CN106380847A - Method for preparing laser sintering molded three-dimensional (3D) printing polyimide/polyether sulfone/nano carbon powder consumable - Google Patents
Method for preparing laser sintering molded three-dimensional (3D) printing polyimide/polyether sulfone/nano carbon powder consumable Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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Abstract
The invention provides a method for preparing a laser sintering molded three-dimensional (3D) printing polyimide/polyether sulfone/nano carbon powder consumable. The method comprises the following steps: (1) adding nano carbon powder into a high-speed mixer, and drying at the temperature of 100 DEG C for 3 hours; (2) adding polyimide, polyether sulfone resin and the nano carbon powder dried in the step (1) into the high-speed mixer according to a mass ratio, performing batch mixing at the temperature of 50 DEG C at a low speed for 30 minutes, and mixing at a high speed for 30 minutes; (3) adding the blended powder in the step (2) into a grinder, and grinding under the condition of 320 revolutions per minute for 1.5 hours; and (4) drying the blended powder in the step (3) at the temperature of 90 DEG C for 2 hours, thereby obtaining the laser sintering molded three-dimensional (3D) printing polyimide/polyether sulfone/nano carbon powder, wherein the mass ratio of polyimide to polyether sulfone resin to the nano carbon powder is (30-60):(100):(0.1-5).
Description
Technical field
The present invention relates to a kind of preparation method for laser sintering rapid forming dusty material, belong to the material of rapid shaping
Material field, more particularly it relates to a kind of laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder
The preparation method of consumptive material.
Background technology
3D printing (3D printing), be a kind of based on mathematical model file, with flow-like, powder, silk
(excellent) shape etc. is curable, bonding, alloying material, carry out the technology of constructed object by way of successively solidification, bonding, fusion.3D
Printing technique occurs in the mid-90 in 20th century, the up-to-date rapid shaping of the technology such as actually utilize photocuring and ply of paper to fold
Device.It is essentially identical with common print operation principle, and printer, built with liquid or powder etc. " printed material ", is connected with computer
After connecing, controlled by computer and " printed material " is stacked up from level to level, finally the blueprint on computer is become in kind.This dozen
Print technology is referred to as 3D three-dimensional printing technology.Traditional manufacture generally requires and raw material is cut or holes, that is, subtract material manufacture,
Can be mass-produced；3D printing is that material stacks bonding, fusion, i.e. increasing material manufacturing from level to level；Can achieve quickly personalized system
Make, the shape that traditional manufacture cannot complete can be produced.
Selective laser sintering (SLS), belongs to a kind of method of 3D printing technique, using controlled laser-light beam melts powder
Material is accumulated the three-dimensional model sintering out complexity layer by layer.In development selective laser sintering this kind of 3D printing technique industrialization
Process in, manufacturing equipment and material foundation research be two big key technologies.Selective laser sintering requires more to raw material
Harshness, material needs to provide with powder；In sintering process, material, after the change of the states of matter such as fast melt and solidification, still must
There is good physics, chemical property.At present, it is usually used in the material of selective laser sintering research, have metal material, ceramic material
Material, polymeric material and the composite between them, but the material being applied to selective laser sintering and moulding is not only planted
Class is few, cost intensive, and processing technology is also more complicated, thus is difficult to industrialization.
Nano carbon powder wide material sources and cheap；Polyethersulfone resin (PES), as the adhesive of composite, has
There is the features such as high mechanical strength, good stability of the dimension and excellent moulding processability.
Polyimides (polyimide, PI) be on main chain containing imide ring to have excellent heat resistance, chemically-resistant stable
One family macromolecule material of property, mechanical property and electrical property, not only can be in traditional Aeronautics and Astronautics and defense-related science, technology and industry
As structural resin based composites and special material, be used as insulating materials in the electronics industry, in some current techiques
It is used as heat absorption and sound-absorbing material, structural adhesive and protective coating, and progressively start in integrated circuit, liquid crystal display, light
It is widely used in the high-tech areas such as device, fuel cell, optical-fibre communications, gas separation.But because it is special
Molecular structure and be limited by very large, main processing is more difficult.
Therefore, the adjustment by polyimide structures for the present invention, synthesizes the fire resistant polyimide of 3D printing technique, uses
In the composite preparing selective laser sintering 3D printing polyimides/polyether sulfone/nano carbon powder, can be convenient and swift
Ground shapes accurate, special-shaped, complicated, the high temperature resistant, part of high mechanical strength, good stability of the dimension.
Content of the invention
The present invention provides a kind of system of laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material
Preparation Method is it is characterised in that comprise the following steps：
(1) it is dried：Nano carbon powder is put in high-speed mixer, under the conditions of 100 DEG C, 3h is dried；
(2) it is blended：Add dried nano carbon powder in polyimides and polyethersulfone resin and step (1) in mass ratio
In high-speed mixer, under the conditions of 50 DEG C, low speed interval mixes 30min, then mixed at high speed 30min at end；
(3) grind：Blended powder in step (2) is added in grinder, under the conditions of 320r/min, grinds 1.5h；
(4) it is dried：Blended powder in step (3) is dried 2h under the conditions of 90 DEG C, obtains laser sintering and moulding 3D printing
Polyimides/polyether sulfone/nano carbon powder；
Wherein, described polyimides and the mass ratio of polyethersulfone resin, nano carbon powder are (30～60)：100：(0.1
～5).
In one embodiment, the monomer of preparing of described polyimides includes dianhydride monomer, diamine monomer；Described diamines
Monomer includes aromatic diamines, imidazoles diamines.
In one embodiment, described dianhydride monomer be selected from 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides), 4,
4 '-oxygen double phthalic anhydride, 5,5 '-oxo (4,1- phenoxy group)] one or more in double phthalic anhydrides.
In one embodiment, described aromatic diamines, the mol ratio of imidazoles diamines are 1：(2～4).
In one embodiment, described aromatic diamines are selected from p-phenylenediamine, Isosorbide-5-Nitrae ,-bis- (4- amino-benzene oxygen) benzene, 1,
4 ,-bis- (3- amino-benzene oxygen) benzene, 1,3, one or more in-bis- (4- amino-benzene oxygen) benzene, 1,4- diaminobenzene；Described miaow
Azoles diamines be selected from 2- (4- aminophenyl) -5 aminophenyl benzimidazole, 2- (3- aminophenyl) -5 aminophenyl benzimidazole,
2,2 '-bis- (4- aminophenyl) -5,5 '-bibenzimidaz sigmale, 2,2 '-bis- (4- aminophenyl) benzimidazoles, 2,2 '-bis- (3- ammonia
Base phenyl) one or more in benzimidazole.
In one embodiment, the particle diameter of described polyimide resin is 40～800 μm.
In one embodiment, the particle diameter of described nano carbon powder is 100～1000nm.
In one embodiment, the particle diameter of described polyethersulfone resin is 10～400 μm.
In one embodiment, described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumption
The preheating temperature of material is 70～80 DEG C；Described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material
Input energy density be 0.1～0.4J/mm3；Described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon
The laser power of powder consumptive material is 5～40W.
In one embodiment, described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumption
The sweep speed of material is 1500～2000mm/s；Described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder
The sintering spacing of last consumptive material is 0.1～0.2mm；Described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder
The thickness in monolayer of last consumptive material is 0.1～0.2mm；Described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder
The processing temperature of last consumptive material is 110～150 DEG C.
It is more readily understood the above-mentioned of the application and other features, aspect and advantage with reference to described further below.
Specific embodiment
The embodiment of the participation in the election detailed description being preferable to carry out method of the invention below and inclusion can be more easily understood this
Bright content.Unless otherwise defined, all technology used herein and scientific terminology have common with art of the present invention
The identical implication that technical staff is generally understood that.When there is contradiction, the definition in this specification is defined.
As used herein term " by ... preparation " synonymous with "comprising".Term "comprising" used herein, " inclusion ",
" having ", " containing " or its any other deformation it is intended that cover non-exclusionism inclusion.For example, comprise the combination of listed elements
Thing, step, method, product or device are not necessarily solely those key elements, but can include not expressly listed other key elements or
This kind of composition, step, method, product or the intrinsic key element of device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this
Phrase will make claim be closed so as to not comprise the material in addition to the material that those describe, but relative normal
Except rule impurity.When phrase " Consists of " occurs in and is rather than immediately following after theme in the clause of claim main body,
It is only limited to the key element described in this clause；Other key elements are not excluded outside as overall described claim.
Equivalent, concentration or other value or parameter are excellent with scope, preferred scope or a series of upper limit preferred value and lower limit
During the Range Representation that choosing value limits, this is appreciated that and specifically discloses by any range limit or preferred value and any scope
All scopes that arbitrary pairing of lower limit or preferred value is formed, regardless of whether whether this scope separately discloses.For example, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When number range is herein described, unless otherwise indicated, otherwise this scope is intended to include its end
Value and all integers within the range and fraction.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise." optional " or " arbitrarily
A kind of " refer to that the item describing thereafter or event may or may not occur, and this description include event generation situation and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this concrete
Quantity, also includes the part of the correction of acceptable change without lead to related basic function close to this quantity.Phase
Answer, modify a numerical value with " about ", " about " etc., mean and the invention is not restricted to this exact numerical.In some examples, approximately
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope limits permissible
Combination and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
Additionally, the quantitative requirement to key element or component for the indefinite article " a kind of " and " one " before key element of the present invention or component
(i.e. occurrence number) unrestriction.Therefore " one " or " a kind of " should be read as including one or at least one, and odd number
The key element of form or component also include plural form, unless the obvious purport of described quantity refers to singulative.
" polymer " means by the polymerizable compound prepared by the monomer of the identical or different type of polymerization.Generic term
" polymer " comprises term " homopolymers ", " copolymer ", " terpolymer " and " EVA ".
" EVA " means the polymer by being polymerized at least two different monomers preparations.Generic term " EVA " includes
(it is general with term " terpolymer " for term " copolymer " (it is typically in order to refer to by the polymer of two kinds of different monomers preparations)
In order to refer to by the polymer of three kinds of different monomers preparations).It also comprises the polymer manufacturing by being polymerized more kinds of monomers.
" blend " means the polymer that two or more polymer is formed by the common mixing of physics or chemistry method.
The present invention provides a kind of system of laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material
Preparation Method is it is characterised in that comprise the following steps：
(1) it is dried：Nano carbon powder is put in high-speed mixer, under the conditions of 100 DEG C, 3h is dried；
(2) it is blended：Add dried nano carbon powder in polyimides and polyethersulfone resin and step (1) in mass ratio
In high-speed mixer, under the conditions of 50 DEG C, low speed interval mixes 30min, then mixed at high speed 30min at end；
(3) grind：Blended powder in step (2) is added in grinder, under the conditions of 320r/min, grinds 1.5h；
(4) it is dried：Blended powder in step (3) is dried 2h under the conditions of 90 DEG C, obtains laser sintering and moulding 3D printing
Polyimides/polyether sulfone/nano carbon powder；
Wherein, described polyimides and the mass ratio of polyethersulfone resin, nano carbon powder are (30～60)：100：(0.1
～5).
Polyimide resin
Polyimides (polyimide, PI) be on main chain containing imide ring to have excellent heat resistance, chemically-resistant stable
One family macromolecule material of property, mechanical property and electrical property.
Polyethersulfone resin
Polyethersulfone resin is amorphous thermoplastic's macromolecular material, and molecular structure is made up of phenyl, ether and sulfuryl.Ether
Make macromolecule chain section have good mobility in the molten state, put forward forming property, sulfuryl award high marks sub- heat resistance with
And rigidity.PES has had the feature of high impact properties, high thermal deformation resistant and excellent formability concurrently, especially permissible at high temperature
Continuously use and still can keep the outstanding advantages such as stable performance itself under conditions of temperature great change.
In one embodiment, the monomer of preparing of described polyimides includes dianhydride monomer, diamine monomer；Described diamines
Monomer includes aromatic diamines, imidazoles diamines.
In one embodiment, described dianhydride monomer be selected from 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides), 4,
4 '-oxygen double phthalic anhydride, 5,5 '-oxo (4,1- phenoxy group)] one or more in double phthalic anhydrides；Preferably,
Described dianhydride monomer is selected from 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides).
In one embodiment, described aromatic diamines, the mol ratio of imidazoles diamines are 1：(2～4)；Preferably, described
Aromatic diamines, the mol ratio of imidazoles diamines are 1：3.
In one embodiment, described aromatic diamines are selected from p-phenylenediamine, Isosorbide-5-Nitrae ,-bis- (4- amino-benzene oxygen) benzene, 1,
4 ,-bis- (3- amino-benzene oxygen) benzene, 1,3, one or more in-bis- (4- amino-benzene oxygen) benzene, 1,4- diaminobenzene；Described miaow
Azoles diamines be selected from 2- (4- aminophenyl) -5 aminophenyl benzimidazole, 2- (3- aminophenyl) -5 aminophenyl benzimidazole,
2,2 '-bis- (4- aminophenyl) -5,5 '-bibenzimidaz sigmale, 2,2 '-bis- (4- aminophenyl) benzimidazoles, 2,2 '-bis- (3- ammonia
Base phenyl) one or more in benzimidazole；Preferably, described aromatic diamines are selected from Isosorbide-5-Nitrae-diaminobenzene；Described imidazoles diamines
Selected from 2- (3- aminophenyl) -5 aminophenyl benzimidazole.
In one embodiment, the particle diameter of described polyimide resin is 40～800 μm；Preferably, described polyamides is sub-
The particle diameter of polyimide resin is 40～600 μm；Preferably, the particle diameter of described polyimide resin is 40～100 μm.
In one embodiment, the preparation method of described 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides), including
Following steps：
(1) 3- monochloro phthalic anhydride is dissolved in acetic anhydride, to being completely dissolved, adds methylamine water solution, heating
After reaction 3.5-5h, it is cooled to room temperature, and is cooled to less than 10 DEG C with frozen water, filter, be dried, obtain final product product A；
(2) the product A in step (1) is dissolved in dimethyl sulfoxide (DMSO) with resorcinol, to being completely dissolved, adds catalyst
And heating reflux reaction, in course of reaction, TLC follows the trail of resorcinol, to system no after resorcinol, continues back flow reaction
0.5-2h, subsequent suction filtration, cooling, washing, centrifugation, drying, obtain final product product B；
(3) the product B in step (2) is mixed with sodium hydroxide solution, be heated to seething with excitement, anti-after solid dissolving
Answer 0.5-2h, being subsequently added concentrated hydrochloric acid and adjusting pH is 7-8, continues to boil 5-15min, is filtered to remove insoluble solids, by filtrate plus
Heat is to boiling, and is 1-2 with concentrated hydrochloric acid regulation pH, and cooling obtains final product product C；
(4) the product C in step (3) is mixed with dehydrating agent, agitating heating, dewatering and filtering, washing, drying, that is,
Obtain 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides).
In one embodiment, the preparation method of described polyimides comprises the following steps：
(1) in the DMAc solution that room temperature is added to diamines under agitation the dianhydride powder weighing up, stirring 6h about
The polyamic acid solution being 10% about to solid content；
(2) add end-capping reagent phthalic anhydride in step (1), continue the polyamic acid solution that stirring 20h obtains phthalic anhydride end-blocking；
(3) a certain amount of acid anhydrides and triethylamine is added to carry out chemical imidization, in ethanol after reaction 20h in step (2)
Middle precipitation, after the polyimide powder ethanol being settled out extracts in apparatus,Soxhlet's, 200 DEG C of vacuum is heat-treated 1h, obtains
Polyimides sample.
In one embodiment, the particle diameter of described nano carbon powder is 100～1000nm；Preferably, described nanometer
The particle diameter of carbon powder is 100～800nm；It is highly preferred that the particle diameter of described nano carbon powder is 200～500nm.
In one embodiment, the tap density of described carbon powder is 0.1～0.2kg/cm2；Preferably, described carbon
The tap density of plain powder is 0.15kg/cm2.
In one embodiment, the particle diameter of described polyethersulfone resin is 10～400 μm；Preferably, described polyether sulfone tree
The particle diameter of fat is 10～200 μm；It is highly preferred that the particle diameter of described polyethersulfone resin is 40～70 μm.
In the present invention, nano carbon powder can reach submicron order or even nanoscale, and it is little to have a meso-position radius grain, size distribution
The feature of narrow range, stable in properties；Thin-walled model or small parts can be manufactured by this rapid shaping powder material, manufacture
Go out product and have that surface gloss is high, intensity is good, the features such as high precision.
Selective Laser Sintering
Selective Laser Sintering (Selective Laser Sintering) is important one in rapid shaping technique
Individual branch, it is integrated with Fundamental Course of Mechanic Manufacturing, laser technology, material science, modern scientist engineering, computer technology, modern survey
The technology such as examination technology and CAD/CAM theoretical foundation and application.It is former that this technology can manufacture out part in the short period of time
Type and mould, are widely used in the every field of machine-building.This technology is based on layering-principle of stacking, using computer control
The movement locus of high energy laser beam processed, using the high energy melting metal dust of laser beam, after treating that laser facula is removed, metal
Liquid and rapid solidification.Whole process is exactly that laser facula moves from point to surface, then the process by face to body, and each part is
It is layering by forming face and form.The technology path of SLS process is to set up corresponding CAD model first against part, will
Model imports formation system and carries out step section, the geological information that each layer of section obtaining comprises section, generates STL form literary composition
Part.Then high energy laser beam is scanned along the track of each layer of section under control of the computer, melts in this region
Metal dust.Repave next layer of powder after one layer is terminated, repeat above procedure up to part forming.
In one embodiment, described laser sintered 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material exists
The application of shaping on 3D printer, feature is：By laser sintered 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material
It is added in the confession powder cylinder of selective laser sintering and moulding machine, dusty material is equably layered in processing plane simultaneously by powdering roller
It is heated to processing temperature, laser instrument sends laser, the switch of computer controlled laser and the angle of scanner so that laser
Bundle is scanned according to corresponding two-dimensional slice shape in processing plane, and after laser beam is inswept, workbench moves down a layer
Thickness, then powdering, laser beam flying, so repeatedly, obtain laser sintered part, the wherein mode of laser beam scanning in processing plane
For subregion scanning.
In one embodiment, described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumption
The preheating temperature of material is 70～80 DEG C；Described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material
Input energy density be 0.1～0.4J/mm3；Described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon
The laser power of powder consumptive material is 5～40W；Preferably, described laser sintering and moulding 3D printing polyimides/polyether sulfone/nanometer
The preheating temperature of carbon powder consumptive material is 70～75 DEG C；Described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano-sized carbon
The input energy density of plain powder consumptive material is 0.12～0.32J/mm3；Described laser sintering and moulding 3D printing polyimides/polyethers
The laser power of sulfone/nano carbon powder consumptive material is 5～30W.
In one embodiment, described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumption
The sweep speed of material is 1500～2000mm/s；Described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder
The sintering spacing of last consumptive material is 0.1～0.2mm；Described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder
The thickness in monolayer of last consumptive material is 0.1～0.2mm；Described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder
The processing temperature of last consumptive material is 110～150 DEG C；Preferably, described laser sintering and moulding 3D printing polyimides/polyether sulfone/receive
The sweep speed of rice carbon powder consumptive material is 1900mm/s；Described laser sintering and moulding 3D printing polyimides/polyether sulfone/nanometer
The sintering spacing of carbon powder consumptive material is 0.15mm；Described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon
The thickness in monolayer of powder consumptive material is 0.15mm；Described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder
The processing temperature of consumptive material is 120～140 DEG C.
First aspect present invention is passed through to prepare a kind of vitrification point height, and what melt temperature was relatively low is suitable for 3D printing making
Using the polyimides of temperature higher " workpiece ", second aspect is passed through to optimize polyimides, polyether sulfone and nano carbon powder
Component ratio, the uniformity of various powder quality, overcome nano carbon powder and polyimide resin, polyethersulfone resin
Compatibility, and by laser sintered principle be under almost without external force applying condition rapidoprint so that sinter out drip molding tool
There are very strong physical property and chemical property, and the scheme of the Design the laboratory material proposing is easy to be quick, when greatly reducing
Between and economize on resources.
Below by embodiment, the present invention is specifically described.Be necessary it is pointed out here that, following examples are only used
In the invention will be further described it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential improvement made according to the content of the invention described above and adjustment, still fall within protection scope of the present invention.
In addition, if not having other explanations, raw materials used is all commercially available, is purchased from traditional Chinese medicines chemical reagent.
Embodiment 1
The preparation method of described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material, including
Following steps：
(1) it is dried：Nano carbon powder is put in high-speed mixer, under the conditions of 100 DEG C, 3h is dried；Described nano-sized carbon
Plain powder is acetylene black；The particle diameter of described nano carbon powder is 1000nm；The tap density of described carbon powder is 0.12kg/
cm2；
(2) it is blended：Add dried nano carbon powder in polyimides and polyethersulfone resin and step (1) in mass ratio
In high-speed mixer, under the conditions of 50 DEG C, low speed interval mixes 30min, then mixed at high speed 30min at end；Described polyamides is sub-
Amine is 30 with the mass ratio of polyethersulfone resin, nano carbon powder：100：0.1；The particle diameter of described polyimide resin is 800 μ
m；The particle diameter of polyethersulfone resin is 400 μm；
(3) grind：Blended powder in step (2) is added in grinder, under the conditions of 320r/min, grinds 1.5h；
(4) it is dried：Blended powder in step (3) is dried 2h under the conditions of 90 DEG C, obtains laser sintering and moulding 3D printing
Polyimides/polyether sulfone/nano carbon powder.
Described laser sintered 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material is molded on 3D printer
Application
Laser sintered 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material is added to selective laser sintering
In the confession powder cylinder of forming machine, dusty material is equably layered in processing plane and is heated to processing temperature by powdering roller, swashs
Light device send laser, the switch of computer controlled laser and the angle of scanner so that laser beam processing plane on basis
Corresponding two-dimensional slice shape is scanned, and after laser beam is inswept, workbench moves down a thickness, then powdering, and laser beam is swept
Retouch, so repeatedly, obtain laser sintered part, wherein laser beam mode of scanning in processing plane scans for subregion；Described
The preheating temperature of laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material is 80 DEG C；Described laser burns
The input energy density forming type 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material is 0.24J/mm3；Described sharp
The laser power of light sinter molding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material is 10W；Described laser sintered
The sweep speed of shaping 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material is 1900mm/s；Described laser sintered one-tenth
The sintering spacing of type 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material is 0.2mm；Described laser sintering and moulding 3D
The thickness in monolayer printing polyimides/polyether sulfone/nano carbon powder consumptive material is 0.2mm；Described laser sintering and moulding 3D printing
The processing temperature of polyimides/polyether sulfone/nano carbon powder consumptive material is 150 DEG C.
The preparation method of described polyimides, comprises the following steps：
(1) weigh 0.05mol 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides) be added to 0.025mol to benzene
Add in there-necked flask in the DMAc solution of 2- (4- aminophenyl) -5 aminophenyl benzimidazole of diamines and 0.025mol, plus
Enter 230mLDMAc, put in low temperature bath (- 5 DEG C), quick stirring, after reaction 6h；
(2) add phthalic anhydride end-capping reagent in step (1), period adds DMAc that solution is progressively diluted, and continues stirring 20h left
The right side obtains the PAA solution of mass concentration 10% phthalic anhydride end-blocking；
(3) 0.3mol acetic anhydride, 0.015mol triethylamine and 0.035mol pyridine is added to carry out chemistry Asia in step (2)
Amination, precipitates after about reacting 20h, the polyimide powder ethanol being precipitated out is in apparatus,Soxhlet's at 60 DEG C in water
After middle extraction, 200 DEG C of heat treatment 1h of vacuum, obtain polyimides.
The synthetic method of described 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides), comprises the following steps：
(1) 3- monochloro phthalic anhydride is placed in reaction vessel, 3- monochloro phthalic anhydride and acetic anhydride are pressed
According to 13g：The proportioning of 45ml, adds acetic anhydride, stirs 30min, be completely dissolved to 3- monochloro phthalic anhydride at 50 DEG C, will
3- monochloro phthalic anhydride and methylamine water solution are according to 13g：The proportioning of 9ml, the methylamine adding mass fraction 30% is water-soluble
Liquid, is heated to reflux, and after toluene band water reaction 5h, is cooled to room temperature, and is cooled to less than 5 DEG C with frozen water, filters, is dried, obtain final product
Product A；
(2) will be according to 1.5：1 quality proportioning weighs product A in step (1) with resorcinol in reaction vessel, and
Add the dimethyl sulfoxide (DMSO) of 100ml, stirring makes raw material be completely dissolved, add mass fraction is total raw material 2% potassium carbonate
And be heated to reflux, back flow reaction 3h, heat filtering, filtrate is cooled to room temperature, pours in water and is stirred continuously, the precipitation warp of precipitation
Centrifuge obtains solid, obtains solid after hydrochloric acid acidifying, washing, being dried, using absolute ethyl alcohol as solvent and with cable-styled
Extractor removes the Resorcino filtering, then with chloroform, until TLC inspection does not measure resorcinol, obtains final product product B；
(3) by the product B in step (2) and mass fraction be 22% sodium hydroxide solution according to 4g：26ml proportioning is entered
Row mixing, is heated to seething with excitement, and reacts 2h after solid dissolving, and being subsequently added the concentrated hydrochloric acid that mass fraction is 38% and adjusting pH is 7-
8, continue to boil 10min, be filtered to remove insoluble solids, filtrate is heated to seething with excitement, and the concentrated hydrochloric acid being 38% with mass fraction
Regulation pH is 1-2, and cooling obtains final product product C；
(4) the product C in step (3) is mixed with acetic anhydride, is heated with stirring to 120 DEG C, dewatering and filtering, washing,
It is dried, obtains final product 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides), yield is 99%.
Embodiment 2
The preparation method of described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material, with real
Apply example 1, difference is that described nano carbon powder is Graphene；The particle diameter of described nano carbon powder is 600nm；Described carbon
The tap density of powder is 0.18kg/cm2；Described polyimides is 40 with the mass ratio of polyethersulfone resin, nano carbon powder：
100：2；The particle diameter of described polyimide resin is 600 μm；The particle diameter of polyethersulfone resin is 100 μm.
Described laser sintered 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material is molded on 3D printer
Application is described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material with embodiment 1, difference
Sintering spacing be 0.15mm；The list of described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material
Thickness degree is 0.15mm；The processing temperature of described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material
Spend for 140 DEG C.
With embodiment 1, difference is that described diamine monomer is p-phenylenediamine and 2- (4- to the preparation method of described polyimides
Aminophenyl) -5 aminophenyl benzimidazoles mixture, and p-phenylenediamine and 2- (4- aminophenyl) -5 aminophenyl benzo
The mol ratio of imidazoles is 1：2.
The synthetic method of described 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides) is with embodiment 1.
Embodiment 3
The preparation method of described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material, with real
Apply example 1, difference is that described nano carbon powder is CNT；The particle diameter of described nano carbon powder is 100nm；Described carbon
The tap density of plain powder is 0.16kg/cm2；Described polyimides with the mass ratio of polyethersulfone resin, nano carbon powder is
60：100：5；The particle diameter of described polyimide resin is 10 μm；The particle diameter of polyethersulfone resin is 10 μm.
Described laser sintered 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material is molded on 3D printer
Application is with embodiment 1, the processing temperature of described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material
Spend for 110 DEG C.
With embodiment 1, difference is that described diamine monomer is p-phenylenediamine and 2- (4- to the preparation method of described polyimides
Aminophenyl) -5 aminophenyl benzimidazoles mixture, and p-phenylenediamine and 2- (4- aminophenyl) -5 aminophenyl benzo
The mol ratio of imidazoles is 1：4.
The synthetic method of described 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides) is with embodiment 1.
Embodiment 4
The preparation method of described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material, with real
Apply example 1, difference is that described nano carbon powder is CNT；The particle diameter of described nano carbon powder is 100nm；Described carbon
The tap density of plain powder is 0.15kg/cm2；Described polyimides with the mass ratio of polyethersulfone resin, nano carbon powder is
45：100：3；The particle diameter of described polyimide resin is 80 μm；The particle diameter of polyethersulfone resin is 60 μm.
Described laser sintered 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material is molded on 3D printer
Application is with embodiment 1, the processing temperature of described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material
Spend for 140 DEG C.
With embodiment 1, difference is that described diamine monomer is p-phenylenediamine and 2- (4- to the preparation method of described polyimides
Aminophenyl) -5 aminophenyl benzimidazoles mixture, and p-phenylenediamine and 2- (4- aminophenyl) -5 aminophenyl benzo
The mol ratio of imidazoles is 1：3.
The synthetic method of described 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides) is with embodiment 1.
Comparative example 1
The preparation method of described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material, with real
Apply example 4.
Described laser sintered 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material is molded on 3D printer
Application is with embodiment 4.
With embodiment 4, difference is that described diamine monomer is p-phenylenediamine to the preparation method of described polyimides.
The synthetic method of described 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides) is with embodiment 1.
Comparative example 2
The preparation method of described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material, with real
Apply example 4.
Described laser sintered 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material is molded on 3D printer
Application is with embodiment 4.
The preparation method of described polyimides with embodiment 4, difference be described diamine monomer be 2- (4- aminophenyl)-
5 aminophenyl benzimidazoles.
The synthetic method of described 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides) is with embodiment 1.
Comparative example 3
The preparation method of described laser sintering and moulding 3D printing polyether sulfone/nano carbon powder consumptive material, comprises the following steps：
(1) it is dried：Nano carbon powder is put in high-speed mixer, under the conditions of 100 DEG C, 3h is dried；Described nano-sized carbon
Plain powder is CNT；The particle diameter of described nano carbon powder is 220nm；The tap density of described carbon powder is
0.15kg/cm2；
(2) it is blended：Add dried nano carbon powder in polyethersulfone resin and step (1) mixed in high speed in mass ratio
In conjunction machine, under the conditions of 50 DEG C, low speed interval mixes 30min, then mixed at high speed 30min；The particle diameter of described polyethersulfone resin
For 200 μm；Described polyethersulfone resin is 1 with the mass ratio of nano carbon powder：0.25；
(3) grind：Blended powder in step (2) is added in grinder, under the conditions of 320r/min, grinds 1.5h；
(4) it is dried：Blended powder in step (3) is dried 2h under the conditions of 90 DEG C, obtains laser sintering and moulding 3D printing
Polyether sulfone/nano carbon powder.
The application that described laser sintered 3D printing polyether sulfone/nano carbon powder consumptive material is molded on 3D printer
Laser sintered 3D printing polyether sulfone/nano carbon powder consumptive material is added to the confession of selective laser sintering and moulding machine
In powder cylinder, dusty material is equably layered in processing plane and is heated to processing temperature by powdering roller, and laser instrument sends sharp
Light, the switch of computer controlled laser and the angle of scanner so that laser beam processing plane on according to corresponding two dimension
Sheet-shaped is scanned, and after laser beam is inswept, workbench moves down a thickness, then powdering, laser beam flying, so instead
Multiple, obtain laser sintered part, wherein laser beam mode of scanning in processing plane scans for subregion；Described laser sintered one-tenth
The preheating temperature of type 3D printing polyether sulfone/nano carbon powder consumptive material is 72 DEG C；Described laser sintering and moulding 3D printing polyether sulfone/
The input energy density of nano carbon powder consumptive material is 0.30J/mm3；Described laser sintering and moulding 3D printing polyether sulfone/nano-sized carbon
The laser power of plain powder consumptive material is 16W；The scanning of described laser sintering and moulding 3D printing polyether sulfone/nano carbon powder consumptive material
Speed is 1900mm/s；The sintering spacing of described laser sintering and moulding 3D printing polyether sulfone/nano carbon powder consumptive material is
0.15mm；The thickness in monolayer of described laser sintering and moulding 3D printing polyether sulfone/nano carbon powder consumptive material is 0.15mm；Described sharp
The processing temperature of light sinter molding 3D printing polyether sulfone/nano carbon powder consumptive material is 125 DEG C.
Performance test
Tensile property:CMT5504 type electronic universal mechanics machine carries out test for tensile strength, by GB/T1040-
1992 standards make standard batten, and draw speed is 5mm/s.
Bending property:CMT5504 type electronic universal mechanics machine carries out bending property test, by GB/T9341-
2008 standards make standard batten, and test speed is 2mm/min.
Non-notch sample simple beam impact strength:XJC-25Z type mechanical combination balance weight impact testing machine is impacted
Test, makes standard batten by GB/T 1043-1993, and impact energy is 2J.
Table 1 the performance test results
| Tensile strength (MPa) | Bending strength (MPa) | Impact strength (MPa) | |
| Embodiment 1 | 87.71 | 152.18 | 78.45 |
| Embodiment 2 | 90.24 | 159.61 | 80.24 |
| Embodiment 3 | 93.66 | 164.21 | 84.52 |
| Embodiment 4 | 105.86 | 176.64 | 98.57 |
| Comparative example 1 | 85.14 | 142.20 | 76.88 |
| Comparative example 2 | 86.03 | 148.33 | 77.15 |
| Comparative example 3 | 84.06 | 136.13 | 75.62 |
As can be seen that the polyimides prepared for p-phenylenediamine with described diamine monomer is obtained from above-mentioned the performance test results
The laser sintering and moulding 3D printing arrived/polyimides polyether sulfone/nano carbon powder consumptive material, described diamine monomer are 2- (4- ammonia
Base phenyl) -5 aminophenyl benzimidazoles preparations laser sintering and moulding 3D printing/polyimides polyethers of obtaining of polyimides
Sulfone/nano carbon powder consumptive material and described laser sintering and moulding 3D printing polyether sulfone/nano carbon powder consumptive material are compared, the present invention
Not only overcome nano carbon powder and polyimide resin, the compatibility of polyethersulfone resin, and by laser sintered principle be
Under almost without external force applying condition, rapidoprint makes the drip molding sintering out have very strong physical property and chemical property,
Also have that high temperature resistant and application is wide.
Aforesaid example is merely illustrative, for explaining some features of the method for the invention.Appended right will
Seek the scope as wide as possible being intended to require to be contemplated that, and embodiments as presented herein is only according to all possible enforcement
The explanation of the embodiment of the selection of combination of example.Therefore, the purpose of applicant is that appended claim is not illustrated this
The selectional restriction of the example of bright feature.Some number ranges used also include sub- model within the claims
Enclose, the change in these scopes also should be construed to be covered by appended claim in the conceived case.
Claims (10)
1. a kind of preparation method of laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material,
It is characterized in that, comprise the following steps：
(1) it is dried：Nano carbon powder is put in high-speed mixer, under the conditions of 100 DEG C, 3h is dried；
(2) it is blended：Add in mass ratio in polyimides and polyethersulfone resin and step (1) dried nano carbon powder in
In high-speed mixer, under the conditions of 50 DEG C, low speed interval mixes 30min, then mixed at high speed 30min；
(3) grind：Blended powder in step (2) is added in grinder, under the conditions of 320r/min, grinds 1.5h；
(4) it is dried：Blended powder in step (3) is dried 2h under the conditions of 90 DEG C, obtains laser sintering and moulding 3D printing polyamides
Imines/polyether sulfone/nano carbon powder；
Wherein, described polyimides and the mass ratio of polyethersulfone resin, nano carbon powder are (30～60)：100：(0.1～
5).
2. the system of laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material according to claim 1
Preparation Method is it is characterised in that the monomer of preparing of described polyimides includes dianhydride monomer, diamine monomer；Described diamine monomer bag
Include aromatic diamines, imidazoles diamines.
3. the system of laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material according to claim 2
Preparation Method it is characterised in that described dianhydride monomer be selected from 3,3 '-(isophthalic two epoxide) double (phthalic anhydrides), 4,4 '-oxygen is double
Phthalic anhydride, 5,5 '-oxo (4,1- phenoxy group)] one or more in double phthalic anhydrides.
4. the system of laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material according to claim 2
Preparation Method is it is characterised in that the mol ratio of described aromatic diamines, imidazoles diamines is 1：(2～4).
5. the system of laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material according to claim 2
Preparation Method is it is characterised in that described aromatic diamines are selected from p-phenylenediamine, Isosorbide-5-Nitrae ,-bis- (4- amino-benzene oxygen) benzene, Isosorbide-5-Nitrae ,-bis- (3-
Amino-benzene oxygen) benzene, 1,3, one or more in-bis- (4- amino-benzene oxygen) benzene, 1,4- diaminobenzene；Described imidazoles diamines choosing
From 2- (4- aminophenyl) -5 aminophenyl benzimidazole, 2- (3- aminophenyl) -5 aminophenyl benzimidazole, 2,2 '-bis-
(4- aminophenyl) -5,5 '-bibenzimidaz sigmale, 2,2 '-bis- (4- aminophenyl) benzimidazoles, 2,2 '-bis- (3- aminophenyls)
One or more in benzimidazole.
6. the system of laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material according to claim 1
Preparation Method is it is characterised in that the particle diameter of described polyimide resin is 10～800 μm.
7. the system of laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material according to claim 1
Preparation Method is it is characterised in that the particle diameter of described nano carbon powder is 100～1000nm.
8. the system of laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material according to claim 1
Preparation Method is it is characterised in that the particle diameter of described polyethersulfone resin is 10～400 μm.
9. the system of laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material according to claim 1
Preparation Method it is characterised in that described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material pre-
Hot temperature is 70～80 DEG C；The input of described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material
Energy density is 0.1～0.4J/mm3；Described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumption
The laser power of material is 5～40W.
10. laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material according to claim 1
Preparation method is it is characterised in that described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumptive material
Sweep speed is 1500～2000mm/s；Described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumption
The sintering spacing of material is 0.1～0.2mm；Described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumption
The thickness in monolayer of material is 0.1～0.2mm；Described laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumption
The processing temperature of material is 110～150 DEG C.
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| CN109749442A (en) * | 2018-12-17 | 2019-05-14 | 浙江大学宁波理工学院 | A kind of selective laser sintering polyimide powder powder material and its preparation method and application |
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