CN106380847B - A kind of laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies preparation method - Google Patents
A kind of laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies preparation method 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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The present invention provides a kind of laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies preparation method, comprising the following steps: (1) nano carbon powder is put into high-speed mixer, dry 3h under the conditions of 100 DEG C；(2) the nano carbon powder in polyimides and polyethersulfone resin and step (1) after drying is added 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；(3) blended powder in step (2) is added in grinder, under the conditions of 320r/min, grinds 1.5h；(4) blended powder in step (3) is dried to 2h under the conditions of 90 DEG C, obtains laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder；The mass ratio of the polyimides and polyethersulfone resin, nano carbon powder is (30~60): 100:(0.1~5).
Description
Technical field
The present invention relates to a kind of preparation methods 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 technique
3D printing (3D printing) is one kind based on digital model file, with flow-like, powdered, silk
(stick) shape etc. is curable, bonds, alloying material, and the technology of object is constructed by way of successively solidifying, bonding, fuse.3D
Printing technique appears in mid-term the 1990s, actually utilizes the newest rapid shaping for the technologies such as photocuring and paper layer be folded
Device.It is essentially identical with common print working principle, and printer is provided with liquid or powder etc. " printed material ", connects with computer
It after connecing, is controlled by computer and " printed material " is stacked up from level to level, the blueprint on computer is finally become in kind.This dozen
Print technology is known as 3D three-dimensional printing technology.Traditional manufacture, which generally requires, to be cut raw material or is drilled, that is, subtracts material manufacture,
It can be mass-produced；3D printing is that material is stacked to bonding, fusion, i.e. increasing material manufacturing from level to level；Quickly personalized system can be achieved
It makes, the impossible shape of traditional manufacture can be produced.
Selective laser sintering (SLS) belongs to a kind of method of 3D printing technique, powdered using controllable laser-light beam melts
Material carries out accumulation layer by layer and is sintered out complicated three-dimensional model.Developing this kind of 3D printing technique industrialization of selective laser sintering
Process in, manufacturing equipment and material foundation research be two big key technologies.Selective laser sintering requires more raw material
Harshness, material are needed with powdered offer；In sintering process, material still must after the states of matters variation such as fast melt and solidification
With good physics, chemical property.Currently, being usually used in the material of selective laser sintering research, there are metal material, ceramic material
Material, polymer material and the composite material between them, but the material for being applied to selective laser sintering and moulding is not only planted
Class is few, expensive, and processing technology is also more complicated, thus is difficult to realize industrialization.
Nano carbon powder is from a wealth of sources and cheap；Adhesive of the polyethersulfone resin (PES) as composite material, tool
There is the features such as high mechanical strength, good stability of the dimension and excellent moulding processability.
Polyimides (polyimide, PI) is that containing imide ring there is excellent heat resistance, chemically-resistant to stablize on main chain
A kind of high molecular 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, in the electronics industry as insulating materials, in some general technologies
It is used as heat absorption and sound-absorbing material, structural adhesive and protective coating, and gradually starts in integrated circuit, liquid crystal display, shines
It is widely used in the high-tech areas such as device, fuel cell, optical-fibre communications, gas separation.But since its is special
Molecular structure and be limited by very large, main processing is more difficult.
Therefore, the present invention synthesizes the fire resistant polyimide of 3D printing technique by the adjustment of polyimide structures, uses
In preparing selective laser sintering 3D printing polyimides/polyether sulfone/nano carbon powder composite material, can be convenient quick
Ground shape precision, abnormal shape, complexity, high temperature resistant, high mechanical strength, good stability of the dimension component.
Summary of the invention
The present invention provides a kind of laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies system
Preparation Method, which comprises the following steps:
(1) dry: nano carbon powder to be put into high-speed mixer, dry 3h under the conditions of 100 DEG C；
(2) it is blended: the nano carbon powder in mass ratio in addition polyimides and polyethersulfone resin and step (1) after drying
End is in high-speed mixer, and under the conditions of 50 DEG C, low speed interval mixes 30min, then mixed at high speed 30min；
(3) it grinds: blended powder in step (2) is added in grinder, under the conditions of 320r/min, grind 1.5h；
(4) it dries: blended powder in step (3) being dried into 2h under the conditions of 90 DEG C, obtains laser sintering and moulding 3D printing
Polyimides/polyether sulfone/nano carbon powder；
Wherein, the mass ratio of the polyimides and polyethersulfone resin, nano carbon powder is (30~60): 100:(0.1
~5).
In one embodiment, the monomer for preparing of the polyimides includes dianhydride monomer, diamine monomer；The diamines
Monomer includes aromatic diamines, imidazoles diamines.
In one embodiment, the dianhydride monomer is selected from 3,3 '-(two oxygroup of isophthalic) bis- (phthalic anhydrides), 4,
4 '-oxygen double phthalic anhydrides, 5,5 '-oxos (4,1- phenoxy group)] it is one or more in double phthalic anhydrides.
In one embodiment, the aromatic diamines, imidazoles diamines molar ratio be 1:(2~4).
In one embodiment, the 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 are one or more in-bis- (4- amino-benzene oxygen) benzene, 1,4- diaminobenzene；The miaow
Azoles diamines be selected from 2- (4- aminophenyl) -5 aminophenyl benzimidazole, -5 aminophenyl benzimidazole of 2- (3- aminophenyl),
2,2 '-bis- (4- aminophenyls) -5,5 '-bibenzimidaz sigmales, 2,2 '-bis- (4- aminophenyl) benzimidazoles, 2,2 '-bis- (3- ammonia
Base phenyl) it is one or more in benzimidazole.
In one embodiment, the partial size of the polyimide resin is 40~800 μm.
In one embodiment, the partial size of the nano carbon powder is 100~1000nm.
In one embodiment, the partial size of the polyethersulfone resin is 10~400 μm.
In one embodiment, the laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumption
The preheating temperature of material is 70~80 DEG C；The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies
Input energy density be 0.1~0.4J/mm3；The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon
The laser power of powder supplies is 5~40W.
In one embodiment, the laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumption
The sweep speed of material is 1500~2000mm/s；The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder
The sintering spacing of last consumptive material is 0.1~0.2mm；The 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；The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder
The processing temperature of last consumptive material is 110~150 DEG C.
The above-mentioned of the application and other features, aspects and advantages are more readily understood with reference to following detailed description.
Specific embodiment
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this hair can be more easily to understand
Bright content.Unless otherwise defined, all technologies used herein and scientific term have common with fields of the present invention
The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.
As used herein term " by ... preparation " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements
Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or
Such composition, step, method, product or the intrinsic element of device.
Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this
Phrase will make claim closed, so that it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body,
It is only limited to element described in the clause；Other elements are not excluded except the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end
Value and all integers and score in the range.
Singular includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item described thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used to modify quantity, and it is specific to indicate that the present invention is not limited to this
Quantity further includes the acceptable modified part without will lead to the change of dependency basis this function close with the quantity.Phase
It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, approximate
Term likely corresponds to the precision of the instrument of measurement numerical value.In present specification and claims, range limits can be with
Combination and/or exchange, these ranges if not stated otherwise include all subranges contained therebetween.
In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component
(i.e. frequency of occurrence) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number
The element or component of form also include plural form, unless the obvious purport of the quantity refers to singular.
" polymer " means polymerizable compound prepared by the monomer by the identical or different type of polymerization.Generic term
" polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " copolymer ".
" copolymer " means the polymer by polymerization at least two different monomers preparation.Generic term " copolymer " includes
(it is general with term " terpolymer " for term " copolymer " (it is generally to refer to the polymer prepared by two kinds of different monomers)
To refer to the polymer prepared by three kinds of different monomers).It also includes the polymer manufactured by polymerizeing more kinds of monomers.
" blend " means that two or more polymer mixes the polymer to be formed by physics or chemical method jointly.
The present invention provides a kind of laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies system
Preparation Method, which comprises the following steps:
(1) dry: nano carbon powder to be put into high-speed mixer, dry 3h under the conditions of 100 DEG C；
(2) it is blended: the nano carbon powder in mass ratio in addition polyimides and polyethersulfone resin and step (1) after drying
End is in high-speed mixer, and under the conditions of 50 DEG C, low speed interval mixes 30min, then mixed at high speed 30min；
(3) it grinds: blended powder in step (2) is added in grinder, under the conditions of 320r/min, grind 1.5h；
(4) it dries: blended powder in step (3) being dried into 2h under the conditions of 90 DEG C, obtains laser sintering and moulding 3D printing
Polyimides/polyether sulfone/nano carbon powder；
Wherein, the mass ratio of the polyimides and polyethersulfone resin, nano carbon powder is (30~60): 100:(0.1
~5).
Polyimide resin
Polyimides (polyimide, PI) is that containing imide ring there is excellent heat resistance, chemically-resistant to stablize on main chain
A kind of high molecular material of property, mechanical property and electrical property.
Polyethersulfone resin
Polyethersulfone resin is amorphous thermoplastic's high molecular material, and molecular structure is made of phenyl, ether and sulfuryl.Ether
Making macromolecule chain section in the molten state has good mobility, improve forming property, sulfuryl award high marks sub- heat resistance with
And rigidity.PES has had both the characteristics of high impact properties, highly resistance deformability and excellent formability, especially at high temperature can be with
Outstanding advantages of being used continuously and performance itself can still be kept to stablize under conditions of temperature great change.
In one embodiment, the monomer for preparing of the polyimides includes dianhydride monomer, diamine monomer；The diamines
Monomer includes aromatic diamines, imidazoles diamines.
In one embodiment, the dianhydride monomer is selected from 3,3 '-(two oxygroup of isophthalic) bis- (phthalic anhydrides), 4,
4 '-oxygen double phthalic anhydrides, 5,5 '-oxos (4,1- phenoxy group)] it is one or more in double phthalic anhydrides；Preferably,
The dianhydride monomer is selected from 3,3 '-(two oxygroup of isophthalic) bis- (phthalic anhydrides).
In one embodiment, the aromatic diamines, imidazoles diamines molar ratio be 1:(2~4)；Preferably, described
Aromatic diamines, imidazoles diamines molar ratio be 1:3.
In one embodiment, the 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 are one or more in-bis- (4- amino-benzene oxygen) benzene, 1,4- diaminobenzene；The miaow
Azoles diamines be selected from 2- (4- aminophenyl) -5 aminophenyl benzimidazole, -5 aminophenyl benzimidazole of 2- (3- aminophenyl),
2,2 '-bis- (4- aminophenyls) -5,5 '-bibenzimidaz sigmales, 2,2 '-bis- (4- aminophenyl) benzimidazoles, 2,2 '-bis- (3- ammonia
Base phenyl) it is one or more in benzimidazole；Preferably, the aromatic diamines are selected from Isosorbide-5-Nitrae-diaminobenzene；The imidazoles diamines
Selected from -5 aminophenyl benzimidazole of 2- (3- aminophenyl).
In one embodiment, the partial size of the polyimide resin is 40~800 μm；Preferably, the polyamides is sub-
The partial size of polyimide resin is 40~600 μm；Preferably, the partial size of the polyimide resin is 40~100 μm.
In one embodiment, the preparation method of described 3,3 '-(two oxygroup of isophthalic) bis- (phthalic anhydrides), including
Following steps:
(1) 3- monochloro phthalic anhydride is dissolved in acetic anhydride, until being completely dissolved, adds methylamine water solution, heated
It after reacting 3.5-5h, is cooled to room temperature, and is cooled to 10 DEG C hereinafter, filtering, dry to get product A with ice water；
(2) the product A in step (1) is dissolved in dimethyl sulfoxide with resorcinol, until being completely dissolved, adds catalyst
And heating reflux reaction, TLC tracks resorcinol in reaction process, until in system without resorcinol after, continue back flow reaction
0.5-2h is then filtered, is cooling, washing, being centrifuged, is dry to get product B；
(3) the product B in step (2) is mixed with sodium hydroxide solution, is heated to boiling, it is anti-after solid dissolution
Answer 0.5-2h, it is 7-8 that concentrated hydrochloric acid, which is then added, and adjusts pH, continue to boil 5-15min, be filtered to remove insoluble solids, by filtrate plus
Heat is extremely boiled, and adjusting pH with concentrated hydrochloric acid is 1-2, cooling to get product C；
(4) the product C in step (3) is mixed with dehydrating agent, agitating and heating, dewatering and filtering, washing, drying, i.e.,
Obtain 3,3 '-(two oxygroup of isophthalic) bis- (phthalic anhydrides).
In one embodiment, the polyimides preparation method the following steps are included:
(1) in the DMAc solution that the dianhydride powder weighed up is added to diamines by room temperature under stiring, stirring 6h or so
The polyamic acid solution for being 10% or so to solid content；
(2) end-capping reagent phthalic anhydride is added into step (1), continues stirring 20h and obtains the polyamic acid solution of phthalic anhydride sealing end；
(3) it to a certain amount of acid anhydrides being added in step (2) and triethylamine carries out chemical imidization, reacts after 20h in ethyl alcohol
Middle precipitating, 200 DEG C of heat treatment 1h of vacuum, obtain after the polyimide powder ethyl alcohol being settled out extracts in Soxhlet extractor
Polyimides sample.
In one embodiment, the partial size of the nano carbon powder is 100~1000nm；Preferably, the nanometer
The partial size of carbon powder is 100~800nm；It is highly preferred that the partial size of the nano carbon powder is 200~500nm.
In one embodiment, the tap density of the carbon powder is 0.1~0.2kg/cm2；Preferably, the carbon
The tap density of plain powder is 0.15kg/cm2。
In one embodiment, the partial size of the polyethersulfone resin is 10~400 μm；Preferably, the polyether sulfone tree
The partial size of rouge is 10~200 μm；It is highly preferred that the partial size of the polyethersulfone resin is 40~70 μm.
Nano carbon powder can reach submicron order even nanoscale in the present invention, have meso-position radius grain small, size distribution
The characteristics of narrow range, property are stablized；Thin-walled model or small parts can be manufactured by this rapid shaping powder material, manufactured
Product has the features such as surface gloss is high, and intensity is good, and precision is high out.
Selective Laser Sintering
Selective Laser Sintering (Selective Laser Sintering) is important one in rapid shaping technique
A branch, it is integrated with Fundamental Course of Mechanic Manufacturing, laser technology, material science, modern scientist engineering, computer technology, modern survey
The technologies such as examination technology and CAD/CAM theoretical basis and application.The technology can manufacture out part original in a relatively short period of time
Type and mold are widely used in the every field of machine-building.The technology is based on layering-principle of stacking, utilizes computer control
The motion profile of high energy laser beam processed utilizes the high energy melting metal powder of laser beam, after removing to laser facula, metal
Liquid quickly solidification again.Whole process is exactly that laser facula moves from point to surface, then by the process in face to body, each part is
It is layering by forming face.The technology path of SLS process is to establish corresponding CAD model first against part, will
Model imports formation system and carries out step section, and each layer of obtained slice includes the geological information in section, generates STL format text
Part.Then the track that high energy laser beam is sliced along each layer under control of the computer is scanned, and is melted in the region
Metal powder.To repave next layer of powder after one layer, above procedure is repeated until part forming.
In one embodiment, the laser sintered 3D printing polyimides/polyether sulfone/nano carbon powder supplies exist
Molding application, feature on 3D printer are as follows: by laser sintered 3D printing polyimides/polyether sulfone/nano carbon powder supplies
It is added in the powder supply cylinder of selective laser sintering and moulding machine, dusty material is equably layered in processing plane simultaneously by powdering idler wheel
It is heated to processing temperature, laser issues laser, the switch of computer controlled laser and the angle of scanner, so that laser
Beam is scanned in processing plane according to corresponding two-dimensional slice shape, and after laser beam is inswept, workbench moves down a layer
Thickness, then powdering, laser beam flying obtain laser sintered part repeatedly, the mode that wherein laser beam scans in processing plane
For subregion scanning.
In one embodiment, the laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumption
The preheating temperature of material is 70~80 DEG C；The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies
Input energy density be 0.1~0.4J/mm3；The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon
The laser power of powder supplies is 5~40W；Preferably, the laser sintering and moulding 3D printing polyimides/polyether sulfone/nanometer
The preheating temperature of carbon powder supplies is 70~75 DEG C；The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano-sized carbon
The input energy density of plain powder supplies is 0.12~0.32J/mm3；The laser sintering and moulding 3D printing polyimides/polyethers
Sulfone/nano carbon powder supplies laser power is 5~30W.
In one embodiment, the laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumption
The sweep speed of material is 1500~2000mm/s；The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder
The sintering spacing of last consumptive material is 0.1~0.2mm；The 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；The 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, the laser sintering and moulding 3D printing polyimides/polyether sulfone/is received
The sweep speed of rice carbon powder supplies is 1900mm/s；The laser sintering and moulding 3D printing polyimides/polyether sulfone/nanometer
The sintering spacing of carbon powder supplies is 0.15mm；The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon
The thickness in monolayer of powder supplies is 0.15mm；The 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 high by preparing a kind of glass transition temperature, and melting temperature is lower to be suitable for 3D printing production
Using the polyimides of temperature higher " workpiece ", second aspect passes through optimization polyimides, polyether sulfone and nano carbon powder
Component ratio, the uniformity of various powder qualities, overcome nano carbon powder and polyimide resin, polyethersulfone resin
Compatibility, and be that rapidoprint has the drip molding being sintered out under the conditions of applying almost without external force by laser sintered principle
There are very strong physical property and chemical property, and the scheme of the Design the laboratory material proposed is easy quickly, greatly when reduction
Between and economize on resources.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
The some nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available, it is purchased from traditional Chinese medicines chemical reagent.
Embodiment 1
The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies preparation method, including
Following steps:
(1) dry: nano carbon powder to be put into high-speed mixer, dry 3h under the conditions of 100 DEG C；The nano-sized carbon
Plain powder is acetylene black；The partial size of the nano carbon powder is 1000nm；The tap density of the carbon powder is 0.12kg/
cm2；
(2) it is blended: the nano carbon powder in mass ratio in addition polyimides and polyethersulfone resin and step (1) after drying
End is in high-speed mixer, and under the conditions of 50 DEG C, low speed interval mixes 30min, then mixed at high speed 30min；The polyamides is sub-
The mass ratio of amine and polyethersulfone resin, nano carbon powder is 30:100:0.1；The partial size of the polyimide resin is 800 μ
m；The partial size of polyethersulfone resin is 400 μm；
(3) it grinds: blended powder in step (2) is added in grinder, under the conditions of 320r/min, grind 1.5h；
(4) it dries: blended powder in step (3) being dried into 2h under the conditions of 90 DEG C, obtains laser sintering and moulding 3D printing
Polyimides/polyether sulfone/nano carbon powder.
The laser sintered 3D printing polyimides/polyether sulfone/nano carbon powder supplies are molding on 3D printer
Using
Laser sintered 3D printing polyimides/polyether sulfone/nano carbon powder supplies are added to selective laser sintering
In the powder supply cylinder of molding machine, dusty material is equably layered in processing plane and is heated to processing temperature by powdering idler wheel, swashs
Light device issues laser, the switch of computer controlled laser and the angle of scanner, so that laser beam basis in processing plane
Corresponding two-dimensional slice shape is scanned, and after laser beam is inswept, workbench moves down a thickness, then powdering, laser beam are swept
It retouches, repeatedly, obtains laser sintered part, the mode that wherein laser beam scans in processing plane is subregion scanning；It is described
Laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies preheating temperature is 80 DEG C；The laser is burnt
Forming type 3D printing polyimides/polyether sulfone/nano carbon powder supplies input energy density is 0.24J/mm3；It is described to swash
Light sinter molding 3D printing polyimides/polyether sulfone/nano carbon powder supplies laser power is 10W；It is described laser sintered
Molding 3D printing polyimides/polyether sulfone/nano carbon powder supplies sweep speed is 1900mm/s；It is described it is laser sintered at
Type 3D printing polyimides/polyether sulfone/nano carbon powder supplies sintering spacing is 0.2mm；The laser sintering and moulding 3D
Printing polyimides/polyether sulfone/nano carbon powder supplies thickness in monolayer is 0.2mm；The laser sintering and moulding 3D printing
Polyimides/polyether sulfone/nano carbon powder supplies processing temperature is 150 DEG C.
The preparation method of the polyimides, comprising the following steps:
(1) weigh 0.05mol 3,3 '-(two oxygroup of isophthalic) bis- (phthalic anhydrides) be added to 0.025mol to benzene
It is added in three-necked flask, adds in the DMAc solution of -5 aminophenyl benzimidazole of 2- (4- aminophenyl) of diamines and 0.025mol
Enter 230mLDMAc, is put into low temperature bath (- 5 DEG C), quickly stirs, after reacting 6h；
(2) phthalic anhydride end-capping reagent is added into step (1), DMAc is during which added, solution is gradually diluted, continues to stir the left side 20h
The right side obtains the PAA solution of 10% phthalic anhydride of mass concentration sealing end；
(3) 0.3mol acetic anhydride, 0.015mol triethylamine and 0.035mol pyridine are added into step (2) and carries out chemistry Asia
Amination precipitates in water after about reacting 20h at 60 DEG C, and the polyimide powder ethyl alcohol being precipitated out is in Soxhlet extractor
200 DEG C of heat treatment 1h of vacuum, obtain polyimides after middle extraction.
The synthetic method of described 3,3 '-(two oxygroup of isophthalic) bis- (phthalic anhydrides), comprising the following steps:
(1) 3- monochloro phthalic anhydride is placed in reaction vessel, 3- monochloro phthalic anhydride is pressed with acetic anhydride
According to the proportion of 13g:45ml, acetic anhydride is added, stirs 30min at 50 DEG C, until 3- monochloro phthalic anhydride is completely dissolved, it will
According to the proportion of 13g:9ml, the methylamine for adding mass fraction 30% is water-soluble for 3- monochloro phthalic anhydride and methylamine water solution
Liquid is heated to reflux, and after toluene band water reaction 5h, is cooled to room temperature, and with ice water be cooled to 5 DEG C hereinafter, filtering, it is dry to get
Product A；
(2) by the product A and resorcinol that are weighed according to the quality proportioning of 1.5:1 in step (1) in reaction vessel, and
The dimethyl sulfoxide of 100ml is added, stirring is completely dissolved raw material, adds 2% potassium carbonate that mass fraction is total raw material
And be heated to reflux, back flow reaction 3h, heat filtering, filtrate is cooled to room temperature, and it pours into water and is stirred continuously, the precipitating warp of precipitation
Centrifuge is centrifuged to obtain solid, obtain solid through hydrochloric acid acidification, washing, it is dry after, using dehydrated alcohol as solvent and with cable-styled
Extractor remove filtering Resorcino, then use chloroform, until TLC examine do not measure resorcinol to get product B；
(3) by step (2) product B and mass fraction be 22% sodium hydroxide solution according to 4g:26ml match into
Row mixing, is heated to boiling, and reacts 2h after solid dissolution, and it is 7- that the concentrated hydrochloric acid that mass fraction is 38%, which is then added, and adjusts pH
8, continue to boil 10min, be filtered to remove insoluble solids, filtrate is heated to boiling, and the concentrated hydrochloric acid for being 38% with mass fraction
Adjusting pH is 1-2, cooling to get 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,
Drying is to get 3,3 '-(two oxygroup of isophthalic) bis- (phthalic anhydrides), yield 99%.
Embodiment 2
The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies preparation method, with real
Example 1 is applied, difference is that the nano carbon powder is graphene；The partial size of the nano carbon powder is 600nm；The carbon
The tap density of powder is 0.18kg/cm2；The mass ratio of the polyimides and polyethersulfone resin, nano carbon powder is 40:
100:2；The partial size of the polyimide resin is 600 μm；The partial size of polyethersulfone resin is 100 μm.
The laser sintered 3D printing polyimides/polyether sulfone/nano carbon powder supplies are molding on 3D printer
Using same embodiment 1, difference is the laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies
Sintering spacing be 0.15mm；The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies list
Layer is with a thickness of 0.15mm；The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies processing temperature
Degree is 140 DEG C.
The preparation method is the same as that of Example 1 for the polyimides, and difference is that the diamine monomer is p-phenylenediamine and 2- (4-
Aminophenyl) -5 aminophenyl benzimidazoles mixture, and -5 aminophenyl benzo of p-phenylenediamine and 2- (4- aminophenyl)
The molar ratio of imidazoles is 1:2.
The synthetic method of 3,3 '-(two oxygroup of isophthalic) bis- (phthalic anhydrides) is the same as embodiment 1.
Embodiment 3
The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies preparation method, with real
Example 1 is applied, difference is that the nano carbon powder is carbon nanotube；The partial size of the nano carbon powder is 100nm；The carbon
The tap density of plain powder is 0.16kg/cm2；The mass ratio of the polyimides and polyethersulfone resin, nano carbon powder is
60:100:5；The partial size of the polyimide resin is 10 μm；The partial size of polyethersulfone resin is 10 μm.
The laser sintered 3D printing polyimides/polyether sulfone/nano carbon powder supplies are molding on 3D printer
Using same embodiment 1, the laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies processing temperature
Degree is 110 DEG C.
The preparation method is the same as that of Example 1 for the polyimides, and difference is that the diamine monomer is p-phenylenediamine and 2- (4-
Aminophenyl) -5 aminophenyl benzimidazoles mixture, and -5 aminophenyl benzo of p-phenylenediamine and 2- (4- aminophenyl)
The molar ratio of imidazoles is 1:4.
The synthetic method of 3,3 '-(two oxygroup of isophthalic) bis- (phthalic anhydrides) is the same as embodiment 1.
Embodiment 4
The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies preparation method, with real
Example 1 is applied, difference is that the nano carbon powder is carbon nanotube；The partial size of the nano carbon powder is 100nm；The carbon
The tap density of plain powder is 0.15kg/cm2；The mass ratio of the polyimides and polyethersulfone resin, nano carbon powder is
45:100:3；The partial size of the polyimide resin is 80 μm；The partial size of polyethersulfone resin is 60 μm.
The laser sintered 3D printing polyimides/polyether sulfone/nano carbon powder supplies are molding on 3D printer
Using same embodiment 1, the laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies processing temperature
Degree is 140 DEG C.
The preparation method is the same as that of Example 1 for the polyimides, and difference is that the diamine monomer is p-phenylenediamine and 2- (4-
Aminophenyl) -5 aminophenyl benzimidazoles mixture, and -5 aminophenyl benzo of p-phenylenediamine and 2- (4- aminophenyl)
The molar ratio of imidazoles is 1:3.
The synthetic method of 3,3 '-(two oxygroup of isophthalic) bis- (phthalic anhydrides) is the same as embodiment 1.
Comparative example 1
The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies preparation method, with real
Apply example 4.
The laser sintered 3D printing polyimides/polyether sulfone/nano carbon powder supplies are molding on 3D printer
Using same embodiment 4.
For the preparation method of the polyimides with embodiment 4, difference is that the diamine monomer is p-phenylenediamine.
The synthetic method of 3,3 '-(two oxygroup of isophthalic) bis- (phthalic anhydrides) is the same as embodiment 1.
Comparative example 2
The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies preparation method, with real
Apply example 4.
The laser sintered 3D printing polyimides/polyether sulfone/nano carbon powder supplies are molding on 3D printer
Using same embodiment 4.
For the preparation method of the polyimides with embodiment 4, difference is that the diamine monomer is 2- (4- aminophenyl)-
5 aminophenyl benzimidazoles.
The synthetic method of 3,3 '-(two oxygroup of isophthalic) bis- (phthalic anhydrides) is the same as embodiment 1.
Comparative example 3
The preparation method of the laser sintering and moulding 3D printing polyether sulfone/nano carbon powder supplies, comprising the following steps:
(1) dry: nano carbon powder to be put into high-speed mixer, dry 3h under the conditions of 100 DEG C；The nano-sized carbon
Plain powder is carbon nanotube；The partial size of the nano carbon powder is 220nm；The tap density of the carbon powder is
0.15kg/cm2；
(2) be blended: the nano carbon powder in mass ratio in addition polyethersulfone resin and step (1) after drying is mixed in high speed
In conjunction machine, under the conditions of 50 DEG C, low speed interval mixes 30min, then mixed at high speed 30min；The partial size of the polyethersulfone resin
It is 200 μm；The mass ratio of the polyethersulfone resin and nano carbon powder is 1:0.25；
(3) it grinds: blended powder in step (2) is added in grinder, under the conditions of 320r/min, grind 1.5h；
(4) it dries: blended powder in step (3) being dried into 2h under the conditions of 90 DEG C, obtains laser sintering and moulding 3D printing
Polyether sulfone/nano carbon powder.
Laser sintered 3D printing polyether sulfone/nano carbon powder supplies molding application on 3D printer
Laser sintered 3D printing polyether sulfone/nano carbon powder supplies are 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 idler wheel, and laser, which issues, to swash
Light, the switch of computer controlled laser and the angle of scanner, so that laser beam is in processing plane according to corresponding two dimension
Sheet-shaped is scanned, and after laser beam is inswept, workbench moves down a thickness, then powdering, and laser beam flying is so anti-
It is multiple, laser sintered part is obtained, the mode that wherein laser beam scans in processing plane is subregion scanning；It is described it is laser sintered at
Type 3D printing polyether sulfone/nano carbon powder supplies preheating temperature is 72 DEG C；The laser sintering and moulding 3D printing polyether sulfone/
The input energy density of nano carbon powder supplies is 0.30J/mm3；The laser sintering and moulding 3D printing polyether sulfone/nano-sized carbon
The laser power of plain powder supplies is 16W；The scanning of the laser sintering and moulding 3D printing polyether sulfone/nano carbon powder supplies
Rate is 1900mm/s；The sintering spacing of the laser sintering and moulding 3D printing polyether sulfone/nano carbon powder supplies is
0.15mm；The thickness in monolayer of the laser sintering and moulding 3D printing polyether sulfone/nano carbon powder supplies is 0.15mm；It is described to swash
Light sinter molding 3D printing polyether sulfone/nano carbon powder supplies processing temperature is 125 DEG C.
Performance test
Tensile property: test for tensile strength is carried out on CMT5504 type electronic universal mechanics machine, by GB/T1040-
Standard batten, tensile speed 5mm/s is made in 1992 standards.
Bending property: bending property test is carried out on CMT5504 type electronic universal mechanics machine, by GB/T9341-
Standard batten, test speed 2mm/min is made in 2008 standards.
Non-notch sample simple beam impact strength: it is impacted on XJC-25Z type mechanical combination balance weight impact testing machine
Test, is made standard batten, impact energy 2J by GB/T 1043-1993.
1 the performance test results of table
| 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 being that polyimides prepared by p-phenylenediamine obtains with the diamine monomer from above-mentioned the performance test results
The laser sintering and moulding 3D printing arrived/polyimides polyether sulfone/nano carbon powder supplies, the diamine monomer are 2- (4- ammonia
Base phenyl) preparation of -5 aminophenyl benzimidazoles the obtained laser sintering and moulding 3D printing/polyimides polyethers of polyimides
Sulfone/nano carbon powder supplies and the laser sintering and moulding 3D printing polyether sulfone/nano carbon powder supplies are compared, the present invention
The compatibility of nano carbon powder and polyimide resin, polyethersulfone resin is not only overcome, and is by laser sintered principle
Rapidoprint makes the drip molding being sintered out have very strong physical property and chemical property under the conditions of applying almost without external force,
Also there is high temperature resistant and application field is wide.
Example above-mentioned is merely illustrative, and is used to explain the present invention some features of the method.Appended right is wanted
The range as wide as possible for being intended to require to be contemplated that is sought, and embodiments as presented herein is only according to all possible implementation
The explanation of the embodiment of the combined selection of example.Therefore, the purpose of applicant is that the attached claims are not illustrated this hair
The exemplary selectional restriction of bright feature.Some numberical ranges used also include sub- model in the claims
It encloses, the variation in these ranges should also be construed to be covered by the attached claims in the conceived case.
Claims (6)
1. a kind of laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies preparation method,
Characterized by comprising the following steps:
(1) dry: nano carbon powder to be put into high-speed mixer, dry 3h under the conditions of 100 DEG C；
(2) be blended: nano carbon powder after dry in addition polyimides and polyethersulfone resin and step (1) in mass ratio in
In high-speed mixer, under the conditions of 50 DEG C, low speed interval mixes 30min, then mixed at high speed 30min；
(3) it grinds: blended powder in step (2) is added in grinder, under the conditions of 320r/min, grind 1.5h；
(4) it dries: blended powder in step (3) being dried into 2h under the conditions of 90 DEG C, obtains laser sintering and moulding 3D printing polyamides
Imines/polyether sulfone/nano carbon powder；
Wherein, the mass ratio of the polyimides and polyethersulfone resin, nano carbon powder is (30~60): 100:(0.1~
5)；The monomer for preparing of the polyimides includes dianhydride monomer and diamine monomer；The diamine monomer includes aromatic diamines and miaow
Azoles diamines；The aromatic diamines, imidazoles diamines molar ratio be 1:(2~4)；The dianhydride monomer is 3,3 '-(isophthalic dioxies
Base) bis- (phthalic anhydrides)；The aromatic diamines are p-phenylenediamine；The imidazoles diamines is 2- (4- aminophenyl) -5 amino
Phenylbenzimidazol.
2. laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies system according to claim 1
Preparation Method, which is characterized in that the partial size of the polyimide resin is 10~800 μm.
3. laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies system according to claim 1
Preparation Method, which is characterized in that the partial size of the nano carbon powder is 100~1000nm.
4. laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies system according to claim 1
Preparation Method, which is characterized in that the partial size of the polyethersulfone resin is 10~400 μm.
5. laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies system according to claim 1
Preparation Method, which is characterized in that the laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies are pre-
Hot temperature is 70~80 DEG C；The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies input
Energy density is 0.1~0.4J/mm3；The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder consumption
The laser power of material is 5~40W.
6. laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies system according to claim 1
Preparation Method, which is characterized in that the laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies are swept
Retouching rate is 1500~2000mm/s；The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies
Sintering spacing be 0.1~0.2mm；The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies
Thickness in monolayer be 0.1~0.2mm；The laser sintering and moulding 3D printing polyimides/polyether sulfone/nano carbon powder supplies
Processing temperature be 110~150 DEG C.
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| CN109749442B (en) * | 2018-12-17 | 2021-07-23 | 浙江大学宁波理工学院 | Polyimide powder material for selective laser sintering and preparation method and application thereof |
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| CN103842422A (en) * | 2011-07-21 | 2014-06-04 | 恩特格里公司 | Nanotube and finely milled carbon fiber polymer composite compositions and methods of making |
| CN103980489A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Low-melt-viscosity thermoplastic polyimide material and 3D printing moulding method thereof |
| CN103980705A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | High-performance polyimide molding powder material suitable for 3D printing and 3D printing molding method |
| CN104140668A (en) * | 2014-07-28 | 2014-11-12 | 中国科学院重庆绿色智能技术研究院 | High-fluidity powder material for selective laser sintering |
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| CN103842422A (en) * | 2011-07-21 | 2014-06-04 | 恩特格里公司 | Nanotube and finely milled carbon fiber polymer composite compositions and methods of making |
| CN103980489A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Low-melt-viscosity thermoplastic polyimide material and 3D printing moulding method thereof |
| CN103980705A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | High-performance polyimide molding powder material suitable for 3D printing and 3D printing molding method |
| CN104140668A (en) * | 2014-07-28 | 2014-11-12 | 中国科学院重庆绿色智能技术研究院 | High-fluidity powder material for selective laser sintering |
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