Thermoplastic biodegradable PBAT modified material and preparation method and application thereof

Abstract

The invention relates to the technical field of thermoplastic biodegradable materials, in particular to a thermoplastic biodegradable PBAT modified material and a preparation method and application thereof. The thermoplastic biodegradable PBAT modified material comprises the following components in parts by weight: 100 parts of PBAT; 5 to 60 parts of polylactic acid; 10 to 100 parts of thermoplastic starch; 0.1 to 4 parts of a chain extender; 0.5 to 6 parts of a compatilizer; 0.1 to 4 parts of an anti-blocking agent; 0.1 to 2 parts of a lubricant; and 0-4 parts of a stabilizer. According to the thermoplastic biodegradable PBAT modified material, the air permeability and water absorption of the thermoplastic biodegradable material are improved on the basis of keeping the mechanical property of the material, and the technical effect is remarkable.

Description

Technical Field

[0001] The present invention relates to the technical field of thermoplastic biodegradable materials, and in particular to a thermoplastic biodegradable PBAT modified material and a preparation method and application thereof. Background Art

[0002] Since 1950, 830 million tons of plastics have been produced worldwide, and 630 million tons have become waste plastics. Of these, 9% have been recycled, 12% have been incinerated, and the remaining 79% (nearly 5 billion tons) have been buried or scattered in the environment. Plastics are closely related to people's daily lives because of their convenience and durability. However, the raw materials of plastics are basically non-degradable materials, which decompose very slowly in nature. It takes decades or even hundreds of years to completely decompose. According to research, plastic microparticles have entered the ecological cycle system.

[0003] Biodegradable materials are considered to be one of the most effective ways to solve the problem of "white pollution" caused by plastic products, because biodegradable materials can be decomposed into carbon dioxide and water by microorganisms in composting plants, with little impact on the environment and low processing costs. In addition, these biodegradable materials come from renewable resources, which to some extent compensates for the consumption of non-renewable energy and reduces greenhouse gas emissions.

[0004] These biodegradable materials are usually produced by mixing starch, biodegradable polymers and fillers under extrusion process conditions to obtain the final degradable composite particles.

[0005] However, there are some problems with current thermoplastic biodegradable materials. The main problem is that biodegradable plastics have good sealing and waterproof properties, so they cannot be used well in fields such as medical and sanitary materials that require certain air permeability and water absorption, and the enhancement of waterproofness is not conducive to natural decomposition. However, the improvement of air permeability and water absorption often causes a significant decrease in the mechanical properties of the material, such as tensile strength and toughness.

[0006] Therefore, how to provide a method for improving the air permeability and water absorption of thermoplastic degradable materials while maintaining the mechanical properties of the materials is a technical problem that needs to be solved at present. Summary of the invention

[0007] In view of the deficiencies in the prior art, the present invention provides a thermoplastic biodegradable PBAT modified material and a preparation method and application thereof. The thermoplastic biodegradable PBAT modified material improves the air permeability and water absorption of the thermoplastic biodegradable material while maintaining the mechanical properties of the material, and has significant technical effects.

[0008] The first aspect of the present invention is to provide a thermoplastic biodegradable PBAT modified material, comprising the following components in parts by weight:

[0009] PBAT: 100 parts; polylactic acid: 5-60 parts; thermoplastic starch: 10-100 parts; chain extender: 0.1-4 parts; compatibilizer: 0.5-6 parts; opening agent: 0.1-4 parts; lubricant: 0.1-2 parts; stabilizer: 0-4 parts.

[0010] For example, when adding materials, the following weight proportions of each component can be adopted: PBAT: 50-100 parts; polylactic acid PLA: 5-30 parts; thermoplastic starch TPS: 10-50 parts; chain extender CE: 0.1-2 parts; compatibilizer: 0.5-3 parts; opening agent: 0.1-2 parts; lubricant: 0.1-1 parts; stabilizer: 0-2 parts.

[0011] PBAT is a copolymer of butylene adipate and butylene terephthalate.

[0012] According to a preferred technical solution of the present invention, the melting point of the PBAT is 110-130° C., and the melt index is 3-10 g / 10 min.

[0013] According to a preferred technical solution of the present invention, the melting point of the polylactic acid (PLA) is 155-178° C., and the melt index is 1-5 g / 10 min.

[0014] According to a preferred technical solution of the present invention, the melting point of thermoplastic starch (TPS) is 130-140° C., and the melt index is 1-5 g / 10 min.

[0015] According to a preferred technical solution of the present invention, the chain extender (CE) is selected from at least one of styrene polymers, including but not limited to BASF ADR-4468 chain extender CE.

[0016] According to a preferred technical solution of the present invention, the opening agent is selected from at least one of erucamide and silicon dioxide.

[0017] According to a preferred technical solution of the present invention, the compatibilizer is selected from AS-K25 (preferably Shanghai Nanosu).

[0018] According to a preferred technical solution of the present invention, the stabilizer includes one or more of antioxidant 1010, thiamine pyrophosphate, phosphate, silicate, polyvinyl alcohol, and gelatin, preferably one or two.

[0019] According to a preferred technical solution of the present invention, the stabilizer includes one or two of antioxidant 1010, thiamine pyrophosphate, phosphate, silicate, polyvinyl alcohol, and gelatin.

[0020] All raw materials in the present invention may be commercially available or prepared by existing techniques. The raw materials used include but are not limited to the raw material models used in the embodiments of the present invention.

[0021] According to a more preferred technical solution of the present invention, the following components are included in parts by weight: PBAT: 100 parts; polylactic acid: 12.5-33.3 parts; thermoplastic starch: 25-50 parts; chain extender: 0.6-1.7 parts; compatibilizer: 1.8-3.3 parts; opening agent: 0.25-1.7 parts; lubricant: 0.35-1.2 parts; stabilizer: 0-0.33 parts.

[0022] For example, preferably, when adding materials, the following weight proportions of each component can be adopted: PBAT: 60-80 parts; polylactic acid PLA: 10-20 parts; thermoplastic starch TPS: 20-30 parts; chain extender CE: 0.5-1 parts; compatibilizer: 1.5-2 parts; opening agent: 0.2-1 parts; lubricant: 0.3-0.7 parts; stabilizer: 0-0.2 parts.

[0023] The second aspect of the present invention is to provide a method for preparing the thermoplastic biodegradable PBAT modified material described in the first aspect, comprising: mixing raw materials including the PBAT, polylactic acid PLA, thermoplastic starch TPS, chain extender CE, compatibilizer, opening agent, lubricant and optional stabilizer according to a ratio to obtain a premix, and melt-extruding, cooling and granulating the premix to obtain the thermoplastic biodegradable PBAT modified material.

[0024] According to the present invention, the preparation method comprises the following components in parts by weight:

[0025] PBAT: 100 parts; polylactic acid: 5-60 parts; thermoplastic starch: 10-100 parts; chain extender: 0.1-4 parts; compatibilizer: 0.5-6 parts; opening agent: 0.1-4 parts; lubricant: 0.1-2 parts; stabilizer: 0-4 parts. For example, when adding materials, the following weight proportions of each component can be used: PBAT: 50-100 parts; polylactic acid PLA: 5-30 parts; thermoplastic starch TPS: 10-50 parts; chain extender CE: 0.1-2 parts; compatibilizer: 0.5-3 parts; opening agent: 0.1-2 parts; lubricant: 0.1-1 parts; stabilizer: 0-2 parts.

[0026] Preferably, the following weight parts of each component are included: PBAT: 100 parts; polylactic acid: 12.5-33.3 parts; thermoplastic starch: 25-50 parts; chain extender: 0.6-1.7 parts; compatibilizer: 1.8-3.3 parts; opening agent: 0.25-1.7 parts; lubricant: 0.35-1.2 parts; stabilizer: 0-0.33 parts. For example, preferably, when adding materials, the following weight parts of each component can be used: PBAT: 60-80 parts; polylactic acid PLA: 10-20 parts; thermoplastic starch TPS: 20-30 parts; chain extender CE: 0.5-1 parts; compatibilizer: 1.5-2 parts; opening agent: 0.2-1 parts; lubricant: 0.3-0.7 parts; stabilizer: 0-0.2 parts.

[0027] According to a preferred technical solution of the present invention, the melting point of the PBAT is 110-130° C., and the melt index is 3-10 g / 10 min.

[0028] According to a preferred technical solution of the present invention, the melting point of the polylactic acid PLA is 155-178° C., and the melt index is 1-5 g / 10 min.

[0029] According to a preferred technical solution of the present invention, the melting point of thermoplastic starch TPS is 130-140° C., and the melt index is 1-5 g / 10 min.

[0030] According to a preferred technical solution of the present invention, the chain extender CE is selected from at least one of styrene polymers, including but not limited to BASF ADR-4468 chain extender CE.

[0031] According to a preferred technical solution of the present invention, the opening agent is selected from at least one of erucamide and silicon dioxide.

[0032] According to a preferred technical solution of the present invention, the lubricant is selected from at least one of stearic acid, zinc stearate, calcium stearate and aluminum stearate.

[0033] According to a preferred technical solution of the present invention, the compatibilizer is selected from AS-K25 (preferably Shanghai Nanosu).

[0034] According to a preferred technical solution of the present invention, the stabilizer is selected from one or more of antioxidant 1010, thiamine pyrophosphate, phosphate, silicate, polyvinyl alcohol, and gelatin, preferably one or two.

[0035] According to a preferred technical solution of the present invention, the melt extrusion is carried out in a twin-screw extruder.

[0036] According to a more preferred technical solution of the present invention, the temperature control of zones 1 to 12 of the twin-screw extruder is: 140-170°C in zones 1 to 12, 140-160°C in die head temperature, 200-300rpm in screw main engine speed, 3-7Hz in main feeding frequency, 8-10Hz in conveyor belt, and 5-12Hz in pelletizer frequency.

[0037] The third aspect of the present invention is to provide an application of the thermoplastic biodegradable PBAT modified material described in the first aspect or the thermoplastic biodegradable PBAT modified material prepared by the preparation method described in the second aspect in medical materials and sanitary materials.

[0038] Through the above technical scheme, the present invention provides a thermoplastic biodegradable PBAT modified material, including the following components in parts by weight: PBAT: 100 parts; polylactic acid: 5-60 parts; thermoplastic starch: 10-100 parts; chain extender: 0.1-4 parts; compatibilizer: 0.5-6 parts; opening agent: 0.1-4 parts; lubricant: 0.1-2 parts; stabilizer: 0-4 parts. Under the above specific raw materials and proportioning conditions, the thermoplastic biodegradable PBAT modified material obtained by the present invention improves the air permeability and water absorption of the thermoplastic biodegradable material on the basis of maintaining the mechanical properties of the material, and has significant technical effects.

[0039] The reason why the present invention has the above technical effects is that the inventors of the present invention believe that: by adopting the above-mentioned specific raw material selection and ratio, the thermoplastic starch increases the permeability of water vapor and enhances the water absorption of the entire plastic, and the chain extender causes PBAT and PLA to undergo a chain extension reaction during the processing, reduces the tension between the two interfaces, and realizes the efficient fusion of PBAT and PLA. Under a specific ratio, PBAT, polylactic acid PLA, thermoplastic starch TPS, chain extender CE, compatibilizer, opening agent, lubricant and optional stabilizer work synergistically, so that the mechanical properties of the material are maintained, and unexpectedly, the air permeability and water absorption of the material are significantly improved.

[0040] The present invention solves the problems in the prior art that the air permeability and water absorption of degradable plastics are poor and it is difficult to have good mechanical properties, high air permeability and high water absorption at the same time, and has a wider application field. DETAILED DESCRIPTION

[0041] The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall within the scope of protection of the present invention.

[0042] The technical solution of the present invention is further described below in conjunction with embodiments.

[0043] The chemicals used in the following examples of the present invention are all commercially available and of analytical grade.

[0044] In the following examples and comparative examples, PBAT (melting point 110-130°C, melt index <5g / 10min); from Kanghui New Material Technology Co., Ltd.;

[0045] Polylactic acid PLA (melting point 155-170°C, melt index 1-5g / 10min), from Zhejiang Hisun Biomaterials Co., Ltd.;

[0046] Thermoplastic starch TPS: (melting point 130-140°C, melt index 1-5g / 10min), from Dongguan Jingke Polymer Co., Ltd.;

[0047] Chain extender CE refers to styrene polymer; model ADR-4468, from BASF;

[0048] The compatibilizer refers to the model AS-K25, model PL0012500884C, from Shanghai Nanosu;

[0049] The stabilizer refers to antioxidant 1010.

[0050] Example 1

[0051] The raw materials in this embodiment are calculated as follows according to parts by weight:

[0052] PBAT: 60 parts, polylactic acid PLA: 10 parts, thermoplastic starch TPS: 20 parts, chain extender CE: 1 part, compatibilizer: 2 parts, erucamide: 0.2 parts, stearic acid: 0.3 parts, stabilizer: 0.1 parts.

[0053] The preparation process of this embodiment includes the following steps:

[0054] Preparation of thermoplastic biodegradable PBAT modified material: Add PBAT, TPS, PLA, CE, compatibilizer, erucic acid amide, stearic acid and stabilizer to a high mixer according to the ratio and stir for 3 to 5 minutes to mix evenly. The mixture is melted and extruded in a twin-screw extruder and air-cooled for granulation. The process conditions of the twin-screw extruder are: 150°C in zones 1 to 12, 155°C in die head temperature, 250rpm in screw main engine speed, 6Hz in main feeding frequency, 8Hz in conveyor belt, and 7Hz in pelletizer frequency.

[0055] Example 2

[0056] The raw materials for preparing the thermoplastic biodegradable PBAT modified material in Example 1 were used as raw materials, and the thermoplastic biodegradable PBAT modified material was prepared according to the method in Example 1, except that the amount of raw materials added was different. The specific formula is shown in Table 1.

[0057] Example 3

[0058] The preparation of the thermoplastic biodegradable PBAT modified material in Example 1 was used as a raw material, and a thermoplastic biodegradable PBAT modified material was prepared according to the method in Example 1, except that different portions of the raw materials were added. The specific formula is shown in Table 1.

[0059] Example 4

[0060] The raw materials for preparing the thermoplastic biodegradable PBAT modified material in Example 1 were used as raw materials, and the thermoplastic biodegradable PBAT modified material was prepared according to the method in Example 1, except that the amount of raw materials added was different. The specific formula is shown in Table 1.

[0061] Example 5

[0062] The raw materials for preparing the thermoplastic biodegradable PBAT modified material in Example 1 were used as raw materials, and the thermoplastic biodegradable PBAT modified material was prepared according to the method in Example 1, except that the amount of raw materials added was different. The specific formula is shown in Table 1.

[0063] Comparative Example 1

[0064] The PBAT biodegradable material (product number: 3130M) purchased from Guangdong Suntech Company was used as a control example to compare the performance with the four embodiments of the present invention.

[0065] Comparative Example 2

[0066] The raw materials for preparing the thermoplastic biodegradable PBAT modified material in Example 1 were used as raw materials, and the thermoplastic biodegradable PBAT modified material was prepared according to the method in Example 1, except that the amount of raw materials added was different. The specific formula is shown in Table 1.

[0067] Comparative Example 3

[0068] The raw materials for preparing the thermoplastic biodegradable PBAT modified material in Example 1 were used as raw materials, and the thermoplastic biodegradable PBAT modified material was prepared according to the method in Example 1, except that the amount of raw materials added was different. The specific formula is shown in Table 1.

[0069] Test Example 1

[0070] The physical properties were tested using the US ASTM test standard, the water absorption was tested using the national standard GB / T1034-2008, and the air permeability was tested using the national standard GB / T5453-1997. The results are shown in Table 2.

[0071] Table 1 Examples and Comparative Examples Raw Material Amounts and Masterbatch Properties and Control Examples

[0072]

[0073] Table 2

[0074]

[0075]

[0076] As can be seen from Table 1, the tensile strength and elongation of the present invention are comparable to the prior art, while the water absorption and air permeability are significantly improved, so that the present invention can be better applied to medical protective clothing and sanitary napkins.

[0077] The thermoplastic biodegradable PBAT modified material of the present invention improves the air permeability and water absorption of the thermoplastic biodegradable material while maintaining the mechanical properties of the material, and has a significant technical effect.

[0078] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

[0079] All publications, patent applications, patents and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings conventionally understood by those skilled in the art. In the event of a conflict, the definition in this specification shall prevail.

[0080] When this specification uses the prefix "well-known to those skilled in the art", "prior art" or similar terms to introduce materials, substances, methods, steps, devices or components, etc., the objects introduced by the prefix cover those commonly used in the art when this application is filed, but also include those that are not commonly used at present but will become recognized in the art as being suitable for similar purposes.

[0081] The endpoints and any values ​​of the scope disclosed in the present application document are not limited to the precise scope or value, and these scopes or values ​​should be understood to include values ​​close to these scopes or values. For numerical ranges, between the endpoint values ​​of each scope, between the endpoint values ​​of each scope and a separate point value, and between separate point values, one or more new numerical ranges can be combined with each other, and these numerical ranges should be considered as specifically disclosed in this article. Hereinafter, in principle, each technical solution can be combined with each other to obtain a new technical solution, which should also be considered as specifically disclosed in this article.

[0082] In the context of the present specification, any matters or items not mentioned are directly applicable to those known in the art without any changes except those explicitly stated.

[0083] Moreover, any embodiment described in this document may be freely combined with one or more other embodiments described in this document, and the technical solutions or technical ideas formed thereby are deemed to be part of the original disclosure or original record of the present invention, and should not be regarded as new content that has not been disclosed or anticipated in this document, unless a person skilled in the art considers that the combination is obviously unreasonable.

Claims

1. A thermoplastic biodegradable PBAT modified material, comprising the following components in parts by weight: PBAT: 100 shares; Polylactic acid: 5-60 parts; Thermoplastic starch: 10-100 parts; Chain extender: 0.1-4 parts; Compatibilizer: 0.5-6 parts; Opening agent: 0.1-4 parts; Lubricant: 0.1-2 parts; Stabilizer: 0-4 parts.

2. The thermoplastic biodegradable PBAT modified material according to claim 1, characterized in that: The melting point of the PBAT is 110-130° C., and the melt index is 3-10 g / 10 min.

3. The thermoplastic biodegradable PBAT modified material according to claim 1, characterized in that: The polylactic acid has a melting point of 155-178° C. and a melt index of 1-5 g / 10 min.

4. The thermoplastic biodegradable PBAT modified material according to claim 1, characterized in that: The melting point of thermoplastic starch is 130-140°C, and the melt index is 1-5g / 10min.

5. The thermoplastic biodegradable PBAT modified material according to claim 1, characterized in that: The chain extender is selected from at least one of styrene polymers; and / or, The opening agent is selected from at least one of erucamide and silicon dioxide; and / or, The lubricant is selected from at least one of stearic acid, zinc stearate, calcium stearate and aluminum stearate.

6. The thermoplastic biodegradable PBAT modified material according to claim 1, characterized in that: The compatibilizer is selected from AS-K25; and / or, The stabilizer is selected from one or more of antioxidant 1010, thiamine pyrophosphate, phosphate, silicate, polyvinyl alcohol, and gelatin.

7. The thermoplastic biodegradable PBAT modified material according to any one of claims 1 to 6, characterized in that: The composition comprises the following components in parts by weight: PBAT: 100 parts; polylactic acid: 12.5-33.3 parts; thermoplastic starch: 25-50 parts; Chain extender: 0.6-1.7 parts; Compatibilizer: 1.8-3.3 parts; Blocking agent: 0.25-1.7 parts; Lubricant: 0.35-1.2 parts; Stabilizer: 0-0.33 parts.

8. A method for preparing the thermoplastic biodegradable PBAT modified material according to any one of claims 1 to 7, comprising: According to the ratio, the raw materials including the PBAT, polylactic acid, thermoplastic starch, chain extender, compatibilizer, opening agent, lubricant and optional stabilizer are mixed to obtain a premix, and the premix is ​​melt-extruded, cooled and granulated to obtain the thermoplastic biodegradable PBAT modified material.

9. The preparation method according to claim 8, characterized in that: The melt extrusion is carried out in a twin-screw extruder, preferably, The temperature control of zones 1 to 12 of the twin-screw extruder is: 140-170°C for zones 1-12, 140-160°C for die head, 200-300rpm for screw main engine, 3-7Hz for main feeding, 8-10Hz for conveyor belt, and 5-12Hz for pelletizer.

10. Use of the thermoplastic biodegradable PBAT modified material according to any one of claims 1 to 7 or the thermoplastic biodegradable PBAT modified material prepared by the preparation method according to claim 8 or 9 in medical materials and sanitary materials.

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