CN105733169A

CN105733169A - Preparation method of low-warpage ABS special-purposed 3D printing material

Info

Publication number: CN105733169A
Application number: CN201410746979.7A
Authority: CN
Inventors: 高海涛; 代汝军; 马俊杰
Original assignee: Heilongjiang Xinda Enterprise Group Co Ltd
Current assignee: Heilongjiang Xinda Enterprise Group Co Ltd
Priority date: 2014-12-10
Filing date: 2014-12-10
Publication date: 2016-07-06

Abstract

The invention relates to a preparation method of a low-warpage ABS special-purposed 3D printing material. According to the invention, SiO2 inorganic powder is modified through a mixed acid ultrasonic treatment; under the effect of a high-temperature coupling agent, blending modification is carried out with ABS, such that the low-warpage ABS special-purposed 3D printing material is obtained.

Description

The preparation method that the special 3D of a kind of low warpage ABS prints material

Technical field

The invention belongs to 3D printing technique field, relate to one and utilize nitration mixture ultrasonic method to process SiO₂Inorganic powder filled ABS prepares the low warpage 3D preparation method printing material.

Background technology

ABS is the thermoplastic engineering plastic that a kind of purposes is extremely wide, it is easily worked, and finished chemical character is stable, glossiness good, there is extremely strong impact resistance, heat-resisting lower temperature resistance and excellent electric property, it is possible to carry out the processing such as surface colour, metalling, plating, welding.So it is a kind of good 3D matrix resin printing PP Pipe Compound.Owing to single ABS resin is difficult to meet different instructions for uses, ABS modified becoming one of focus of research both at home and abroad in recent years, its Main Means has fiber reinforcement ABS, particles filled ABS, ABS surface modified and polyblend etc..So it is possible not only to reduce goods cost, moreover it is possible to improve moulding processability and the serviceability of ABS.Wherein inorganic fill ABS composite material, especially SiO₂Inorganic powder filled ABS composite material has great significance for ABS warpage is modified, but owing to usually 3D printing ABS resin exists warpage serious problems, it is common to inorganic fill dispersibility is difficult to improve, cause printing difficulty, improve DeGrain, affect the mechanical property of 3D printout.

Summary of the invention

It is an object of the invention to provide one utilizes one to utilize nitration mixture ultrasonic method to process SiO₂The preparation method that inorganic particle reduces ABS warpage.Nitration mixture ultrasonic method is utilized to process SiO₂Inorganic particle and ABS, by physical blending, are simultaneously introduced high temperature coupling agent, prepare the special 3D of low warpage ABS and print material.Specifically comprise the following steps that

One, SiO₂The surface modification treatment of inorganic particle

First with acetone soak method to SiO₂Inorganic particle is modified, and removes SiO₂Inorganic powder surface epoxy layer.Comparatively good surface microscopic state is provided for its after-treatment.Wherein the acetone soak time is 20-30min.Nitric acid is selected to prepare into nitration mixture with concentrated sulphuric acid mass ratio 2:1, by ultrasound transfer device to SiO₂Inorganic particle carries out twice-modified

Two, SiO₂Inorganic particle is blended with PA6 resin

By PA6 and the SiO processed through nitration mixture ultrasonic method₂Inorganic particle carries out physical blending according to a certain percentage, adds high temperature coupling agent, melt extrudes.SiO₂SiO in inorganic particle₂Particle produces for resin-based internal stress to be had good counteracting and internal stress dispersion is had good facilitation.

As no specific instructions, the various raw materials of the present invention all can pass through to be commercially available;Or the conventional method according to this area prepares.Unless otherwise defined or described herein, the same meaning that all specialties used herein are familiar with scientific words and those skilled in the art.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.

Below in conjunction with specific embodiment, the present invention is expanded on further.These embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention.In the following example unreceipted specifically with torture experimental technique, generally conventionally condition, or according to manufacturer it is proposed that condition carry out.Unless otherwise indicated, otherwise all of mark is weight portion, and all of percentage ratio is weight percentage, and described polymer molecular weight is number-average molecular weight.

Step 1,

SiO used in following example₂The surface treatment of inorganic particle, processes step as follows: select the Hefei Kai Er SiO provided₂The surface treatment of inorganic particle, processes step as follows: select the Hefei Kai Er SiO provided₂Inorganic particle is immersed among acetone (analytical pure) and takes out after 20-30min.

Step 2,

By 2:1, nitric acid is carried out room temperature with concentrated sulphuric acid mix, adopt the SiO that ultrasound transfer device will be crossed at acetone soak₂Inorganic particle is immersed in nitration mixture and carries out nitration mixture supersound process.Wherein ultrasound transfer matching requirements alternator output frequency 20KHz, power 225W, total recombination time 3min, ultrasonic density 0.1-0.3W/ml, translational speed 0.5-1.0m/min.Nitration mixture supersound process is complete, by SiO₂Inorganic particle is with after distilled water wash pH=7, stand-by after putting into oven for drying 4h.

Step 3,

The preparation of high temperature coupling agent selects titanate esters, biphenyl dianhydride, rare propyl group amine and triethoxysilane to be raw material, by imidization reaction, and obtains special high temperature resistant silane coupler with the physical mixed of titanate esters

According to above step by through twice-modified SiO₂Inorganic particle and high temperature coupling agent, PA6 resin melting blending extrusion, can be prepared by the special 3D of low warpage PA6 of the present invention and print material.

Specific performance is referring to following table:

The each constituent content of table 1 different formulations

Table 2 different formulations Performance comparision

Plane warping degree %	Formula 1 formula 2 formula 3
		Y	2.3 0.34 1.1

By in table it can be seen that by the SiO of nitration mixture supersound process₂The special 3D of inorganic powder filled PA6 prints material and compares the SiO that the conventional oxidation method of equal proportion processes₂The special 3D of inorganic powder filled PA6 prints material, more excellent in plane warping degree performance.

Below it is only the concrete exemplary applications of the present invention, protection scope of the present invention is not constituted any limitation.The technical scheme that all employing equivalents or equivalence are replaced and formed, all falls within rights protection scope of the present invention.

Claims

1. the preparation method that the special 3D of low warpage ABS prints material, utilizes the modified SiO of nitration mixture supersound process₂Inorganic particle, under the effect of high temperature coupling agent, by carrying out blending and modifying with ABS, prepares the special 3D of low warpage ABS and prints material.

2. select metatitanic acid fat, biphenyl dianhydride, allyl amine and triethoxysilane to be raw material according to the told high temperature coupling agent preparation of claim 1, by imidization reaction, and obtain special high temperature silane coupler with the physical mixed of metatitanic acid fat.

3. SiO according to claim 1₂Inorganic particle, be provided by Hefei Kai Er white, purity more than 99%, particle mean size 60nm, specific surface area is more than 400m²·g^-1, once modified is by acetone soak method, it is modified, and removes surface epoxy layer, twice-modified utilizes nitration mixture ultrasonic method to SiO₂Inorganic particle carries out surface treatment.

4. according to claim 1 by nitration mixture ultrasonic method to its carry out twice-modified in, nitration mixture is made up of nitric acid and concentrated sulphuric acid, and each constituent content is by weight for 2:1, by the Ultrasonic treatment SiO to carrying out acetone soak₂Inorganic particle carries out twice-modified.