阅读说明：本技术 一种玻璃抗菌微珠及玻璃抗菌树脂 (Glass antibacterial micro-beads and glass antibacterial resin ) 是由 唐晓峰 王瑞平 逯琪 余子涯 毕彤彤 于 2020-08-13 设计创作，主要内容包括：本发明公开了一种玻璃抗菌微珠及玻璃抗菌树脂。该玻璃抗菌微珠包括如下摩尔含量的组分：B<Sub>2</Sub>O<Sub>3</Sub>：35～55mol％；SiO<Sub>2</Sub>：15～40mol％；碱金属氧化物：2～25mol％；ZnO：5～30mol％；抗菌性氧化物：0.02～5mol％,抗菌性氧化物为Ag<Sub>2</Sub>O和/或CuO；mol％为各组分占所述玻璃抗菌微珠总摩尔量的百分比；玻璃抗菌微珠通过火焰漂浮法制得；火焰漂浮法中,火焰的温度为920～990℃。本发明的玻璃抗菌微珠不仅具有优良的耐热性、抗菌性,同时在应用于制备玻璃抗菌树脂时,能够保持制品表面光滑平整、且粒径分布均匀、均一性较好。(The invention discloses a glass antibacterial bead and glass antibacterial resin. The glass antibacterial micro-bead comprises the following components in molar content: b is 2 O 3 ：35～55mol％；SiO 2 : 15-40 mol%; alkali metal oxides: 2-25 mol%; ZnO: 5-30 mol%; antibacterial oxide: 0.02-5 mol% of antibacterial oxide Ag 2 O and/or CuO; the mol% is the percentage of each component in the total molar weight of the glass antibacterial micro-beads; the glass antibacterial micro-beads are floated by flamePreparing by a float method; in the flame floating method, the temperature of the flame is 920-990 ℃. The glass antibacterial microspheres have excellent heat resistance and antibacterial property, and can keep the surface of a product smooth and flat, and have uniform particle size distribution and good uniformity when being applied to preparation of glass antibacterial resin.)

1. The glass antibacterial bead is characterized by comprising the following components in molar content:

B₂O₃：35～55mol％；

SiO₂：15～40mol％；

alkali metal oxides: 2-25 mol%;

ZnO：5～30mol％；

antibacterial oxide: 0.02-5 mol%, the antibacterial oxide is Ag₂O and/or CuO; the Ag is₂The content of O is 0 to 0.3 mol% but not 0; the content of the CuO is 0-5 mol% but not 0; the mol% is the percentage of the molar weight of each component in the total molar weight of the glass antibacterial micro-beads;

the glass antibacterial micro-beads are prepared by a flame floating method;

in the flame floating method, the temperature of flame is 920-990 ℃.

2. The glass antimicrobial microbead according to claim 1, wherein B is₂O₃The content of (A) is 40-51 mol%;

and/or, the SiO₂The content of (A) is 20-35 mol%;

and/or the content of the alkali metal oxide is 5-15 mol%;

and/or, the kind of the alkali metal oxide is Na₂O and/or K₂O；

And/or the content of ZnO is 8-20 mol%;

and/or the content of the antibacterial oxide is 0.03-4.0 mol%;

and/or, said Ag₂The content of O is 0.02-0.03 mol%;

and/or the content of the CuO is 0.68-4.0 mol%;

and/or, the glass antibacterial micro-beads also comprise alkaline earth metal oxide.

3. The glass antimicrobial microbead according to claim 2, wherein B is₂O₃Is 40 mol%, 45 mol% or 51 mol%;

and/or, the SiO₂Is 20 mol%, 25 mol%, 30 mol% or 35 mol%;

and/or the content of the alkali metal oxide is 5 mol%, 5.3 mol%, 11 mol% or 15 mol%;

and/or, the Na₂The content of O is 3.3-15 mol%, and the mol% is the percentage of the total molar weight of the glass antibacterial micro-beads;

and/or, said K₂The content of O is 1-3 mol%, and the mol% is the percentage of the total molar weight of the glass antibacterial micro-beads;

and/or the content of ZnO is 8 mol%, 15 mol% or 20 mol%;

and/or the content of the antibacterial oxide is 0.03 mol%, 0.7 mol%, 3 mol% or 4 mol%;

and/or, said Ag₂The content of O is 0.02 mol% or 0.03 mol%;

and/or the content of the CuO is 0.68 mol%, 3 mol% or 4 mol%;

and/or the content of the alkaline earth metal oxide is 0-15 mol% but not 0, and the mol% is the percentage of the total molar weight of the glass antibacterial micro-beads;

and/or, the kind of the alkaline earth metal oxide is MgO and/or CaO;

and/or, the glass antibacterial micro-beads also comprise P₂O₅、Al₂O₃、Y₂O₃And CeO₂One or more of (A), e.g. Al₂O₃。

4. The glass antimicrobial microbead according to claim 3, wherein the Na is₂The content of O is 3.3 mol%, 5 mol%, 11 mol% or 15 mol%, and the mol% is the percentage of the total molar weight of the glass antibacterial micro-beads;

and/or, said K₂The content of O is 2mol percent, and the mol percent is the percentage of the total molar weight of the glass antibacterial micro-beads;

and/or the content of the alkaline earth metal oxide is 2-4 mol%, such as 2 mol%, 3.97 mol% or 4 mol%, and the mol% is the percentage of the total molar weight of the glass antibacterial micro-beads;

and/or, the content of the MgO is 1 to 4 mol%, for example, 1 mol% or 3.97 mol%, and mol% is a percentage of the total molar amount of the glass antibacterial micro-beads;

and/or the content of the CaO is 2-3 mol%, for example 2 mol% or 3 mol%, and the mol% is the percentage of the total molar weight of the glass antibacterial micro-beads;

and/or, the Al₂O₃The content of (a) is 1-3 mol%, for example 2 mol%, and the mol% is the percentage of the total molar weight of the glass antibacterial micro-beads.

5. The glass antimicrobial microspheres of claim 1, wherein the glass antimicrobial microspheres are composed of the following components in molar amounts: b is₂O₃：40mol％、SiO₂：25mol％、MgO：3.97mol％、Na₂O：11mol％、ZnO：20mol％、Ag₂O: 0.03mol percent, wherein the mol percent is the percentage of the molar weight of each component in the total molar weight of the glass antibacterial micro-beads;

or, the glass antibacterial micro-beads comprise the following components in molar content: b is₂O₃：45mol％、SiO₂：20mol％、CaO：2mol％、Na₂O: 15 mol%, ZnO: 15 mol%, CuO: 3 mol%, wherein the mol% is the percentage of the molar weight of each component in the total molar weight of the glass antibacterial micro-beads;

or, the glass antibacterial micro-beads comprise the following components in molar content: b is₂O₃：51mol％、SiO₂：35mol％、Na₂O：3.3mol％、K₂O：2mol％、ZnO：8mol％、Ag₂O: 0.02 mol%, CuO: 0.68 mol%, wherein the mol% is the percentage of the molar weight of each component in the total molar weight of the glass antibacterial micro-beads;

or, the glass antibacterial micro-beads comprise the following components in molar content: b is₂O₃：40mol％、SiO₂：30mol％、MgO：1mol％、CaO：3mol％、Na₂O：5mol％、ZnO：15mol％、CuO：4mol％、Al₂O₃: 2mol percent, and the mol percent is the percentage of the molar weight of each component in the total molar weight of the glass antibacterial micro-beads.

6. The glass antimicrobial microbeads of any one of claims 1-5, wherein the flame temperature is 950-970 ℃, such as 950 ℃;

and/or, the particles of the glass antibacterial micro-beads are preheated before the flame floating method is carried out; the temperature of the preheating is, for example, 400 ℃;

and/or the time for carrying out the flame floating method on the particles of the glass antibacterial microspheres is 20-40 min;

and/or, cooling is carried out after the flame floating method, wherein the cooling is carried out to below 300 ℃;

wherein, preferably, the cooling is followed by a sieving operation, and the mesh number of the sieve for sieving is 100 meshes or 200 meshes;

and/or, the preparation method of the particles of the glass antibacterial microbeads comprises the following steps: preparing raw materials according to the components of the glass antibacterial microspheres, mixing, melting, cooling, drying and pulverizing to obtain the glass antibacterial microspheres.

7. The glass antimicrobial microbeads of claim 6 wherein said melting temperature is 1100-1350 ℃, such as 1200 ℃;

and/or the melting time is 20-120 min;

and/or, prior to the flame floating method, the particles of the glass antimicrobial microbeads D10 have a particle size of 2.5 to 3 microns, such as 2.7 microns, 2.8 microns, or 2.9 microns; the particle size of D50 of the particles of the glass antibacterial micro-beads is 10-10.5 microns, such as 10.1 microns, 10.2 microns or 10.3 microns; the particle diameter of D99 of the glass antibacterial bead particles is 59-61 microns, such as 59.4 microns, 59.6 microns, 60.3 microns or 61 microns.

8. A glass antibacterial resin comprising the glass antibacterial bead as claimed in any one of claims 1 to 7 and a resin material.

9. The glass antibacterial resin according to claim 8, wherein the mass ratio of the glass antibacterial beads to the resin material is (0.4-1.5): (98.5 to 99.6), for example, 1: 99;

and/or the resin material is polypropylene resin, thermoplastic polyurethane or ABS resin; wherein the polypropylene resin is, for example, M800E; the grade of the ABS resin is PA-758 or PA-757K for example;

and/or the surface roughness of the glass antibacterial resin is 0.7-1 μm, such as 0.8 μm;

and/or the preparation method of the glass antibacterial resin comprises the following steps: and mixing the glass antibacterial beads with the resin material, and then granulating and injection molding to obtain the antibacterial glass bead.

10. The glass antimicrobial resin according to claim 9, wherein the granulation is extrusion granulation; wherein the temperature of the extrusion granulation is preferably 195-205 ℃, for example 200 ℃;

and/or the injection molding temperature is 210-230 ℃, such as 220 ℃.

Technical Field

The invention relates to glass antibacterial beads and glass antibacterial resin.

Background

In recent years, with the development of science and technology, the physical living standard of people is increasing, and more people begin to aim at environmental sanitation. In life, problems due to the growth of bacteria are frequently encountered, and therefore, antibacterial products are urgently needed. The antibacterial agent is a key component of antibacterial products and mainly comprises inorganic and organic antibacterial agents. The inorganic antibacterial agent has higher heat resistance and is more stable in the processing process, so the market share of the inorganic antibacterial agent is continuously improved.

The commonly used inorganic antibacterial agent is a composition prepared by mixing silver, zinc and a composition thereof as antibacterial ingredients and an inorganic material as a carrier, and comprises zeolite, zirconium phosphate, glass and the like. Because the inorganic antibacterial glass has safe, stable and controllable performance, the inorganic antibacterial glass is widely applied to resin products.

At present, plastic products are widely applied, however, in the fields of electronics, aviation, aerospace, instruments and meters and the like, the surface roughness of the plastic is highly required. The glass antibacterial product is prepared by processing glass with antibacterial components obtained by melting into powder by adopting a ball milling or airflow crushing method, screening the powder and testing the particle size of the powder by a laser particle sizer. For example, in the extrusion process, the powder blocks the filter screen, so that the actual content of the antibacterial component in the product is reduced, and the filtering pressure of equipment is increased, so that the process is unstable. In other applications, such as coating or weaving, although the particle size range displayed by the laser particle sizer meets the application requirements, the deviation between the result and the actual particle size and distribution is large due to the test mechanism, and a plurality of process adverse factors or product surface roughness and other problems occur in the application process. Based on the above problems, the range of use of glass antibacterial products is limited.

Disclosure of Invention

The invention aims to solve the technical problems of uneven particle size distribution, larger surface roughness and poorer antibacterial performance of glass antibacterial powder in the prior art and the defect that more antibacterial oxides need to be added, and provides the glass antibacterial microspheres and the glass antibacterial resin. The glass antibacterial microspheres have excellent heat resistance and antibacterial property, and can keep the surface of a product smooth and flat, the particle size distribution is uniform and the uniformity of a final product is good when the glass antibacterial microspheres are applied to preparation of glass antibacterial resin.

The present invention solves the above technical problems by the following technical solutions.

The invention provides a glass antibacterial bead which comprises the following components in molar content:

B₂O₃：35～55mol％；

SiO₂：15～40mol％；

alkali metal oxides: 2-25 mol%;

ZnO：5～30mol％；

antibacterial oxide: 0.02-5 mol%, the antibacterial oxide is Ag₂O and/or CuO; the Ag is₂The content of O is 0 to 0.3 mol% but not 0; the content of the CuO is 0-5 mol% but not 0; the mol% is the percentage of the molar weight of each component in the total molar weight of the glass antibacterial micro-beads;

the glass antibacterial micro-beads are prepared by a flame floating method;

in the flame floating method, the temperature of flame is 920-990 ℃.

In the present invention, said B₂O₃Preferably in an amount of 40 to 51 mol%, for example40 mol%, 45 mol% or 51 mol%.

In the present invention, the SiO₂The content of (b) is preferably 20 to 35 mol%, for example 20 mol%, 25 mol%, 30 mol% or 35 mol%. SiO in the invention₂Less than 15 mol% is not beneficial to forming glass state, ceramics are easy to appear in the melting process, if the melting temperature is higher than 55 mol%, the melting temperature is improved, and the antibacterial performance is not easy to present.

In the present invention, the content of the alkali metal oxide is preferably 5 to 15 mol%, for example, 5 mol%, 5.3 mol%, 11 mol% or 15 mol%. In the present invention, if the alkali metal oxide is less than 2 mol%, it will cause difficulty in melting, and if it is more than 25 mol%, it will reduce the antibacterial property of the glass antibacterial beads.

In the present invention, the alkali metal oxide may be an alkali metal oxide conventionally used in the art for preparing glass antibacterial products. The alkali metal oxide may be Na₂O and/or K₂O。

When the alkali metal oxide contains Na₂When O is, the Na is₂The content of O is preferably 3.3 to 15 mol%, such as 3.3 mol%, 5 mol%, 11 mol% or 15 mol%, and the mol% is the percentage of the total molar amount of the glass antibacterial micro-beads.

When said alkali metal oxide contains K₂When O is, the K is₂The content of O is preferably 1 to 3 mol%, for example 2 mol%, and the mol% is the percentage of the total molar amount of the glass antibacterial micro-beads.

In the present invention, the content of ZnO is preferably 8 to 20 mol%, for example, 8 mol%, 15 mol%, or 20 mol%. In the invention, the content of ZnO is less than 5 mol%, the antibacterial property of the glass is not easy to embody, and the content of ZnO is more than 30 mol%, the glass melting temperature is increased.

In the present invention, the content of the antibacterial oxide is preferably 0.03 to 4.0 mol%, for example, 0.03 mol%, 0.7 mol%, 3 mol% or 4 mol%.

In the present invention, the Ag is₂The content of O is preferably 0.02 to 0.03 mol%, for example 0.02 mol% or 0.03 mol%. When the antibacterial oxide of the present invention is Ag₂When O is required, only 0.02-0.03 mol of oxygen is addedThe content below percent can achieve better antibacterial property, and the cost for preparing the glass antibacterial micro-beads is reduced.

In the present invention, the content of CuO is preferably 0.68 to 4.0 mol%, for example, 0.68 mol%, 3 mol% or 4 mol%.

In the invention, the glass antibacterial beads can also comprise alkaline earth metal oxide.

The content of the alkaline earth metal oxide is conventional in the art, preferably 0 to 15 mol% but not 0, more preferably 2 to 4 mol%, such as 2 mol%, 3.97 mol% or 4 mol%, where mol% is the percentage of the total molar amount of the glass antimicrobial micro-beads.

The kind of the alkaline earth metal oxide may be a kind of an alkaline earth metal oxide that is conventional in the art. The alkaline earth metal oxide is typically MgO and/or CaO.

When the glass antibacterial beads contain MgO, the content of MgO is preferably 1 to 4 mol%, for example, 1 mol% or 3.97 mol%, where mol% is the percentage of the total molar amount of the glass antibacterial beads.

When the glass antibacterial beads contain CaO, the content of CaO is preferably 2 to 3 mol%, for example, 2 mol% or 3 mol%, where mol% is the percentage of the total molar amount of the glass antibacterial beads.

In the invention, the glass antibacterial micro-beads can also comprise P₂O₅、Al₂O₃、Y₂O₃And CeO₂One or more of (A), e.g. Al₂O₃。

Wherein, when the glass antibacterial micro-beads contain Al₂O₃When being made of Al₂O₃The content of (b) is preferably 1 to 3 mol%, for example 2 mol%, and the mol% is the percentage of the total molar amount of the glass antibacterial micro-beads.

In a preferred embodiment of the present invention, the glass antimicrobial micro-beads are composed of the following components by mole: b is₂O₃：40mol％、SiO₂：25mol％、MgO：3.97mol％、Na₂O：11mol％、ZnO：20mol％、Ag₂O：0.03mol％And the mol% is the percentage of the molar weight of each component in the total molar weight of the glass antibacterial micro-beads.

In a preferred embodiment of the present invention, the glass antimicrobial micro-beads are composed of the following components by mole: b is₂O₃：45mol％、SiO₂：20mol％、CaO：2mol％、Na₂O: 15 mol%, ZnO: 15 mol%, CuO: 3mol percent, wherein the mol percent is the percentage of the molar weight of each component in the total molar weight of the glass antibacterial micro-beads.

In a preferred embodiment of the present invention, the glass antimicrobial micro-beads are composed of the following components by mole: b is₂O₃：51mol％、SiO₂：35mol％、Na₂O：3.3mol％、K₂O：2mol％、ZnO：8mol％、Ag₂O: 0.02 mol%, CuO: 0.68mol percent, wherein the mol percent is the percentage of the molar weight of each component in the total molar weight of the glass antibacterial micro-beads.

In a preferred embodiment of the present invention, the glass antimicrobial micro-beads are composed of the following components by mole: b is₂O₃：40mol％、SiO₂：30mol％、MgO：1mol％、CaO：3mol％、Na₂O：5mol％、ZnO：15mol％、CuO：4mol％、Al₂O₃: 2mol percent, and the mol percent is the percentage of the molar weight of each component in the total molar weight of the glass antibacterial micro-beads.

In the present invention, the temperature of the flame is preferably 950 to 970 ℃, for example 950 ℃.

In the flame floating method, the particle state of the glass antibacterial micro-beads is laminar flow movement; the laminar motion may be in the sense conventionally understood by those skilled in the art, and generally refers to the laminar flow of a fluid. In the flame floating method, when the movement mode of the particles of the glass antibacterial micro-beads in the furnace is laminar flow movement, the Reynolds number of the particles is usually less than 1.

In the present invention, it is known to those skilled in the art that the particles of the glass antibacterial beads are generally preheated before the flame floating method.

Wherein the temperature of said preheating may be conventional in the art, e.g. 400 ℃.

Wherein the preheating generally further comprises preheating natural gas and combustion supporting gas that produce the flame.

In the invention, the time for carrying out the flame floating method on the particles of the glass antibacterial beads can be conventional in the field, and is preferably 20-40 min. The time generally refers to the time during which the temperature of the flame is maintained.

In the present invention, it is known to those skilled in the art that the flame floating method is generally followed by a cooling operation. The cooling is usually referred to as rapid cooling. Wherein, the cooling generally means cooling to below 300 ℃.

Wherein said cooling is generally followed by a sieving operation. And the screen during screening is selected according to the particle size of the glass antibacterial micro-beads before the flame floating method is carried out. The mesh number of the screen is, for example, 100 mesh or 200 mesh.

In the present invention, the preparation method of the particles of the glass antibacterial beads may be a preparation method of a glass antibacterial product that is conventional in the art. Preferably comprising the steps of: preparing raw materials according to the components of the glass antibacterial microspheres, mixing, melting, cooling, drying and pulverizing to obtain the glass antibacterial microspheres.

Wherein, the sources of the raw materials in the glass antibacterial micro-beads can be conventional sources in the field.

B is₂O₃Can include B₂O₃And/or H₃BO₃。

The SiO₂Can include SiO₂And/or silica sand.

When the alkali metal oxide contains Na₂When O is, the Na is₂The source of O may include Na₂CO₃And NaHCO₃One or more of (a).

When the alkali metal oxide contains K₂When O is, the K is₂Sources of O may include K₂CO₃And/or KHCO₃。

The Ag is₂The source of O may include Ag₂O and/or AgNO₃。

The source of ZnO may comprise ZnO.

The source of CuO may include CuO and/or Cu (OH)₂。

When the glass antimicrobial beads include MgO, the source of MgO may include MgO and/or MgCO₃。

When the glass antibacterial micro-beads contain CaO, the source of the CaO can be CaO or CaCO₃。

Wherein the melting temperature can be 1100-1350 ℃, such as 1200 ℃.

Wherein the melting time can be 20-120 min.

Wherein the cooling can be performed by using cold water. The temperature of the cold water is typically room temperature. In the invention, the room temperature is generally 10-30 ℃.

Wherein the drying temperature can be 50-110 ℃. The drying time may be 2 to 12 hours, for example 6 hours.

Wherein, the powder preparation can adopt a mode of airflow crushing and/or ball milling and sieving. The milling preferably comprises the steps of: and ball-milling the crude glass obtained after drying by adopting a ball mill, and then sieving.

In the present invention, before the flame floating method is performed, the particle size of D10 of the particles of the glass antimicrobial beads may be 2.5 to 3 micrometers, for example, 2.7 micrometers, 2.8 micrometers, or 2.9 micrometers; the particle size of D50 of the particles of the glass antibacterial micro-beads can be 10-10.5 microns, such as 10.1 microns, 10.2 microns or 10.3 microns; the particle size of D99 of the particles of the glass antimicrobial beads may be 59 to 61 micrometers, such as 59.4 micrometers, 59.6 micrometers, 60.3 micrometers, or 61 micrometers.

The invention also provides glass antibacterial resin which comprises the glass antibacterial micro-beads and a resin material.

In the present invention, the mass ratio of the glass antibacterial beads to the resin material may be a mass ratio conventionally used in the art, for example (0.4 to 1.5): (98.5 to 99.6), for example, 1: 99.

in the present invention, the kind of the resin material may be a resin material that is conventional in the art, for example, a polypropylene resin, a thermoplastic polyurethane, or an ABS resin. Wherein the polypropylene resin has a trade name of, for example, M800E; the ABS resin is, for example, PA-758 or PA-757K.

In the present invention, the surface roughness of the glass antibacterial resin may be 0.7 to 1 μm, for example, 0.8 μm. The surface roughness refers to the arithmetic mean of the roughness profile of the glass antibacterial resin prepared into a plate-shaped structure.

In the present invention, the preparation method of the glass antibacterial resin may be a preparation method that is conventional in the art. The preparation method of the antibacterial resin preferably comprises the following steps: and mixing the glass antibacterial beads with the resin material, and then granulating and injection molding to obtain the antibacterial glass bead.

Wherein, the mixing can be a conventional mixing mode in the field, and the glass antibacterial micro-beads and the resin material are uniformly mixed.

Wherein, the granulating process can be a conventional granulating process in the field. The granulation is typically extrusion granulation. The temperature of the extrusion granulation is preferably 195-205 ℃, for example 200 ℃.

Wherein, the injection molding process can be the conventional injection molding process in the field. The injection molding temperature is preferably 210 to 230 ℃, for example 220 ℃.

On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.

The reagents and starting materials used in the present invention are commercially available.

The positive progress effects of the invention are as follows: according to the invention, through the matching of all components in the particles of the glass antibacterial microspheres, the antibacterial performance of the particles of the glass antibacterial microspheres is excellent, and the glass antibacterial microspheres with better and uniform particle size distribution are prepared by combining a specific flame floating method. The D10 particle size distribution of the glass antibacterial beads is 3.8-4.5 microns, the D50 particle size distribution is 10-10.5 microns, the D99 particle size distribution is 32-33.5 microns, and the particle size distribution is uniform. Will be provided withWhen the glass antibacterial microspheres are mixed with a resin material to prepare the antibacterial resin, the antibacterial property is further improved, and the resin product has a smooth and flat surface and low roughness. Compared with the antibacterial effect of the product prepared from the particles of the glass antibacterial microspheres which are not subjected to the specific flame floating method and the resin material, the antibacterial effect of the antibacterial resin prepared from the antibacterial microspheres is improved by 7-19%. The final resin product has better antibacterial effect on escherichia coli and staphylococcus aureus, and the antibacterial performance value can reach 3CFU/cm²Above, up to 5.9CFU/cm²。

Drawings

Fig. 1 is a schematic view of the glass antibacterial beads and particles thereof in example 1, wherein fig. 1a is a schematic view of the particles of the glass antibacterial beads, and fig. 1b is a schematic view of the glass antibacterial beads.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.

The polypropylene resin PP in each of the following examples and comparative examples was derived from: the product is produced by China petrochemical Shanghai petrochemical industry Co., Ltd, and the model number is as follows: M800E.