CN108342050A - A kind of ABS modified materials that can be used for 3D printing - Google Patents

Abstract

The invention belongs to polymeric material field, more particularly to it is a kind of can be with the scratch-resistant ABS material and preparation method thereof of 3D printing.Functional material of the present invention is at least grouped as by following three kinds of groups：ABS plastic, polymethyl methacrylate, MMB methyl methacrylate butadiene styrol copolymer can also contain other auxiliary agents.The modified material both has excellent scraping and wiping resistance performance, also has the comprehensive mechanical property more balanced, and can be used for 3D printing.This high molecular material can be processed into the strand that can be used for 3D printing by squeezing out；By the method for 3D printing, easily by this file printing at the product with arbitrary shape, size；Resulting product also with excellent scraping and wiping resistance performance and excellent mechanical property, has broad application prospects.

Description

A modified ABS material that can be used for 3D printing

technical field

The invention belongs to the field of polymer materials, and in particular relates to an ABS modified material that can be used for 3D printing.

Background technique

As a new type of additive manufacturing technology, 3D printing has received more and more attention in recent years. 3D printing is based on digital models, using thermoplastic resins, photosensitive resins, powdered metals, ceramics and other materials to manufacture objects with different topological structures by layer-by-layer printing. Compared with the traditional manufacturing mode, 3D printing does not require molds, and can produce very complex and highly personalized objects, which can meet various needs. At present, 3D printing has been used in medicine and medical engineering, electronic devices, aerospace, construction industry and other fields. According to different printing technologies and printing materials, 3D printing can be mainly divided into fused deposition method (FDM), selected laser sintering method (SLS), stereolithography method (SLA), inkjet printing method (3DP) and so on. Among many 3D printing technologies, FDM technology has the advantages of simple printing principle, low technical threshold, abundant raw materials, and relatively cheap equipment, so it has always been the focus of research. FDM technology requires materials to be processed into filaments with a specified diameter, and then use the principle of melting-solidification to prepare objects with arbitrary topological structures. After nearly thirty years of development, FDM technology has become increasingly mature. In recent years, people have paid more and more attention to 3D printing materials suitable for FDM.

Acrylonitrile-butadiene-styrene graft copolymer (ABS) is one of the most common FDM printing materials. The microstructure of ABS resin is composed of two phases, the copolymer of styrene and acrylonitrile (SAN) is the continuous phase, and the polybutadiene particles or butadiene copolymer grafted with SAN are the dispersed phase. The rubber particles grafted with SAN have excellent compatibility with the SAN matrix, and have good dispersion in the SAN matrix, so the ABS resin presents a typical "sea-island" two-phase structure. The SAN matrix gives ABS high strength, good chemical resistance, excellent fluidity and surface gloss, and the rubber particles provide ABS with good room temperature toughness and low temperature toughness. ABS has excellent processing performance and can be easily processed into filaments with specified diameters for further use in FDM printing. Moreover, the glass transition temperature of ABS is relatively low, about 110°C, so FDM printing can be performed at a relatively low temperature. In addition, ABS resin is a non-crystalline polymer, and there is no transition from amorphous to crystalline during the melting-solidification process, so the shrinkage rate during the cooling and setting process is small, and the precision and dimensional stability of the product are good. Because ABS resin has many of the above characteristics, it is especially suitable for FDM 3D printing.

At present, there are many ABS grades specially used for FDM printing on the market. ABS can be endowed with different functions and applications by selecting appropriate production processes and different modifiers. Stratasys has developed high-strength ABS-M30, ABS-ESD7 with static dissipative capacity, and ABSplus with various colors; 3D Systems has introduced ABS-Armor with excellent tensile strength and ABS-Armor with good thermal stability. M3X; Polymaker has developed ABS-Polylite with less odor and less warping during printing. These existing commercial products and related research on the market have greatly expanded the functions and applications of ABS resin in the field of FDM printing. In the fields of auto parts, architectural design, toy models, fixtures and fixtures, and daily consumer goods, the scratch resistance and comprehensive mechanical properties of materials are very important. However, there is currently no ABS modified material on the market that is specially used for FDM 3D printing and has excellent scratch resistance and balanced mechanical properties.

In the present invention, the strategy of polymer blending is adopted, with various commercial ABS resins as the matrix, various commercial polymethyl methacrylate (PMMA), methyl methacrylate-butadiene-styrene copolymer (MBS ) as a modified substance, and an ABS modified material with excellent scratch resistance, excellent comprehensive mechanical properties and 3D printing by fused deposition method was prepared. The ABS modified material can be prepared by common polymer processing methods such as internal mixing, open milling, extrusion and the like. The ABS modified material can use a single-screw extruder to prepare filaments with a specified diameter and uniform thickness, so that it can be 3D printed with FDM technology. The invented ABS modified material can be used to 3D print objects with arbitrary topology by fused deposition method, and the printed objects have excellent scratch resistance and balanced comprehensive mechanical properties.

Contents of the invention

The purpose of the present invention is to provide an ABS modified material that can be 3D printed by fusion deposition method with excellent scratch resistance and balanced mechanical properties.

The ABS modified material that can be used for 3D printing provided by the present invention is made up of following three kinds of components at least: ABS resin, polymethyl methacrylate (PMMA) and methyl methacrylate-butadiene-styrene (MBS), may also contain related additives. The modified material is characterized by excellent scratch resistance and balanced mechanical properties, and can be used for 3D printing.

The components of the ABS modified material are as follows by mass:

ABS resin 100 parts

Polymethyl methacrylate 5-80 parts

Methyl methacrylate-butadiene-styrene copolymer 0.5-20 parts

Auxiliary 0-100 parts.

In the present invention, the ABS resin is prepared by emulsion grafting method, emulsion grafting-blending method, bulk-suspension method, emulsion grafting-suspension method or continuous bulk polymerization method.

In the present invention, the polymethyl methacrylate is selected from various commercial grades of polymethyl methacrylate; a certain grade can be used alone or multiple grades can be used in combination.

In the present invention, the methyl methacrylate-butadiene-styrene terpolymer has a core-shell structure, and the core of the particle is a slightly cross-linked polybutadiene core or butadiene with a low shear modulus. Styrene rubber core; shell grafted from styrene and methyl methacrylate.

In the present invention, the auxiliary agent is antioxidant, dyeing agent, dispersant or inorganic filler, which can be used according to actual conditions.

The composition ratio (parts by mass) of several main components in the present invention is determined by the compatibility between polymers, the scratch resistance of the modified material, and the comprehensive mechanical properties of the modified material.

ABS modified material provided by the invention, concrete steps are as follows:

The ABS resin matrix, polymethyl methacrylate and methyl methacrylate-butadiene-styrene copolymer are fully mixed, and the blended material is prepared by using a twin-screw extruder and a method of melt blending.

When blending, add relevant additives as required.

For different materials, suitable methods can be selected for mixing, usually using a twin-screw extruder.

In the present invention, the blended blend is further processed into a filament with a specified diameter, and is extruded by a single-screw extruder. The filaments have a specified diameter and roundness. The filament with specified diameter is used for fused deposition 3D printing to prepare the desired product.

The 3D printed product of the present invention can have any shape and size, and has excellent scratch resistance and balanced mechanical properties.

The processing methods involved in the present invention are conventional methods for processing and modifying general-purpose polymer materials, such as mixing and extrusion.

The ABS modified material that can be 3D printed by the fused deposition method proposed by the present invention has excellent scratch resistance and balanced mechanical properties, and has the characteristics of cheap raw materials, simple preparation methods, and convenience for large-scale production. It is used in automotive parts, It has broad application prospects in architectural design and daily consumer goods.

Detailed ways

Specifically, the present invention is further described through the following implementation regulations, and the components and contents involved are all by weight.

Example 1.

ABS resin (China Lanzhou Petrochemical Company, grade 301), polymethyl methacrylate (PMMA, China Zhenjiang Chimei Chemical Co., Ltd., grade CM205), methyl methacrylate-butadiene-styrene copolymer (MBS, South Korea LG Chemical Co., Ltd., brand EM500A) was dried, and 700 g ABS, 300 g PMMA, and 20 g MBS were weighed, blended and extruded by a twin-screw extruder, pelletized, and dried in an oven at 80 °C for 3 h. The prepared blended pellets were then extruded into filaments with a diameter of about 1.75 mm using a single-screw extruder. The extruded filaments are printed into various types of splines by a commercial FDM 3D printer for scratch resistance testing, tensile testing, bending testing, and impact testing. The standard used for the scratch resistance test is: Volkswagen PV3952; the standard used for the tensile test is: GB/T 1040-92; the standard used for the bending test is: GB/T 9341-2008; the standard used for the impact test is: GB /T 1043-2008. The obtained ABS modified material has a scratch width of 145 μm, a tensile modulus of 573 MPa, a tensile strength of 44 MPa, an elongation at break of 14%, a flexural modulus of 2223 MPa, and a flexural strength of 62 MPa. is 17 kJ/m ² .

Example 2.

ABS resin, polymethyl methacrylate, and methyl methacrylate-butadiene-styrene copolymer were dried, wherein ABS was 700 g, PMMA was 300 g, and MBS was 40 g. Using a twin-screw extruder to blend and extrude various materials and pelletize. The above-mentioned mixture pellets are then extruded by a single-screw extruder, and filaments with a diameter range of about 1.75 mm can be obtained by adjusting the processing parameters. The extruded filaments are printed into various types of splines by a commercial FDM 3D printer for scratch resistance testing, tensile testing, bending testing, and impact testing. The standard used for the scratch resistance test is: Volkswagen PV3952; the standard used for the tensile test is: GB/T 1040-92; the standard used for the bending test is: GB/T 9341-2008; the standard used for the impact test is: GB /T 1043-2008. The obtained ABS modified material has a scratch width of 146 μm, a tensile modulus of 551 MPa, a tensile strength of 43 MPa, an elongation at break of 16%, a flexural modulus of 2092 MPa, a flexural strength of 58 MPa, and an impact strength of is 17 kJ/m ² .

Example 3.

ABS resin, polymethyl methacrylate, and methyl methacrylate-butadiene-styrene copolymer were dried, wherein ABS was 700 g, PMMA was 300 g, and MBS was 60 g. Using a twin-screw extruder to blend and extrude various materials and pelletize. The above-mentioned mixture pellets are then extruded by a single-screw extruder, and filaments with a diameter range of about 1.75 mm can be obtained by adjusting the processing parameters. The extruded filaments are printed into various types of splines by a commercial FDM 3D printer for scratch resistance testing, tensile testing, bending testing, and impact testing. The standard used for the scratch resistance test is: Volkswagen PV3952; the standard used for the tensile test is: GB/T 1040-92; the standard used for the bending test is: GB/T 9341-2008; the standard used for the impact test is: GB /T 1043-2008. The prepared ABS modified material has a scratch width of 149 μm, a tensile modulus of 519 MPa, a tensile strength of 43 MPa, an elongation at break of 17%, a flexural modulus of 1994 MPa, and a flexural strength of 56 MPa. The impact strength is 18 kJ/m ² .

Example 4.

Dry ABS resin, polymethyl methacrylate, and methyl methacrylate-butadiene-styrene copolymer, wherein ABS is 500 g, PMMA is 500 g, and MBS is 5 g. Using a twin-screw extruder to blend and extrude various materials and pelletize. The above-mentioned mixture pellets are then extruded by a single-screw extruder, and filaments with a diameter range of about 1.75 mm can be obtained by adjusting the processing parameters. The extruded filaments are printed into various types of splines by a commercial FDM 3D printer for scratch resistance testing, tensile testing, bending testing, and impact testing. The standard used for the scratch resistance test is: Volkswagen PV3952; the standard used for the tensile test is: GB/T 1040-92; the standard used for the bending test is: GB/T 9341-2008; the standard used for the impact test is: GB /T 1043-2008. The obtained ABS modified material has a very small scratch width value, and the scratch resistance, tensile modulus, tensile strength, flexural modulus, and flexural strength are all further improved, but the elongation at break, impact strength decreased significantly.

Claims (5)

1. A kind of ABS modified material that can be used for 3D printing is characterized in that, each component by mass is: ABS resin 100 parts Polymethyl methacrylate 5-80 parts Methyl methacrylate-butadiene-styrene copolymer 0.5-20 parts Auxiliary 0-100 parts. 2. The ABS modified material according to claim 1, wherein the ABS resin adopts emulsion grafting method, emulsion grafting-blending method, bulk-suspension method, emulsion grafting-suspension method or continuous bulk prepared by polymerization. 3. ABS modified material according to claim 1, is characterized in that, described methyl methacrylate-butadiene-styrene terpolymer is core-shell structure, and the core of particle is through slight cross-linking Polybutadiene or styrene-butadiene rubber core with low shear modulus; shell grafted from styrene and methyl methacrylate. 4. ABS modified material according to claim 1, is characterized in that, described auxiliary agent is antioxidant, dyeing agent, dispersant or inorganic filler. 5. a preparation method for preparing the ABS modified material as claimed in claim 1, is characterized in that, concrete steps are as follows: The ABS resin matrix, polymethyl methacrylate and methyl methacrylate-butadiene-styrene copolymer are fully mixed, and the blended material is prepared by using a twin-screw extruder and a method of melt blending.