阅读说明：本技术 一种多形貌、多尺寸无机填料掺杂可降解薄膜的制备方法 (Preparation method of multi-morphology multi-size inorganic filler doped degradable film ) 是由 苗磊 陈焰 胡广齐 郑明东 冼慧敏 于 2020-12-31 设计创作，主要内容包括：本发明公开了一种多形貌、多尺寸无机填料掺杂可降解薄膜的制备方法,方法包括：将厚度为0.1-5μm、直径为1-20μm的片状粉体,长度为0.5-10μm、直径为10-100nm的条状粉体,直径为3nm-10μm的颗粒状粉体与PBAT颗粒按0.1-60：40-99.9比例加入至搅拌机中,搅拌5-15min,共混均匀,得到共混原料；将共混原料加入至螺杆挤出机中,挤出机区间温度设置为120-150℃,机头温度为155-165℃,挤出吹膜,水冷,得到厚度为5-300μm多形貌、多尺寸无机填料掺杂可降解薄膜。通过多形貌多尺寸的的无机粉体对PBAT进行改性,大大提高了可降解薄膜的综合性能。(The invention discloses a preparation method of a multi-morphology and multi-size inorganic filler doped degradable film, which comprises the following steps: flaky powder with the thickness of 0.1-5 mu m and the diameter of 1-20 mu m, strip powder with the length of 0.5-10 mu m and the diameter of 10-100nm, granular powder with the diameter of 3-10 mu m and PBAT granules are mixed according to the weight ratio of 0.1-60: adding 40-99.9 of the mixture into a stirrer, stirring for 5-15min, and uniformly blending to obtain blending raw materials; adding the blending raw materials into a screw extruder, setting the temperature of the extruder at 150-. The PBAT is modified by the inorganic powder with multiple shapes and sizes, so that the comprehensive performance of the degradable film is greatly improved.)

1. A preparation method of a multi-morphology multi-size inorganic filler doped degradable film is characterized by comprising the following steps:

flaky powder with the thickness of 0.1-5 mu m and the diameter of 1-20 mu m, strip powder with the length of 0.5-10 mu m and the diameter of 10-100nm, granular powder with the diameter of 3-10 mu m and PBAT granules are mixed according to the weight ratio of 0.1-60: adding 40-99.9 of the mixture into a stirrer, stirring for 5-15min, and uniformly blending to obtain blending raw materials;

adding the blending raw materials into a screw extruder, setting the temperature of the extruder at 150-.

2. The method of claim 1, comprising:

flaky powder with the thickness of 0.2-4 mu m and the diameter of 5-15 mu m, strip powder with the length of 2-9 mu m and the diameter of 25-85nm, granular powder with the diameter of 5-7 mu m and PBAT granules are mixed according to the proportion of 10-55: adding the mixture into a stirrer in a ratio of 45-90, stirring for 6-12min, and uniformly blending to obtain blending raw materials;

adding the blending raw materials into a screw extruder, setting the temperature of the extruder at 130-145 ℃, the temperature of a machine head at 158-162 ℃, extruding and blowing a film, and performing water cooling to obtain the multi-morphology and multi-size inorganic filler doped degradable film with the thickness of 20-150 mu m.

3. The method of manufacturing according to claim 2, comprising:

flaky powder with the thickness of 3 mu m and the diameter of 8 mu m, strip powder with the length of 6 mu m and the diameter of 50nm, granular powder with the diameter of 5 mu m and PBAT granules are mixed according to the proportion of 30: adding the mixture into a stirrer in a ratio of 70, stirring for 8min, and uniformly blending to obtain blending raw materials;

adding the blending raw materials into a screw extruder, setting the temperature of the extruder at 145 ℃ for 120-.

4. The preparation method according to claim 1, wherein the flake powder, strip powder and granular powder are one or more of barium sulfate, calcium carbonate, silica, mica powder, alumina, talc, montmorillonite and calcium sulfate.

5. The method according to claim 4, wherein the flake powder, the strip powder and the granular powder are three of barium sulfate, silica, alumina, talc and calcium sulfate.

6. The preparation method according to claim 4, wherein the flaky powder is aluminum oxide, the strip-shaped powder is silicon dioxide, and the granular powder is barium sulfate.

7. The preparation method according to claim 1, wherein the mass ratio of the flaky powder, the strip powder and the granular powder is 1-3: 0.5-2: 3-5.

8. The preparation method according to claim 7, wherein the mass ratio of the flaky powder, the strip powder and the granular powder is 1: 0.8: 4.

Technical Field

The invention relates to the technical field of degradable films, in particular to a preparation method of a multi-shape and multi-size inorganic filler doped degradable film.

Background

Poly (butylene adipate-butylene terephthalate) (PBAT for short) is a conventional degradable polymer, and compared with common polyethylene and polypropylene, when PBAT is directly applied to the preparation of a film, the poly (butylene adipate-butylene terephthalate) (PBAT for short) has two defects, namely, the cost of PBAT is too high, and the stiffness of the film is not enough. The reasons of the two aspects greatly limit the wide popularization and application and the use effect of the PBAT.

Most of the prior PBAT is doped and modified to modify the comprehensive performance of the PBAT. In the prior art, degradable polymers with higher brittleness are mainly added to increase the stiffness of the film, for example, patent CN201910219597.1 improves the impact strength and toughness of the film by adding polylactic acid (PLA). However, in the method, the cost of PLA is far higher than that of PBAT, and the application and popularization of the degradable plastic are limited.

Disclosure of Invention

In view of the above, the invention provides a preparation method of a multi-morphology and multi-size inorganic filler doped degradable film, and the method modifies PBAT through multi-morphology and multi-size inorganic powder, thereby greatly improving the comprehensive performance of the degradable film.

A preparation method of a multi-morphology multi-size inorganic filler doped degradable film comprises the following steps:

flaky powder with the thickness of 0.1-5 mu m and the diameter of 1-20 mu m, strip powder with the length of 0.5-10 mu m and the diameter of 10-100nm, granular powder with the diameter of 3-10 mu m and PBAT granules are mixed according to the weight ratio of 0.1-60: adding 40-99.9 of the mixture into a stirrer, stirring for 5-15min, and uniformly blending to obtain blending raw materials;

adding the blending raw materials into a screw extruder, setting the temperature of the extruder at 150-.

Preferably, the method comprises:

flaky powder with the thickness of 0.2-4 mu m and the diameter of 5-15 mu m, strip powder with the length of 2-9 mu m and the diameter of 25-85nm, granular powder with the diameter of 5-7 mu m and PBAT granules are mixed according to the proportion of 10-55: adding the mixture into a stirrer in a ratio of 45-90, stirring for 6-12min, and uniformly blending to obtain blending raw materials;

adding the blending raw materials into a screw extruder, setting the temperature of the extruder at 130-145 ℃, the temperature of a machine head at 158-162 ℃, extruding and blowing a film, and performing water cooling to obtain the multi-morphology and multi-size inorganic filler doped degradable film with the thickness of 20-150 mu m.

Preferably, the method comprises:

flaky powder with the thickness of 3 mu m and the diameter of 8 mu m, strip powder with the length of 6 mu m and the diameter of 50nm, granular powder with the diameter of 5 mu m and PBAT granules are mixed according to the proportion of 30: adding the mixture into a stirrer in a ratio of 70, stirring for 8min, and uniformly blending to obtain blending raw materials;

adding the blending raw materials into a screw extruder, setting the temperature of the extruder at 145 ℃ for 120-.

Preferably, the flaky powder, the strip-shaped powder and the granular powder are one or more of barium sulfate, calcium carbonate, silica, mica powder, alumina, talcum powder, montmorillonite and calcium sulfate.

Preferably, the flaky powder, the strip-shaped powder and the granular powder are three of barium sulfate, silicon dioxide, aluminum oxide, talcum powder and calcium sulfate.

Preferably, the flaky powder is aluminum oxide, the strip-shaped powder is silicon dioxide, and the granular powder is barium sulfate.

Preferably, the mass ratio of the flaky powder, the strip-shaped powder and the granular powder is 1-3: 0.5-2: 3-5.

Preferably, the mass ratio of the flaky powder, the strip-shaped powder and the granular powder is 1: 0.8: 4.

the invention provides an inorganic filler doped degradable film material and a preparation method thereof, wherein the method comprises the steps of adding inorganic powder with multiple shapes and sizes into PBAT particles to modify the PBAT particles; namely, the flaky powder can form two-dimensional orientation arrangement in the film blowing process, so that the stiffness of the film is effectively improved, and the whiteness of the film can be adjusted by adjusting the size of the flaky powder; the strip-shaped powder can form one-dimensional orientation arrangement in the film blowing process, so that the tensile modulus of the film in the one-dimensional direction is effectively improved, and the stiffness of the film can also be improved; the small-sized granular powder can improve the addition of the powder, simultaneously influence the whiteness of the film and the processability of the blend material as little as possible, greatly reduce the production cost, controllably adjust the mechanical strength, the whiteness, the stiffness and other series indexes of the film, and greatly improve the comprehensive performance.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.

It should be further understood that the term "and/or" as used in this specification and the appended claims refers to and includes any and all possible combinations of one or more of the associated listed items.

A preparation method of a multi-morphology multi-size inorganic filler doped degradable film comprises the following steps:

flaky powder with the thickness of 0.1-5 mu m and the diameter of 1-20 mu m, strip powder with the length of 0.5-10 mu m and the diameter of 10-100nm, granular powder with the diameter of 3-10 mu m and PBAT granules are mixed according to the weight ratio of 0.1-60: adding 40-99.9 of the mixture into a stirrer, stirring for 5-15min, and uniformly blending to obtain blending raw materials;

adding the blending raw materials into a screw extruder, setting the temperature of the extruder at 150-.

Wherein the mass ratio of the flaky powder to the strip powder to the granular powder is 1-3: 0.5-2: 3-5; preferably, the mass ratio of the flaky powder to the strip powder to the granular powder is 1: 0.8: 4; the flaky powder, the strip-shaped powder and the granular powder are one or more of barium sulfate, calcium carbonate, silicon dioxide, mica powder, aluminum oxide, talcum powder, montmorillonite and calcium sulfate; generally, the flaky powder, the strip powder and the granular powder are three of barium sulfate, silicon dioxide, aluminum oxide, talcum powder and calcium sulfate; usually, the flake powder is alumina, the strip powder is silica, and the granular powder is barium sulfate.

Detailed description of the preferred embodiment 1

A preparation method of a multi-morphology multi-size inorganic filler doped degradable film comprises the following steps:

calcium carbonate with the thickness of 0.1 mu m and the diameter of 20 mu m, mica powder with the length of 10 mu m and the diameter of 10nm, talcum powder with the diameter of 10 mu m and PBAT particles are mixed according to the weight ratio of 0.1: adding 99.9 parts of the mixture into a stirrer, stirring for 5min, and uniformly blending to obtain blending raw materials;

adding the blending raw materials into a screw extruder, setting the temperature of the extruder at 150 ℃ and the head temperature at 155 ℃, extruding and blowing a film, and cooling by water to obtain the multi-morphology and multi-size inorganic filler doped degradable film with the thickness of 5 mu m.

Specific example 2

Barium sulfate with the thickness of 0.2 mu m and the diameter of 15 mu m, montmorillonite with the length of 2 mu m and the diameter of 85nm, calcium sulfate with the diameter of 5nm and PBAT particles are mixed according to the proportion of 10: adding the mixture into a stirrer in a ratio of 90, stirring for 6min, and uniformly blending to obtain blending raw materials;

adding the blending raw materials into a screw extruder, setting the temperature of the extruder at 145 ℃ for 130-.

Specific example 3

Mixing silica with thickness of 5 μm and diameter of 1 μm, calcium carbonate with length of 0.5 μm and diameter of 100nm, granular powder with diameter of 3nm and PBAT granules according to a ratio of 60: adding the mixture into a stirrer in a ratio of 40, stirring for 15min, and uniformly blending to obtain blending raw materials; the mass ratio of the flaky powder to the strip powder to the granular powder is 1: 2: 3;

adding the blending raw materials into a screw extruder, setting the temperature of the extruder at 150 ℃ and the head temperature at 165 ℃, extruding and blowing a film, and cooling by water to obtain the inorganic filler doped degradable film with more shapes and sizes of 300 mu m thickness.

Specific example 4

Alumina with a thickness of 4 μm and a diameter of 5 μm, silica with a length of 9 μm and a diameter of 25nm, barium sulfate with a diameter of 7 μm and PBAT particles were mixed in a ratio of 55: adding the mixture into a stirrer at a ratio of 45, stirring for 12min, and uniformly blending to obtain blending raw materials; the mass ratio of aluminum oxide to silicon dioxide to barium sulfate is 1: 0.8: 4;

adding the blending raw materials into a screw extruder, setting the temperature of the extruder at 145 ℃ for 130-.

Specific example 5

Barium sulfate with a thickness of 3 μm and a diameter of 8 μm, alumina with a length of 6 μm and a diameter of 50nm, calcium sulfate with a diameter of 5 μm, and PBAT particles were mixed in a ratio of 30: adding the mixture into a stirrer in a ratio of 70, stirring for 8min, and uniformly blending to obtain blending raw materials; the mass ratio of barium sulfate to aluminum oxide to calcium sulfate is 2: 0.8: 3;

adding the blending raw materials into a screw extruder, setting the temperature of the extruder at 145 ℃ for 120-.

The inorganic filler-doped degradable film composite materials prepared by the preparation methods of specific examples 1 to 5 were compared with commercially available PBAT films, and tested for cost, strength, whiteness, and stiffness, wherein the test standards refer to: (1) strength testing using GB/T8809-2015; (2) whiteness measurements using GB/T2913-1982; (3) testing the stiffness by using GB/T7689.4-2013; the following table shows the results of the measurement using commercially available PBAT characterization data of 1:

group of	Cost (Yuan/ton)	Strength of	Whiteness degree	Stiffness of the sheet
					Detailed description of the preferred embodiment 1	21500	1.1	1.2	1.2
Specific example 2	18500	1.3	1.4	1.5
					Specific example 3	13500	1.5	1.6	1.7
Specific example 4	12500	1.8	2	1.6
					Specific example 5	15500	1.4	1.9	1.6
Comparative example 1	22000	1	1	1

As can be seen from the table, compared with the existing PBAT film, the production cost can be greatly reduced by adding inorganic powder with multiple shapes and sizes, and the comprehensive performance is greatly improved by controllably adjusting the mechanical strength, whiteness, stiffness and other series indexes of the film.

The steps in the method of the embodiment of the invention can be sequentially adjusted, combined and deleted according to actual needs.

The present invention has been described in detail, and the principle and embodiments of the present invention are explained by applying specific examples, which are only used to help understanding the method and the core idea of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.

It is clear to those skilled in the art that, for convenience and brevity of description, the specific working processes of the above-described systems and units may refer to the corresponding processes in the foregoing method embodiments, and are not described herein again.