阅读说明：本技术 一种pbat/pla淀粉基完全生物降解材料及其制备方法 (PBAT/P L A starch-based completely biodegradable material and preparation method thereof ) 是由 何莉 何炬帅 于 2020-03-27 设计创作，主要内容包括：本发明属于高分子材料技术领域,提供了一种PBAT/PLA淀粉基完全生物降解材料及其制备方法。该生物降解材料的原料包括：PBAT、PLA、改性淀粉、单分散介孔分子筛、生物质活性炭、粘合助剂、消泡剂和脱模剂。该生物降解材料的制备方法包括：(1)制得柑橘皮渣活性炭；(2)将柑橘皮渣活性炭和纳米二氧化硅进行超声混合得到混合物；(3)将PBAT、PLA、改性淀粉、混合物、粘合助剂、消泡剂份以及脱模剂加入高速剪切设备混合分散后,通过双螺杆机造粒,制得降解母粒；(4)通过吹膜设备将降解母粒吹制得到生物降解材料。该生物降解材料与传统的降解材料相比,力学性能有较大提高,并且能达到完全生物降解的效果,降解时间可控。该制备方法简单,容易操作。(The invention belongs to the technical field of high polymer materials, and provides a PBAT/P L A starch-based completely biodegradable material and a preparation method thereof.)

1. The PBAT/P L A starch-based completely biodegradable material is characterized by comprising, by weight, 3-6 parts of PBAT35-55 parts, 25-35 parts of P L A25-35 parts, 25-35 parts of modified starch, 0.8-2.5 parts of monodisperse mesoporous molecular sieve, 3-6 parts of biomass activated carbon, 0.05-0.15 part of bonding auxiliary agent, 0.05-0.15 part of defoaming agent and 0.05-0.15 part of release agent.

2. The PBAT/P L A starch-based complete biodegradable material according to claim 1, characterized by comprising, in parts by weight, PBAT40 parts, P L A30 parts, modified starch 30 parts, monodisperse mesoporous molecular sieve 2 parts, biomass activated carbon 5 parts, binding assistant 0.1 part, defoaming agent 0.1 part, and mold release agent 0.1 part.

3. The PBAT/P L A starch-based fully biodegradable material according to claim 1 or 2, characterized in that the biomass activated carbon comprises citrus pomace activated carbon.

4. The PBAT/P L A starch-based completely biodegradable material of claim 3, characterized in that the monodisperse mesoporous molecular sieve employs monodisperse microspheroidal nanosilica.

5. The PBAT/P L A starch-based fully biodegradable material according to claim 1, characterized in that the modified starch is a modified acetylated starch.

6. The PBAT/P L A starch-based fully biodegradable material according to claim 1, characterized in that the defoamer comprises at least one of zinc stearate, polyoxyethylene polyoxypropylene pentaerythritol ether, polyether ether ketone emulsion.

7. The PBAT/P L A starch-based fully biodegradable material according to claim 1, characterized in that the binding aid is a mixed liquid made from polymerized grease, mineral white oil and glycerol.

8. The PBAT/P L A starch-based fully biodegradable material according to claim 7, characterized in that the volume ratio of the polymerized grease, the mineral white oil and the glycerol is 0.8-1.2: 0.8-1.2: 1.8-2.2.

9. The PBAT/P L A starch-based fully biodegradable material according to claim 1, characterized in that the release agent comprises at least one of ethylene bis stearamide, ethylene bis stearamide and stearic acid amide.

10. The preparation method of the PBAT/P L A starch-based completely biodegradable material of claim 4, characterized by comprising the following steps:

(1) cleaning citrus peel, drying and crushing to obtain pretreated citrus peel, and mixing the pretreated citrus peel with a zinc chloride solution according to the ratio of 1: 3, activating, and carbonizing at 600 ℃ for 1.5h to obtain the citrus peel residue activated carbon;

(2) ultrasonically mixing the citrus peel residue activated carbon and the nano silicon dioxide according to the weight part, and filtering and drying to obtain a mixture;

(3) adding the PBAT, the P L A, the modified starch, the mixture, the bonding auxiliary agent, the defoaming agent and the release agent into high-speed shearing equipment according to the parts by weight, mixing and dispersing, and granulating by a double-screw machine to prepare a degradation master batch;

(4) and blowing the degradable master batches by using film blowing equipment to obtain the biodegradable material.

Technical Field

The invention belongs to the technical field of high polymer materials, and particularly relates to a PBAT/P L A starch-based completely biodegradable material and a preparation method thereof.

Background

PBAT belongs to thermoplastic biodegradable plastic, is a copolymer of butanediol adipate and butanediol terephthalate, and has good ductility and elongation at break as well as good heat resistance and impact resistance; in addition, the biodegradable plastic has excellent biodegradability, and is one of the best degradable materials for active research and market application of biodegradable plastics. However, they are expensive and have drawbacks in terms of mechanical properties and thermal stability.

Polylactic acid (P L A) is a novel bio-based and renewable biodegradable material, has good biodegradability, can be completely degraded by microorganisms in the nature under specific conditions after being used, finally generates carbon dioxide and water, and does not pollute the environment.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides the PBAT/P L A starch-based completely biodegradable material, which has greatly improved mechanical properties compared with the traditional biodegradable material, can achieve the effect of complete biodegradation and has controllable degradation time.

Aiming at the defects in the prior art, the second purpose of the invention is to provide a preparation method of PBAT/P L A starch-based completely biodegradable material, which is simple and easy to operate, and can prepare completely degradable biodegradable material with excellent mechanical property.

In order to achieve the above purpose, the solution adopted by the invention is as follows:

the PBAT/P L A starch-based completely biodegradable material comprises, by weight, PBAT35-55 parts, P L A25-35 parts, modified starch 25-35 parts, monodisperse mesoporous molecular sieve 0.8-2.5 parts, biomass activated carbon 3-6 parts, adhesion auxiliary agent 0.05-0.15 part, defoaming agent 0.05-0.15 part, and mold release agent 0.05-0.15 part.

A preparation method of the PBAT/P L A starch-based completely biodegradable material comprises the steps of (1) cleaning orange peel, drying and crushing the orange peel to obtain pretreated orange peel, activating the pretreated orange peel and a zinc chloride solution according to a ratio of 1: 3 by a one-step activation method, carbonizing the pretreated orange peel and the zinc chloride solution at 600 ℃ for 1.5 hours to obtain orange peel residue activated carbon, (2) ultrasonically mixing the orange peel residue activated carbon and nano-silica according to parts by weight, filtering and drying the mixture to obtain a mixture, (3) adding PBAT, P L A, modified starch, the mixture, an adhesive aid, a defoaming agent and a release agent into high-speed shearing equipment according to parts by weight, mixing and dispersing the mixture, and granulating the mixture through a double-screw machine to obtain degradable master batches, and (4) blowing the degradable master batches through film blowing equipment to obtain the completely biodegradable material.

The PBAT/P L A starch-based completely biodegradable material and the preparation method thereof provided by the invention have the beneficial effects that:

(1) the PBAT/P L A starch-based completely biodegradable material provided by the invention has the advantages that the monodisperse mesoporous molecular sieve and the biomass active carbon are added into a mixture of the PBAT and the P L A, other auxiliary materials are added, the composite material is compounded within the range of the mixture ratio required by the application, the tensile strength and the fracture growth rate of the biodegradable material can be greatly improved, and the completely biodegradable material can be completely degraded.

(2) The preparation method of the PBAT/P L A starch-based completely biodegradable material provided by the invention can be used for preparing the citrus peel residue activated carbon with high specific surface area and preparing the completely degradable and mechanically excellent biodegradable material.

Drawings

FIG. 1 is a film obtained in example 3 provided in Experimental example 2 of the present invention;

FIG. 2 is a drawing showing a film obtained in example 3 of the present invention in example 2 mixed with ordinary compost soil;

FIG. 3 is a view showing that the film obtained in example 3 according to the present invention in Experimental example 2 was mixed with general compost soil, sealed and put into the general compost soil;

FIG. 4 is a graph of the film provided in Experimental example 2 of the invention after disintegration in compost for one month;

FIG. 5 is a graph of the film provided in inventive Experimental example 2 after two months of disintegration in compost soil;

FIG. 6 is a graph of the film provided in inventive Experimental example 2 after three months of disintegration in compost soil.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The following is a detailed description of the PBAT/P L A starch-based completely biodegradable material provided by the embodiment of the invention.

The PBAT/P L A starch-based completely biodegradable material comprises, by weight, PBAT35-55 parts, P L A25-35 parts, modified starch 25-35 parts, monodisperse mesoporous molecular sieve 0.8-2.5 parts, biomass activated carbon 3-6 parts, adhesion auxiliary agent 0.05-0.15 part, defoaming agent 0.05-0.15 part and release agent 0.05-0.15 part.

Further, the biodegradable material prepared in the range of 40 parts by weight of PBAT, 30 parts by weight of P L A, 30 parts by weight of modified starch, 2 parts by weight of monodisperse mesoporous molecular sieve, 5 parts by weight of biomass activated carbon, 0.1 part by weight of an adhesion promoter, 0.1 part by weight of a defoaming agent and 0.1 part by weight of a mold release agent can obtain the best mechanical property and thermal stability.

It should be noted that, in this embodiment, the monodisperse microspherical nano-silica is adopted as the monodisperse mesoporous molecular sieve, and the monodisperse microsphere herein has the same composition shape and uniform particle size, and the monodisperse microspherical nano-silica is a non-toxic, tasteless and pollution-free non-metallic material, and is dispersed in the mixture of PBAT and P L a, which can greatly improve the strength of the polymer.

In the present example, the inventors have creatively found that a biodegradable material prepared by adding the citrus peel residue activated carbon prepared by the preparation method of the present example and the monodisperse mesoporous molecular sieve described above to a mixture of PBAT and P L a has excellent tensile strength and elongation at break, and is completely decomposed.

In this example, modified acetylated starch was used as the modified starch. The defoaming agent is at least one of zinc stearate, polyoxyethylene polyoxypropylene pentaerythritol ether and polyether ether ketone emulsion. The release agent adopts at least one of ethylene bis stearamide, ethylene bis stearamide and stearic acid amide.

In this example, the adhesion promoter was a mixed liquid prepared from a polymerized fat and oil, a mineral white oil, and glycerin. Wherein the volume ratio of the polymerized grease to the mineral white oil to the glycerol is 0.8-1.2: 0.8-1.2: 1.8-2.2, and the prepared bonding auxiliary agent can further enhance the mechanical property of the biodegradable material.

The embodiment also provides a preparation method of the PBAT/P L A starch-based completely biodegradable material, which comprises the following steps:

(1) the preparation method comprises the steps of (1) cleaning citrus peel, drying, crushing to obtain pretreated citrus peel, activating the pretreated citrus peel and a zinc chloride solution according to a ratio of 1: 3 by a one-step activation method, and carbonizing at 600 ℃ for 1.5 hours to obtain citrus peel activated carbon, wherein the obtained citrus peel activated carbon has an excellent specific surface area, (2) ultrasonically mixing the citrus peel activated carbon and nano-silica according to the weight parts, filtering and drying to obtain a mixture, uniformly mixing nano-carbon dioxide with the citrus peel activated carbon by using mixed ultrasound, and (3) adding PBAT, P L A, modified starch, the mixture, an adhesion aid, a defoaming agent and a release agent into a high-speed shearing double-screw device for mixing and dispersing, and then granulating by using a double-screw extruder to obtain degraded master batches, and (4) blowing the degraded master batches to obtain a biodegradable material by using a film blowing device.

The features and properties of the present invention are described in further detail below with reference to examples.