阅读说明：本技术 一种自清洁多级微孔结构abs材料及制备方法 (Self-cleaning multistage microporous structure ABS material and preparation method thereof ) 是由 李志成 于 2021-08-06 设计创作，主要内容包括：本发明公开了一种自清洁多级微孔结构ABS材料及制备方法,涉及丙烯腈-丁二烯-苯乙烯共聚物(ABS)材料改性技术领域,其中该自清洁多级微孔结构ABS材料包括以下按照重量份计的原料：ABS 31-38份、SAN 22-28份、PDMS 40-47份、CMC分子筛0.1-1.0份、白油0.1-2份、抗氧剂0.1-2份；与常规的ABS发泡材料相比,本发明不仅为热塑性材料,符合可循环利用的环保理念,而且结合常规的加工方式和热水处理,也有利于产品的高效加工。(The invention discloses a self-cleaning multistage microporous structure ABS material and a preparation method thereof, relating to the technical field of modification of acrylonitrile-butadiene-styrene copolymer (ABS) materials, wherein the self-cleaning multistage microporous structure ABS material comprises the following raw materials in parts by weight: 31-38 parts of ABS, 22-28 parts of SAN, 40-47 parts of PDMS, 0.1-1.0 part of CMC molecular sieve, 0.1-2 parts of white oil and 0.1-2 parts of antioxidant; compared with the conventional ABS foaming material, the ABS foaming material is a thermoplastic material, accords with the environment-friendly concept of recycling, combines the conventional processing mode and hot water treatment, and is beneficial to the high-efficiency processing of products.)

1. The self-cleaning multistage microporous structure ABS material is characterized by comprising the following raw materials in parts by weight:

31-38 parts of ABS;

22-28 parts of SAN;

40-47 parts of PDMS;

0.1-1.0 part of CMC molecular sieve;

0.1-2 parts of white oil;

0.1-2 parts of antioxidant.

2. The self-cleaning multistage microporous structure ABS material of claim 1, which is characterized by comprising the following raw materials in parts by weight:

35 parts of ABS;

SAN 25 parts;

43 parts of PDMS;

0.5 part of CMC molecular sieve;

1 part of white oil;

and 1 part of antioxidant.

3. The ABS material of claim 1 or 2, wherein the ABS has a butadiene content of 20 to 30%.

4. The ABS material of claim 1 or 2, wherein the ABS has a melt index of 5-15g/10min, a test condition of 200 ℃ and a load of 5 kg.

5. The ABS material according to claim 1 or 2, wherein the SAN has an acrylonitrile content of 25-33%.

6. The ABS material of claim 1 or 2, wherein the SAN has a melt index of 10-25g/10min, a test condition of 220 ℃ and a load of 10 kg.

7. The ABS material of claim 1 or 2, wherein the PDMS has a viscosity of 10000-50000(25 ℃ Ccp).

8. The ABS material of claim 1 or 2, wherein the CMC molecular sieve is an A-type spherical molecular sieve and is one of 3A, 4A and 5A, and after grinding, solid powder with a particle size of 0.1mm is obtained.

9. A method for preparing a self-cleaning multilevel cellular structure ABS material according to any of claims 1-8, comprising the steps of:

melt-extruding ABS, SAN and PDMS to obtain ABS/SAN/CMC composite material particles;

step two, blending and extruding ABS/SAN/CMC composite material particles and PDMS to obtain a nanoparticle modified ABS/SAN/PDMS/CMC quaternary composite material;

thirdly, taking the ABS/SAN/PDMS/CMC quaternary composite material as a template, and obtaining a product through a required molding mode;

and step four, performing post-treatment on the product for more than 30 minutes by hot water at the temperature of more than 95 ℃, removing PDMS by the hot water, and obtaining the ABS/SAN/CMC composite material with the micron-sized open pore structure.

10. The method for preparing the self-cleaning multistage microporous structure ABS material according to claim 9, wherein the molding manner required in the third step is extrusion, injection molding, film blowing, and casting.

Technical Field

The invention relates to the technical field of modification of acrylonitrile-butadiene-styrene (ABS) materials, in particular to a self-cleaning multi-stage microporous ABS material and a preparation method thereof.

Background

ABS is a common thermoplastic material with a chemical structure of acrylonitrile-butadiene-styrene terpolymer. Compared with polyolefin materials, ABS not only has higher melt strength, but also has better regulation and control performance in structure, and different monomer proportions can be designed according to different requirements to realize the application in different fields. The common ABS foaming material is mainly a chemical foaming method of the material, and simultaneously, a cross-linking agent is added into the material, and the material is extrudedAnd the ABS foamed material is subjected to a crosslinking reaction with ABS during processing to obtain ABS foamed profiles, such as foamed pipes, foamed plates and the like. In recent years, however, supercritical fluids, such as supercritical CO, have been used₂To obtain a physically foamed material.

The ABS material prepared by chemical foaming has cross-linking reaction, so the obtained product is reused and does not meet the requirement of environmental protection and recycling. And supercritical CO is adopted₂The ABS material is prepared by physical foaming, and special supercritical fluid preparation, pressure resistance, low temperature resistance and storage sealing equipment are needed, and the thickness of the product is only several centimeters, so that the equipment investment and maintenance cost are high, and much inconvenience is brought to production.

Disclosure of Invention

The invention aims to provide a self-cleaning multi-stage microporous-structure ABS material to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme:

the self-cleaning multistage microporous structure ABS material comprises the following raw materials in parts by weight:

31-38 parts of ABS;

22-28 parts of SAN;

40-47 parts of PDMS;

0.1-1.0 part of CMC molecular sieve;

0.1-2 parts of white oil;

0.1-2 parts of antioxidant.

As a further scheme of the invention: the invention comprises the following raw materials in parts by weight:

35 parts of ABS;

SAN 25 parts;

43 parts of PDMS;

0.5 part of CMC molecular sieve;

1 part of white oil;

and 1 part of antioxidant.

As a further scheme of the invention: the butadiene content in the ABS is 20-30%.

As a further scheme of the invention: the melt index of the ABS is 5-15g/10min, the test condition is 200 ℃, and the load is 5 kg.

As a further scheme of the invention: the content of acrylonitrile in the SAN is 25-33%.

As a further scheme of the invention: the melt index of the SAN is 10-25g/10min, the test condition is 220 ℃, and the load is 10 kg.

As a further scheme of the invention: the PDMS is one of 10000-50000 (cp at 25 ℃), the CMC molecular sieve is an A-type spherical molecular sieve and is one of 3A, 4A and 5A, and solid powder with the particle size of 0.1mm is obtained after grinding.

The invention also aims to provide a preparation method of the self-cleaning multistage microporous structure ABS material, which comprises the following steps:

melt-extruding ABS, SAN and PDMS to obtain ABS/SAN/CMC composite material particles;

step two, blending and extruding ABS/SAN/CMC composite material particles and PDMS to obtain a nanoparticle modified ABS/SAN/PDMS/CMC quaternary composite material;

thirdly, taking the ABS/SAN/PDMS/CMC quaternary composite material as a template, and obtaining a product through a required molding mode;

and step four, performing post-treatment on the product for more than 30 minutes by hot water at the temperature of more than 95 ℃, removing PDMS by the hot water, and obtaining the ABS/SAN/CMC composite material with the micron-sized open pore structure.

As a further scheme of the invention: the forming modes required in the third step are extrusion, injection molding, film blowing and casting.

Compared with the prior art, the invention has the beneficial effects that: the ABS is selected as matrix resin, the styrene acrylonitrile copolymer (SAN) is used as a melt reinforcing material, the CMC molecular sieve is used as a nano-structure template, the three are melted and extruded to obtain ABS/SAN/CMC composite material particles, and the CMC molecular sieve is easily distributed on the surfaces of the composite material particles due to the shape-loss principle, so that CMC precipitates are formed and stay on the particles. Then blending and extruding with Polydimethylsiloxane (PDMS) to obtain the nano-particle modified ABS/SAN/PDMS/CMC quaternary composite material. Because PDMS and ABS/SAN composite substrate are poorly compatible, according to the principle that polymer materials are incompatible, a 'sea-island structure' can be formed in the composite material, and the CMC molecular sieve is an inorganic material and is easily dispersed in the interface of the PDMS and the ABS/SAN. Then taking the ABS/SAN/PDMS/CMC quaternary composite material as a template, and carrying out post-treatment for more than 30 minutes by using hot water at the temperature of more than 95 ℃ through different forming modes, such as extrusion, injection molding, film blowing, tape casting and the like to obtain a product, wherein PDMS is removed by the hot water, and the ABS/SAN/CMC composite material with a micron-sized open pore structure is obtained, and a small amount of PDMS is still remained on an interface, and meanwhile, a CMC molecular sieve dispersed on the interface can form numerous nano structures in pores, so that a uniform and special micro-nano structure of 'nano tip-micron pore' can be formed on the inner surface of the material, and a silicon-oxygen (Si-O) chemical structure of PDMS is added, so that a bionic multi-level microporous structure of lotus leaves can be effectively formed, the self-cleaning function of the composite material is realized, and a new function is endowed to the ABS material with the multi-level micropores. Compared with the conventional ABS foaming material, the ABS foaming material is a thermoplastic material, accords with the environment-friendly concept of recycling, combines the conventional processing mode and hot water treatment, and is beneficial to the high-efficiency processing of products.

Drawings

FIG. 1 is a SEM result chart of example 1 of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. 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.

Example 1:

the self-cleaning multistage microporous structure ABS material comprises the following raw materials in parts by weight:

31 parts of ABS with the butadiene content of 25 percent;

SAN 22 parts with the acrylonitrile content of 30 percent;

44 portions of PDMS with a viscosity of 30000 (cp at 25 ℃);

0.5 part of A-type spherical CMC molecular sieve;

1 part of white oil;

0.5 part of antioxidant.

The preparation method comprises the following steps:

melt-extruding ABS, SAN and PDMS to obtain ABS/SAN/CMC composite material particles;

step two, blending and extruding ABS/SAN/CMC composite material particles and PDMS to obtain a nanoparticle modified ABS/SAN/PDMS/CMC quaternary composite material;

thirdly, taking the ABS/SAN/PDMS/CMC quaternary composite material as a template, and obtaining a product through a required molding mode;

and step four, performing post-treatment on the product for more than 30 minutes by hot water at the temperature of more than 95 ℃, removing PDMS by the hot water, and obtaining the ABS/SAN/CMC composite material with the micron-sized open pore structure.

Example 2:

the self-cleaning multistage microporous structure ABS material comprises the following raw materials in parts by weight:

38 portions of ABS with 26 percent of butadiene content;

SAN 23 parts with the acrylonitrile content of 28 percent;

47 parts of PDMS with a viscosity of 25000(25 ℃ cp);

0.5 part of A-type spherical CMC molecular sieve;

1 part of white oil;

0.5 part of antioxidant.

The preparation method is the same as that of example 1.

Example 3:

the self-cleaning multistage microporous structure ABS material comprises the following raw materials in parts by weight:

38 portions of ABS with 24 percent of butadiene content;

SAN 28 parts with the acrylonitrile content of 263 percent;

40 portions of PDMS with a viscosity of 30000 (cp at 25 ℃);

0.5 part of A-type spherical CMC molecular sieve;

1 part of white oil;

0.5 part of antioxidant.

The preparation method is the same as that of example 1.

Example 4:

the self-cleaning multistage microporous structure ABS material comprises the following raw materials in parts by weight:

31 parts of ABS with the butadiene content of 23 percent;

SAN 22 parts with the acrylonitrile content of 29 percent;

40 parts of PDMS with viscosity of 20000 (cp at 25 ℃);

0.1 part of A-type spherical CMC molecular sieve;

0.1 part of white oil;

0.1 part of antioxidant.

The preparation method is the same as that of example 1.

Example 5:

the self-cleaning multistage microporous structure ABS material comprises the following raw materials in parts by weight:

35 parts of ABS with the butadiene content of 30 percent;

SAN 25 parts of acrylonitrile (acrylonitrile) with the content of 33 percent;

43 parts of PDMS with a viscosity of 50000 (cp at 25 ℃);

0.5 part of A-type spherical CMC molecular sieve;

1 part of white oil;

and 1 part of antioxidant.

The preparation method is the same as that of example 1.

Example 6:

the self-cleaning multistage microporous structure ABS material comprises the following raw materials in parts by weight:

38 portions of ABS with 20 percent of butadiene content;

SAN 28 parts with the acrylonitrile content of 25 percent;

47 portions of PDMS with viscosity of 10000(25 ℃ cp);

1 part of A-type spherical CMC molecular sieve;

2 parts of white oil;

and 2 parts of an antioxidant.

The preparation method is the same as that of example 1.

The raw materials of the examples and the comparative examples in parts by weight are shown in the following table:

name of raw materials	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Comparative example 1	Comparative example 2	Comparative example 3
										ABS	31	38	38	31	35	38	56	31	52
SAN	22	23	28	22	25	28	/	23	46
										PDMS	44	47	40	40	43	47	42	44	/
CMC	0.5	0.5	0.5	0.1	0.5	1	0.5	/	0.5
										White oil	1	1	1	0.1	1	2	1	1	1
Antioxidant agent	0.5	0.5	0.5	0.1	1	2	0.5	1	0.5

Characterization data and Effect data for the products of examples and comparative examples

Note: the melt index was measured at 220 ℃ and 5 kg.

The ABS is selected as matrix resin, the styrene acrylonitrile copolymer (SAN) is used as a melt reinforcing material, the CMC molecular sieve is used as a nano-structure template, the three are melted and extruded to obtain ABS/SAN/CMC composite material particles, and the CMC molecular sieve is easily distributed on the surfaces of the composite material particles due to the shape-loss principle, so that CMC precipitates are formed and stay on the particles. Then blending and extruding with Polydimethylsiloxane (PDMS) to obtain the nano-particle modified ABS/SAN/PDMS/CMC quaternary composite material. Because PDMS and ABS/SAN composite substrate are poorly compatible, according to the principle that polymer materials are incompatible, a 'sea-island structure' can be formed in the composite material, and the CMC molecular sieve is an inorganic material and is easily dispersed in the interface of the PDMS and the ABS/SAN. Then taking the ABS/SAN/PDMS/CMC quaternary composite material as a template, and carrying out post-treatment for more than 30 minutes by using hot water at the temperature of more than 95 ℃ through different forming modes, such as extrusion, injection molding, film blowing, tape casting and the like to obtain a product, wherein PDMS is removed by the hot water, and the ABS/SAN/CMC composite material with a micron-sized open pore structure is obtained, and a small amount of PDMS is still remained on an interface, and meanwhile, a CMC molecular sieve dispersed on the interface can form numerous nano structures in pores, so that a uniform and special micro-nano structure of 'nano tip-micron pore' can be formed on the inner surface of the material, and a silicon-oxygen (Si-O) chemical structure of PDMS is added, so that a bionic multi-level microporous structure of lotus leaves can be effectively formed, the self-cleaning function of the composite material is realized, and a new function is endowed to the ABS material with the multi-level micropores. Compared with the conventional ABS foaming material, the ABS foaming material is a thermoplastic material, accords with the environment-friendly concept of recycling, combines the conventional processing mode and hot water treatment, and is beneficial to the high-efficiency processing of products.

All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.