200 r / min.

24. The application of the polyglycolic acid composite material according to any one of claims 1-19 or the polyglycolic acid composite material prepared by any one of claims 20-23 as a film material or injection molding material.

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