CN105542166B - A kind of alternative laser sintering and moulding polyimide powder and preparation method thereof - Google Patents

A kind of alternative laser sintering and moulding polyimide powder and preparation method thereof Download PDF

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CN105542166B
CN105542166B CN201610117620.2A CN201610117620A CN105542166B CN 105542166 B CN105542166 B CN 105542166B CN 201610117620 A CN201610117620 A CN 201610117620A CN 105542166 B CN105542166 B CN 105542166B
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moulding
laser sintering
polyimide powder
alternative laser
warming
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CN105542166A (en
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尤庆亮
付华
刘继延
于洁
阮敏
刘学清
陈妤红
张玲
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Jianghan University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties

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Abstract

The invention discloses a kind of alternative laser sintering and moulding polyimide powders and preparation method thereof, which includes the following steps：1) under nitrogen or argon gas are protected, diamines is added in ion solvent, 25~60 DEG C of stirrings is warming up to and is allowed to after fully dissolving, be cooled to room temperature spare；2) dianhydride is added in batches in step 1) acquired solution, every batch of interval time is 20~40min, then is gradually warming up to 120~260 DEG C, and sustained response is after 2~24 hours, washed successively, drying process is to get alternative laser sintering and moulding polyimide powder.The present invention is using diamines step imidization in ion solvent, and not only imidization degree is high, heat-resistant stability is high, but also the parameters such as its particle diameter distribution, apparent density, pattern meet selective laser sintering and moulding technological requirement for the polyimide powder of preparation.

Description

A kind of alternative laser sintering and moulding polyimide powder and preparation method thereof
Technical field
The present invention relates to technical field of polymer materials, in particular to a kind of alternative laser sintering and moulding polyimides Powder and preparation method thereof.
Background technology
Polyimides is containing imide ring and the more regular rigid chain polymer of chemical constitution in a kind of main chain.As 20 generation The resin of the highest temperature classification of discipline exploitation at the beginning of the sixties, is widely used in the necks such as aerospace, microelectronics, liquid crystal, laser Domain.
The performance of polyimide powder is not only related with the molecular structure of reaction monomers, also with the dicyandiamide solution that reacts and poly- It is closely bound up to close technique etc..To obtain the polyimide powder of high imidization degree and high temperature classification, often in non-proton pole Property solvent (n,N-Dimethylformamide, N-Methyl pyrrolidone) in prepared using high temperature one-step method, but the stabilization of solvent in itself Property relatively low, toxicity is higher and high temperature under form complex compound with polyimides and the disadvantages such as be difficult to eliminate, limit a step high temperature method Application on polyimide powder is prepared.
The one kind of selective laser sintering and moulding (SLS) as increasing material manufacturing in 3D printing field has manufacturing process letter The single, advantages such as stock utilization is good, formed precision is high and be concerned.Material is the key that the development of SLS technologies, to drip molding Precision and physical mechanical property play decisive role, become the research and development hot spot of this field.It has been developed that at present a variety of SLS materials, including following several classes：Metal base powder, ceramic based powders, precoated sand, polymer-based powder.Macromolecule and metal, Ceramic material is compared, and has many advantages, such as that the laser power that forming temperature is low, sintering is required is small, and since its surface can be low, melt Melt-viscosity is higher, without it is metal powder sintered when more formidable spherical effect, therefore, polymer-based powder is most early in SLS works It is applied in skill and at present using most, most successful SLS materials.At present, the high molecular material for having been used for SLS is main It is thermal plastic high polymer and its composite material, thermal plastic high polymer can be divided into two kinds of amorphism and crystallinity again, wherein non-knot Crystalline substance macromolecule includes makrolon (PC), polystyrene (PS), high impact polyethylene (HIPS) etc., and crystalline polymer has Buddhist nun Imperial (PA), polypropylene (PP), high density polyethylene (HDPE) (HDPE), polyether-ether-ketone (PEEK) etc..Especially for high temperature classification The shortcomings that toner material largely overcomes conventional thermocompression, and injection molding process is numerous and diverse.It has developed at present high-grade Heat proof material only has polyether-ether-ketone (PEEK) one kind, and because of the expensive of polyether-ether-ketone (PEEK), is led in certain applications Although domain PEEK has good performance but is difficult to large-scale promotion for fear of price and utilizes (Shi Yusheng, Yan Chunze, Wei Qing Pine waits selective laser sintering 3D printing polymer composite Chinese sciences:Information science, 2015,45:204).
Therefore, many researchers are dedicated to preparing the heat-proof macromolecule material for being suitable for SLS modes using all kinds of methods, However, there are following defects for existing polyimide powder：(1) mode that powder is made is to freeze ball milling, the material prepared Grain size is larger, and the requirement of SLS materials molding fineness is not achieved；(2) in polyimides preparation method general at present, slurry It is polyamide acid prepolymer, is polyamic acid with powder prepared by the slurry, needs further imidization that could meet material Applied at elevated temperature demand；(3) prepare polyimides slurry even with chemical imidization, building-up process largely using acetic anhydride, The reagents such as pyridine, triethylamine, process pollution is bigger, of high cost, and this method rarely has use in the industry.Thus, new The polyimide powder for meeting selective laser sintering and moulding technological requirement is prepared in type green solvent has extremely important warp Benefit of helping and market value.
Invention content
Present invention aim to provide a kind of alternative laser sintering and moulding polyimide powder and its preparation side Method, this method use diamines step imidization in ion solvent, and not only imidization degree is high, resistance to for the polyimide powder of preparation Thermal stability is high, and the parameters such as its particle diameter distribution, apparent density, pattern meet selective laser sintering and moulding technological requirement.
To achieve the above object, a kind of alternative laser sintering and moulding polyimide powder provided by the present invention, institute The general structure for stating alternative laser sintering and moulding polyimide powder is as follows：
In formula, n is 100~105Interior integer.
Further, the grain size of the alternative laser sintering and moulding polyimide powder is 5~100 μm, apparent Density is 0.2~0.5g/cm3。
Preferably, the grain size of the alternative laser sintering and moulding polyimide powder is 5~40 μm, Apparent density is 0.3~0.4g/cm3。
A kind of method for preparing alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas are protected, diamines is added in ion solvent, 25~60 DEG C of stirrings is warming up to and is allowed to fully molten Xie Hou is cooled to room temperature spare；
2) dianhydride is added in batches in step 1) acquired solution, every batch of interval time is 20~40min, then is gradually risen Temperature is to 120~260 DEG C, and sustained response is after 2~24 hours, it is washed successively, be dried to get it is alternative it is laser sintered into Type polyimide powder.
Further, in the step 1), the mass ratio of diamines and ion solvent is 1:10~60.
Preferably, in the step 1), the mass ratio of diamines and ion solvent is 1:15~45.
Further, in the step 1), diamines is aromatic diamine, one kind in fats diamines, alicyclic diamine It is or several.
Further, the diamines for p-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenylsulfone, 3,4 '-diaminodiphenylsulfone, 3,3 '-diaminodiphenylsulfone, 3,4 '-diamino-diphenyl ether, neighbour Phenylenediamine, 2,6- diaminotoluenes, 2,4- diaminochlorobenzenes, 3,3 '-dimethyl -4,4 '-benzidine, 4,4 '-diamino Diphenyl sulfide, 1,4- diaminobutanes, 1,4- diaminocyclohexanes, 1,2- diaminocyclohexanes, 3,4- diamino-pyridines or 1, One or more of 4- diamino -2- butanone.
Preferably, the diamines is the purifying p-phenylenediamine to distil through high-temperature pressure-reduction, the p-phenylenediamine Purifying the specific steps are：Under nitrogen protective effect, add in 5~10g rufous p-phenylenediamine to 500mL volume apophorometers, if 125~133 DEG C of temperature is put, condensed water is opened in heating simultaneously, and is vacuumized using oil pump, 0.01~5mmHg of vacuum degree, sublimation time 4~6 hours, you can obtain faint yellow nearly water white transparency p-phenylenediamine crystal.
Further, in the step 1), ion solvent is 1- butyl -3- methyl imidazolium bromides, chlorination 1, bis- (2- of 3- Methoxyl group -2- oxygen ethyl) imidazoles, 1,3- bis- (2- methoxyl group -2- oxygen ethyl) limidazolium hexafluorophosphate, 1,3- bis- (2- methoxyl groups - 2- oxygen ethyl) imidazoles acetate, one kind in tetramethylguanidine tetrafluoroborate ion liquid.
Preferably, the ion solvent is 1- butyl -3- methyl imidazolium bromide solvents.
Further, in the step 2), the molar ratio of dianhydride and diamines is 1：1, wherein, dianhydride is aromatic series tetracarboxylic acid One or more of acid anhydride, aliphatic tetracarboxylic anhydride, Alicyclic tetracarboxylic acid acid anhydride, heterocyclic tetracarboxylic anhydride.
Preferably, the dianhydride is 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl four Carboxylic acid dianhydride, 2,3,3 ', 4 '-biphenyltetracarboxylic dianhydride, pyromellitic acid dianhydride, 2,3,3 ', 4 '-benzophenone tetracarboxylic dianhydride, 2, In 2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 6,6 '-biphenyltetracarboxylic dianhydride, butane -1,2,3,4- tetracarboxylic dianhydrides It is a kind of.
Still further, in the step 2), gradually in temperature-rise period first with the rate of 5~20 DEG C/min by room temperature liter Temperature is to 100 DEG C, and the 20 DEG C of heat preservation 20min that then often heat up are until temperature reaches 120~260 DEG C.
Further, in the step 2), washing, drying process process is first add in suitable methanol and deionized water Washing, it is lasting to stir, it treats that powder is all precipitated, the mixture of powders of gained is depressurized and is filtered, after repeating above-mentioned steps several times, It is dried under the conditions of being 50~120 DEG C in temperature.
Compared with prior art, the invention has the advantages that：
First, the present invention is using diamines step imidization in ion solvent, gained polyimide powder imidization degree It is high；
Second, the present invention uses ionic liquid that is pollution-free, easily recycling not only to widen for solvent and prepared polyimides Dicyandiamide solution, and avoid a step high temperature method during synthesis of polyimides using the aprotonic polar with toxicity it is molten Agent；
Third, the present invention uses symmetrical rigid chain reaction monomers, by introducing bibenzene tetracarboxylic dianhydride and contraposition diamines Structure, the polyimide powder of preparation have higher temperature classification；
Fourth, the grain size of polyimide powder produced by the present invention is 5~100 μm, about 10~30 μm of Average Particle Diameters, Its apparent density is 0.2~0.5g/cm3, pattern is uniform, particle diameter distribution is uniform, excellent heat stability, meets selective laser burning Form type technological requirement；
Fifth, present invention process is simple, energy conservation and environmental protection, conducive to storage-stable, solvent is easily recycled, and has higher market Value.
Description of the drawings
Fig. 1 is the infrared spectrogram of alternative laser sintering and moulding polyimide powder obtained；
Fig. 2 is the thermogravimetric analysis figure of alternative laser sintering and moulding polyimide powder obtained；
Fig. 3 is the thermogravimetric analysis figure of polyimides made from conventional two-step；
Fig. 4 is the differential scanning calorimetry figure of alternative laser sintering and moulding polyimide powder obtained；
Fig. 5 is the differential scanning calorimetry figure of polyimides made from conventional two-step；
Fig. 6 is the scanning electron microscope (SEM) photograph that alternative laser sintering and moulding polyimide powder obtained amplifies 12000 times；
Fig. 7 is the scanning electron microscope (SEM) photograph that alternative laser sintering and moulding polyimide powder obtained amplifies 500 times；
Fig. 8 is the grain size distribution of alternative laser sintering and moulding polyimide powder obtained.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail.
Embodiment 1：
A kind of preparation method of alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas are protected, 1.0814g (10mmol) p-phenylenediamine is added in into 23g1- butyl -3- methylimidazoles In bromide solvent (solid content 15%), it is warming up to 50 DEG C of stirrings and is allowed to after fully dissolving, be cooled to room temperature spare；
2) 2.9422g (10mmol) 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydride is added in into step 1) acquired solution in batches In, every batch of interval time is 30min, then is gradually warming up to 180 DEG C, gradually first with the rate of 20 DEG C/min in temperature-rise period 100 DEG C are warming up to by room temperature, the 20 DEG C of heat preservation 20min that then often heat up are until temperature reaches 180 DEG C, and sustained response is after 8 hours, according to Secondary washed, drying process, wherein, suitable methanol and deionized water washing are first added in washing, drying process process, is continued Stirring treats that powder is all precipitated, the mixture of powders of gained is depressurized and is filtered, after repeating above-mentioned steps several times, is in temperature It is dried under the conditions of 80 DEG C to get flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 2：
A kind of preparation method of alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas are protected, 2.1628g (20mmol) p-phenylenediamine is added in into 45g1- butyl -3- methylimidazoles In bromide solvent (solid content 5%), it is warming up to 50 DEG C of stirrings and is allowed to after fully dissolving, be cooled to room temperature spare；
2) 5.8844g (20mmol) 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydride is added in into step 1) acquired solution in batches In, every batch of interval time is 20min, then is gradually warming up to 180 DEG C, gradually first with the rate of 20 DEG C/min in temperature-rise period 100 DEG C are warming up to by room temperature, the 20 DEG C of heat preservation 20min that then often heat up are until temperature reaches 180 DEG C, and sustained response is after 8 hours, according to Secondary washed, drying process, wherein, suitable methanol and deionized water washing are first added in washing, drying process process, is continued Stirring treats that powder is all precipitated, the mixture of powders of gained is depressurized and is filtered, after repeating above-mentioned steps several times, is in temperature It is dried under the conditions of 80 DEG C to get flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 3：
A kind of preparation method of alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas are protected, by 1.2415g (5mmol) 3,4 '-diaminodiphenylsulfone and 1.2415g (5mmol) 4,4'-diaminodiphenyl sulfone is added in 25.2977g 1- butyl -3- methyl imidazolium bromides solvents (solid content 15%), heating It is allowed to after fully dissolving, is cooled to room temperature spare to 50 DEG C of stirrings；
2) by 1.9813g (10mmol) butane -1,2,3,4- tetracarboxylic dianhydrides are added in batches in step 1) acquired solution, Every batch of interval time is 40min, then is gradually warming up to 180 DEG C, gradually in temperature-rise period first with the rate of 20 DEG C/min by Room temperature is warming up to 100 DEG C, and the 20 DEG C of heat preservation 20min that then often heat up are until temperature reaches 180 DEG C, and sustained response is after 12 hours, according to Secondary washed, drying process, wherein, suitable methanol and deionized water washing are first added in washing, drying process process, is continued Stirring treats that powder is all precipitated, the mixture of powders of gained is depressurized and is filtered, after repeating above-mentioned steps several times, is in temperature It is dried under the conditions of 120 DEG C to get flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 4：
A kind of preparation method of alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas are protected, 1.6221g (15mmol) p-phenylenediamine is added in into 32g1- butyl -3- methylimidazoles In bromide solvent (solid content 5% or so), it is warming up to 50 DEG C of stirrings and is allowed to after fully dissolving, be cooled to room temperature spare；
2) 4.4133g (15mmol) 2,3,3 ', 4 '-biphenyltetracarboxylic dianhydride is added in into step 1) acquired solution in batches In, every batch of interval time is 30min, then is gradually warming up to 180 DEG C, gradually first with the rate of 20 DEG C/min in temperature-rise period 100 DEG C are warming up to by room temperature, the 20 DEG C of heat preservation 20min that then often heat up are until temperature reaches 180 DEG C, and sustained response is after 8 hours, according to Secondary washed, drying process, wherein, suitable methanol and deionized water washing are first added in washing, drying process process, is continued Stirring treats that powder is all precipitated, the mixture of powders of gained is depressurized and is filtered, after repeating above-mentioned steps several times, is in temperature It is dried under the conditions of 120 DEG C to get flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 5：
A kind of preparation method of alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas are protected, 2.7035g (25mmol) p-phenylenediamine is added in into 157.6g1- butyl -3- methyl miaows In azoles bromide solvent (solid content 6%), it is warming up to 50 DEG C of stirrings and is allowed to after fully dissolving, be cooled to room temperature spare；
2) 7.3555g (25mmol) 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydride is added in into step 1) acquired solution in batches In, every batch of interval time is 30min, then is gradually warming up to 180 DEG C, gradually first with the rate of 20 DEG C/min in temperature-rise period 100 DEG C are warming up to by room temperature, the 20 DEG C of heat preservation 20min that then often heat up are until temperature reaches 180 DEG C, after reacting 14 hours, successively Washed, drying process washs, suitable methanol and deionized water washing is first added in drying process process, lasting to stir, and treats Powder is all precipitated, and the mixture of powders of gained is depressurized and is filtered, and is 120 DEG C of items in temperature after repeating above-mentioned steps several times It is dried under part to get flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 6：
A kind of preparation method of alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas protection, by the 4 of 1.7763g (9mmol), 4 '-diaminodiphenyl-methane and 0.2002g The 4,4 '-diaminodiphenyl ether of (1mmol) adds in 46.7892g 1- butyl -3- methyl imidazolium bromide solvent (solid contents 10%) in, 30 DEG C of stirrings is warming up to and are allowed to after fully dissolving, are cooled to room temperature spare；
2) 3.2223g (10mmol) 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides are added in into step 1) acquired solution in batches In, every batch of interval time is 30min, then is gradually warming up to 180 DEG C, gradually first with the rate of 20 DEG C/min in temperature-rise period 100 DEG C are warming up to by room temperature, the 20 DEG C of heat preservation 20min that then often heat up are until temperature reaches 180 DEG C, after reacting 20 hours, successively Washed, drying process washs, suitable methanol and deionized water washing is first added in drying process process, lasting to stir, and treats Powder is all precipitated, and the mixture of powders of gained is depressurized and is filtered, and is 120 DEG C of items in temperature after repeating above-mentioned steps several times It is dried under part to get flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 7：
A kind of preparation method of alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas are protected, by the 4,4'-diaminodiphenyl sulfone and 1.0815g of 1.2415g (5mmol) The 4,4 '-diaminodiphenyl sulfide of (5mmol) adds in 49.9077g 1- butyl -3- methyl imidazolium bromide solvent (solid contents 10%) in, 30 DEG C of stirrings is warming up to and are allowed to after fully dissolving, are cooled to room temperature spare；
2) 3.2223g (10mmol) 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydrides are added in into step 1) acquired solution in batches In, every batch of interval time is 20min, then is gradually warming up to 180 DEG C, gradually first with the rate of 20 DEG C/min in temperature-rise period 100 DEG C are warming up to by room temperature, the 20 DEG C of heat preservation 20min that then often heat up are until temperature reaches 180 DEG C, after reacting 18 hours, successively Washed, drying process washs, suitable methanol and deionized water washing is first added in drying process process, lasting to stir, and treats Powder is all precipitated, and the mixture of powders of gained is depressurized and is filtered, and is 120 DEG C of items in temperature after repeating above-mentioned steps several times It is dried under part to get flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 8：
A kind of preparation method of alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas protection, by the 3 of 0.6579g (3mmol), 3 '-dimethyl -4,4 '-benzidine and The 1,4- diaminocyclohexanes of 0.7993g (7mmol) add in 42.1155g 1- butyl -3- methyl imidazolium bromides solvent (admittedly contain In measuring 10%), it is warming up to 50 DEG C of stirrings and is allowed to after fully dissolving, be cooled to room temperature spare；
2) 3.2223g (10mmol) 2,3 ', 3,4 '-benzophenone tetracarboxylic dianhydrides are added in into step 1) acquired solution in batches In, every batch of interval time is 40min, then is gradually warming up to 220 DEG C, gradually first with the rate of 20 DEG C/min in temperature-rise period 100 DEG C are warming up to by room temperature, the 20 DEG C of heat preservation 20min that then often heat up are until temperature reaches 220 DEG C, after reacting 16 hours, successively Washed, drying process washs, suitable methanol and deionized water washing is first added in drying process process, lasting to stir, and treats Powder is all precipitated, and the mixture of powders of gained is depressurized and is filtered, and is 120 DEG C of items in temperature after repeating above-mentioned steps several times It is dried under part to get flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 9：
A kind of preparation method of alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas are protected, by the o-phenylenediamine of 0.5407 (5mmol) and 1, the 2- bis- of 0.5710g (5mmol) Aminocyclohexane is added in 36.4851g 1- butyl -3- methyl imidazolium bromides solvents (solid content 10%), is warming up to 60 DEG C and is stirred It mixes after being allowed to fully dissolve, is cooled to room temperature spare；
2) 2.9422g (10mmol) 2,2 ', 6,6 '-biphenyltetracarboxylic dianhydride is added in into step 1) acquired solution in batches In, every batch of interval time is 40min, then is gradually warming up to 240 DEG C, gradually first with the rate of 20 DEG C/min in temperature-rise period 100 DEG C are warming up to by room temperature, the 20 DEG C of heat preservation 20min that then often heat up are until temperature reaches 240 DEG C, after reacting 12 hours, successively Washed, drying process washs, suitable methanol and deionized water washing is first added in drying process process, lasting to stir, and treats Powder is all precipitated, and the mixture of powders of gained is depressurized and is filtered, and is 120 DEG C of items in temperature after repeating above-mentioned steps several times It is dried under part to get flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 10：
A kind of preparation method of alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas are protected, by the Isosorbide-5-Nitrae of 0.7002 (4mmol)-diamino -2- butanone and 0.9664g (6mmol) 1,4-Diaminobutane add in 34.6302g 1- butyl -3- methyl imidazolium bromides solvents (solid content 10%), be warming up to 60 DEG C of stirrings are allowed to after fully dissolving, and are cooled to room temperature spare；
2) 2.1812g (10mmol) pyromellitic acid dianhydride is added in batches in step 1) acquired solution, every batch of minor tick Time is 40min, then is gradually warming up to 260 DEG C, is gradually warming up to first with the rate of 20 DEG C/min by room temperature in temperature-rise period 100 DEG C, the 20 DEG C of heat preservation 20min that then often heat up are until temperature reaches 260 DEG C, after reacting 18 hours, at washed successively, drying Reason washs, suitable methanol and deionized water washing is first added in drying process process, lasting to stir, and treats powder all precipitations, The mixture of powders of gained is depressurized and is filtered, after repeating above-mentioned steps several times, under the conditions of being 120 DEG C in temperature drying to get Flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 11：
A kind of preparation method of alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas protection, by 2, the 6- diaminotoluenes of 0.2443g (2mmol) and 1.1407g (8mmol) 2,4- diaminochlorobenzenes are added in 32.0958g 1- butyl -3- methyl imidazolium bromides solvents (solid content 10%), are warming up to 40 DEG C stirring be allowed to fully dissolve after, be cooled to room temperature spare；
2) 2.1812g (10mmol) pyromellitic acid dianhydride is added in batches in step 1) acquired solution, every batch of minor tick Time is 40min, then is gradually warming up to 200 DEG C, is gradually warming up to first with the rate of 20 DEG C/min by room temperature in temperature-rise period 100 DEG C, the 20 DEG C of heat preservation 20min that then often heat up are until temperature reaches 200 DEG C, after reacting 12 hours, at washed successively, drying Reason washs, suitable methanol and deionized water washing is first added in drying process process, lasting to stir, and treats powder all precipitations, The mixture of powders of gained is depressurized and is filtered, after repeating above-mentioned steps several times, under the conditions of being 120 DEG C in temperature drying to get Flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 12：
A kind of preparation method of alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas are protected, 3, the 4- diamino-pyridines of 1.0913 (10mmol) are added in into 36.3015g 1- fourths In base -3- methyl imidazolium bromides solvent (solid content 10%), it is warming up to 60 DEG C of stirrings and is allowed to after fully dissolving, be cooled to room temperature It is spare；
2) 2.9422g (10mmol) 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydride is added in into step 1) acquired solution in batches In, every batch of interval time is 40min, then is gradually warming up to 200 DEG C, gradually first with the rate of 20 DEG C/min in temperature-rise period 100 DEG C are warming up to by room temperature, the 20 DEG C of heat preservation 20min that then often heat up after reaction 6 hours, are passed through successively until temperature reaches 200 DEG C Washing is dried, and suitable methanol and deionized water washing are first added in washing, drying process process, lasting to stir, and treats powder It is last to be all precipitated, the mixture of powders of gained is depressurized and is filtered, is 120 DEG C of conditions in temperature after repeating above-mentioned steps several times Lower drying is to get flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 13：
A kind of preparation method of alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas protection, by the 3 of 1.2415g (5mmol), 3 '-diaminodiphenylsulfone and 1.2415g The addition 48.8268g1- butyl -3- methyl imidazolium bromide solvent (solid contents of 3,4 '-diamino-diphenyl ether of (5mmol) 10%) in, 60 DEG C of stirrings is warming up to and are allowed to after fully dissolving, are cooled to room temperature spare；
2) 2.9422g (10mmol) 2,2 ', 6,6 '-biphenyltetracarboxylic dianhydride is added in into step 1) acquired solution in batches In, every batch of interval time is 40min, then is gradually warming up to 200 DEG C, gradually first with the rate of 20 DEG C/min in temperature-rise period 100 DEG C are warming up to by room temperature, the 20 DEG C of heat preservation 20min that then often heat up are until temperature reaches 220 DEG C, after reacting 24 hours, successively Washed, drying process washs, suitable methanol and deionized water washing is first added in drying process process, lasting to stir, and treats Powder is all precipitated, and the mixture of powders of gained is depressurized and is filtered, and is 120 DEG C of items in temperature after repeating above-mentioned steps several times It is dried under part to get flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 14：
A kind of preparation method of alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas are protected, 1.0814g (10mmol) p-phenylenediamine is added in into 23g1- butyl -3- methylimidazoles In tetrafluoro boric acid salt solvent (solid content 15%), it is warming up to 50 DEG C of stirrings and is allowed to after fully dissolving, be cooled to room temperature spare；
2) 2.9422g (10mmol) 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydride is added in into step 1) acquired solution in batches In, every batch of interval time is 30min, then is gradually warming up to 200 DEG C, gradually first with the rate of 20 DEG C/min in temperature-rise period 100 DEG C are warming up to by room temperature, the 20 DEG C of heat preservation 20min that then often heat up are until temperature reaches 200 DEG C, and sustained response is after 14 hours, Washed successively, drying process, wherein, suitable methanol and deionized water washing are first added in washing, drying process process, is held Continuous stirring treats that powder is all precipitated, the mixture of powders of gained is depressurized and is filtered, after repeating above-mentioned steps several times, in temperature It is dried under the conditions of being 120 DEG C to get flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 15：
A kind of preparation method of alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas are protected, 1.0814g (10mmol) p-phenylenediamine is added in into 23g tetramethylguanidine tetrafluoroborates In (solid content 15%), it is warming up to 60 DEG C of stirrings and is allowed to after fully dissolving, be cooled to room temperature spare；
2) 2.9422g (10mmol) 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride is added in into step 1) acquired solution in batches In, every batch of interval time is 30min, then is gradually warming up to 240 DEG C, gradually first with the rate of 20 DEG C/min in temperature-rise period 100 DEG C are warming up to by room temperature, the 20 DEG C of heat preservation 20min that then often heat up are until temperature reaches 240 DEG C, and sustained response is after 20 hours, Washed successively, drying process, wherein, suitable methanol and deionized water washing are first added in washing, drying process process, is held Continuous stirring treats that powder is all precipitated, the mixture of powders of gained is depressurized and is filtered, after repeating above-mentioned steps several times, in temperature It is dried under the conditions of being 100 DEG C to get flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 16：
A kind of preparation method of alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas are protected, by 2.0024g (10mmol) 4,4 '-diaminodiphenyl ether adds in 23.7070g1- fourths In base -3- methyl imidazolium bromides solvent (solid content 15%), it is warming up to 60 DEG C of stirrings and is allowed to after fully dissolving, be cooled to room temperature It is spare；
2) 2.1812g (10mmol) pyromellitic acid dianhydride is added in batches in step 1) acquired solution, every batch of minor tick Time is 20min, then is gradually warming up to 200 DEG C, is gradually warming up to first with the rate of 20 DEG C/min by room temperature in temperature-rise period 100 DEG C, for the 20 DEG C of heat preservation 20min that then often heat up until temperature reaches 200 DEG C, sustained response is washed successively, dry after 20 hours Dry processing, wherein, suitable methanol and deionized water washing are first added in washing, drying process process, it is lasting to stir, treat powder It is all precipitated, the mixture of powders of gained is depressurized and is filtered, after repeating above-mentioned steps several times, under the conditions of temperature is 100 DEG C Drying is to get flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 17：
A kind of preparation method of alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas are protected, by 2.0024g (10mmol) 4,4 '-diaminodiphenyl ether adds in 23.7070g chlorinations In 1,3- bis- (2- methoxyl group -2- oxygen ethyl) imidazoles (solid content 15%), it is warming up to 60 DEG C of stirrings and is allowed to after fully dissolving, cooling It is spare to room temperature；
2) 2.1812g (10mmol) pyromellitic acid dianhydride is added in batches in step 1) acquired solution, every batch of minor tick Time is 20min, then is gradually warming up to 200 DEG C, is gradually warming up to first with the rate of 20 DEG C/min by room temperature in temperature-rise period 100 DEG C, for the 20 DEG C of heat preservation 20min that then often heat up until temperature reaches 200 DEG C, sustained response is washed successively, dry after 20 hours Dry processing, wherein, suitable methanol and deionized water washing are first added in washing, drying process process, it is lasting to stir, treat powder It is all precipitated, the mixture of powders of gained is depressurized and is filtered, after repeating above-mentioned steps several times, under the conditions of temperature is 100 DEG C Drying is to get flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 18：
A kind of preparation method of alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas are protected, by the 4,4'-diaminodiphenyl sulfone and 1.0815g of 1.2415g (5mmol) The 4,4 '-diaminodiphenyl sulfide of (5mmol) adds in 49.9077g1,3- bis- (2- methoxyl group -2- oxygen ethyl) imidazoles hexafluorophosphoric acid In salt (solid content 10%), it is warming up to 50 DEG C of stirrings and is allowed to after fully dissolving, be cooled to room temperature spare；
2) 3.2223g (10mmol) 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydrides are added in into step 1) acquired solution in batches In, every batch of interval time is 20min, then is gradually warming up to 180 DEG C, gradually first with the rate of 20 DEG C/min in temperature-rise period 100 DEG C are warming up to by room temperature, the 20 DEG C of heat preservation 20min that then often heat up are until temperature reaches 180 DEG C, after reacting 18 hours, successively Washed, drying process washs, suitable methanol and deionized water washing is first added in drying process process, lasting to stir, and treats Powder is all precipitated, and the mixture of powders of gained is depressurized and is filtered, and is 120 DEG C of items in temperature after repeating above-mentioned steps several times It is dried under part to get flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 19：
A kind of preparation method of alternative laser sintering and moulding polyimide powder, includes the following steps：
1) under nitrogen or argon gas are protected, 2.1628g (20mmol) p-phenylenediamine is added in into the 45g1, (2- methoxyl groups -2- of 3- bis- Oxygen ethyl) in imidazoles acetate (solid content 5%), it is warming up to 40 DEG C of stirrings and is allowed to after fully dissolving, be cooled to room temperature spare；
2) 5.8844g (20mmol) 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydride is added in into step 1) acquired solution in batches In, every batch of interval time is 20min, then is gradually warming up to 180 DEG C, gradually first with the rate of 20 DEG C/min in temperature-rise period 100 DEG C are warming up to by room temperature, the 20 DEG C of heat preservation 20min that then often heat up are until temperature reaches 180 DEG C, and sustained response is after 8 hours, according to Secondary washed, drying process, wherein, suitable methanol and deionized water washing are first added in washing, drying process process, is continued Stirring treats that powder is all precipitated, the mixture of powders of gained is depressurized and is filtered, after repeating above-mentioned steps several times, is in temperature It is dried under the conditions of 80 DEG C to get flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 20：Effect example
The polyimide powder of gained is tested for the property, Fig. 1 is infrared spectrogram, by Fig. 1 it is found that 1708cm-1 And 1354cm-1The stretching vibration of the symmetrical stretching vibration and C-N of C=O in imide group, 1074cm are corresponded to respectively-1With 733cm-1The flexural vibrations peak of C-O and C=O in imide ring is corresponded to respectively, it is known that the powder of preparation is polyimides, while fragrant Stretching vibration peak (the 1855cm of carbonyl in fragrant monomer-1And 1770cm-1), diamine groups (3400-3500cm-1), two level amide groups Group (1640cm-1And 1540cm-1) vibration peak is invisible, illustrate that reaction carries out complete and prepared polyimide powder Imidization degree is high.
Thermogravimetric analysis figures of the Fig. 2 for alternative laser sintering and moulding polyimide powder obtained, weight-loss ratio 1%, 5%th, 10% corresponding temperature is respectively 447.37 DEG C, 609.15 DEG C, 625.7 DEG C.Fig. 3 (first synthesizes polyamides for conventional two-step Amino acid high temperature curing of coating again) made from polyimides thermogravimetric analysis figure, weight-loss ratio 1%, 5%, 10% corresponding temperature point It Wei not be 412 DEG C, 561.67 DEG C, 601.37 DEG C.In contrast, the polyimides prepared by the present invention has superior thermostabilization Property.
Fig. 4 is the differential scanning calorimetry figure of alternative laser sintering and moulding polyimide powder obtained, compared to Fig. 5 The differential scanning calorimetry figure of polyimides is prepared for conventional two-step, as can be seen from the figure there are apparent crosslinking curing peak, Illustrate that polyimides prepared by the present invention has better machine-shaping property；
Fig. 6 is the scanning electron microscope (SEM) photograph that alternative laser sintering and moulding polyimide powder obtained amplifies 12000 times, is schemed 7 the scanning electron microscope (SEM) photograph of alternative 500 times of laser sintering and moulding polyimide powder amplification is made for embodiment 1, can from figure Polyimide powder obtained by knowing is well dispersed, uniform particle diameter, and the spherical morphology of rule is presented in amount of powder.
Fig. 8 is the grain size distribution of alternative laser sintering and moulding polyimide powder obtained, and powder diameter is in just State is distributed, and grain size is 5~100 μm, and apparent density is 0.2~0.5g/cm3.Alternative laser is made for embodiment 1 in table 1 Sinter molding polyimide powder granularity is mainly distributed on 5~60 μm with percentage by volume table in range, grain size.
Table 1
Granularity (μm) Range inner volume % Granularity (μm) Range inner volume % Granularity (μm) Range inner volume %
0.891-1.000 0.06 3.548-3.981 1.15 14.125-15.849 6.86
1.000-1.122 0.14 3.981-4.467 1.46 15.849-17.783 6.73
1.122-1.259 0.26 4.467-5.012 1.85 17.783-19.953 6.4
1.259-1.413 0.33 5.012-5.623 2.33 19.953-22.387 5.9
1.413-1.585 0.39 5.623-6.310 2.9 22.387-25.119 5.25
1.585-1.778 0.44 6.310-7.079 3.54 25.119-28.184 4.52
1.778-1.995 0.47 7.079-7.943 4.21 28.184-31.623 3.74
1.995-2.239 0.51 7.943-8.913 4.9 31.623-35.481 2.98
2.239-2.515 0.57 8.913-10.000 5.53 35.481-39.811 2.24
2.515-2.818 0.64 10.000-11.220 6.1 39.811-44.668 1.54
2.818-3.162 0.76 11.220-12.589 6.53 44.668-50.119 0.88
3.162-3.548 0.92 12.589-14.125 6.79 50.119-56.234 0.18
The above description is merely a specific embodiment, it is noted that any those skilled in the art exist Disclosed herein technical scope in, the change or replacement that can readily occur in, should all cover protection scope of the present invention it It is interior.

Claims (4)

1. a kind of alternative laser sintering and moulding polyimide powder, which is characterized in that the alternative it is laser sintered into The general structure of type polyimide powder is as follows：
In formula, n is 100~105Interior integer；
The grain size of the alternative laser sintering and moulding polyimide powder is 5~100 μm, apparent density for 0.2~ 0.5g/cm3。
2. a kind of method for preparing alternative laser sintering and moulding polyimide powder described in claim 1, feature exist In including the following steps：
1) under nitrogen or argon gas are protected, diamines is added in ion solvent, 25~60 DEG C of stirrings is warming up to and is allowed to after fully dissolving, It is cooled to room temperature spare；Wherein, the diamines is p-phenylenediamine；The ion solvent for 1- butyl -3- methyl imidazolium bromides, Chlorination 1,3- bis- (2- methoxyl group -2- oxygen ethyl) imidazoles, 1,3- bis- (2- methoxyl group -2- oxygen ethyl) limidazolium hexafluorophosphate, 1, One kind in 3- bis- (2- methoxyl group -2- oxygen ethyl) imidazoles acetate, tetramethylguanidine tetrafluoroborate ion liquid；
2) dianhydride is added in batches in step 1) acquired solution, wherein dianhydride is 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydride, often Batch interval time is 20~40min, then is gradually warming up to 120~260 DEG C, gradually in temperature-rise period first with 5~20 DEG C/ The rate of min is warming up to 100 DEG C by room temperature, and the 20 DEG C of heat preservation 20min that then often heat up are until temperature reaches 120~260 DEG C, persistently After reaction 2~24 hours, washed successively, drying process is to get alternative laser sintering and moulding polyimide powder.
3. the preparation method of alternative laser sintering and moulding polyimide powder according to claim 2, feature exist In in the step 1), the mass ratio of diamines and ion solvent is 1:10~60.
4. the preparation method of alternative laser sintering and moulding polyimide powder according to claim 2, feature exist In in the step 2), the molar ratio of dianhydride and diamines is 1：1.
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