CN105542166A - Selective laser sintered polyimide powder and preparation method thereof - Google Patents

Selective laser sintered polyimide powder and preparation method thereof Download PDF

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CN105542166A
CN105542166A CN201610117620.2A CN201610117620A CN105542166A CN 105542166 A CN105542166 A CN 105542166A CN 201610117620 A CN201610117620 A CN 201610117620A CN 105542166 A CN105542166 A CN 105542166A
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polyimide powder
moulding
laser sintering
alternative laser
preparation
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CN105542166B (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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    • 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 selective laser sintered polyimide powder and a preparation method thereof. The preparation method comprises steps as follows: 1) under the protection of nitrogen or argon, diamine is added to an ion solvent, the mixture is heated to 25-60 DEG C and stirred for full dissolution, and the solution is cooled to the normal temperature for use; 2) dianhydride is added to the solution obtained in Step 1) in batches at the time interval of 20-40 min, then the solution is gradually heated to 120-260 DEG C, the continuous reaction is performed for 2-24 h, washing and drying treatment are performed sequentially, and the selective laser sintered polyimide powder is obtained. The diamine is imidized in the ion solvent in one step, the prepared polyimide powder is high in imidization degree and heat-resistant stability, and parameters of particle size distribution, apparent density, morphology and the like of the polyimide powder meet the requirement of the selective laser sintering forming technology.

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, refer to a kind of alternative laser sintering and moulding polyimide powder and preparation method thereof particularly.
Background technology
Polyimide is containing imide ring and the comparatively regular rigid chain polymer of chemical structure in a class main chain.As the resin of the highest temperature classification of early 1960s exploitation, it is widely used in aerospace, microelectronics, liquid crystal, the fields such as laser.
The performance of polyimide powder is not only relevant with the molecular structure of reaction monomers, also closely bound up with the solvent system reacted and polymerization technique etc.For obtaining the polyimide powder of high imidization degree and high temperature classification, often at aprotic polar solvent (N, dinethylformamide, N-Methyl pyrrolidone) preparation of middle employing high temperature single stage method, but the stability of solvent itself is lower, toxicity is higher, and form complex compound with polyimide under high temperature and be difficult to inferior positions such as eliminating, limit a step pyroprocess and prepare the application on polyimide powder.
Selective laser sintering and moulding (SLS), as the one increasing material manufacture in 3D printing field, has the advantages such as manufacturing process is simple, material use efficiency good, formed precision is high and receives much concern.Material is the key of SLS technical development, plays decisive role, become the research and development focus of this area to the precision of drip molding and physical and mechanical properties.Develop multiple SLS material at present, comprise following a few class: metal base powder, ceramic base powder, precoated sand, polymer-based powder.Polymer is compared with metal, stupalith, there is the advantages such as low, needed for sintering the laser power of forming temperature is little, and due to its surface energy low, melt viscosity is higher, more formidable spherical effect when not having metal powder sintered, therefore, polymer-based powder is applied in SLS technique, be also at present application at most, the most successful SLS material.At present, for macromolecular material mainly thermal plastic high polymer and the matrix material thereof of SLS, thermal plastic high polymer can be divided into again amorphism and crystallinity two kinds, wherein amorphism polymer comprises polycarbonate (PC), polystyrene (PS), high impact polyethylene (HIPS) etc., and crystalline polymer has nylon (PA), polypropylene (PP), high density polyethylene(HDPE) (HDPE), polyether-ether-ketone (PEEK) etc.Especially for the toner material of high temperature classification, conventional thermocompression is largely overcomed, the shortcoming that injection molding process is numerous and diverse.The high-grade heat-stable material developed at present only has polyether-ether-ketone (PEEK) a kind of, and because polyether-ether-ketone (PEEK) expensive, although there is good performance at some Application Areas PEEK but be difficult to large-scale promotion utilization (Shi Yusheng for fear of price, Yan Chunze, Wei Qingsong, Deng. selective laser sintering 3D printing polymer composite. Chinese science: information science, 2015,45:204).
Therefore, many investigators are had to be devoted to adopt each class methods to prepare the heat-proof macromolecule material being applicable to SLS mode, but, there is following defect in existing polyimide powder: the mode that (1) makes powder is freezing ball milling, the material particle size prepared is comparatively large, does not reach the requirement of SLS forming materials fineness; (2) in general at present polyimide preparation method, its slurry is polyamide acid prepolymer, and the powder prepared with this slurry is polyamic acid, needs further imidization could meet the applied at elevated temperature demand of material; (3) even if adopt chemical imidization to prepare polyimide slurry, its building-up process uses the reagent such as diacetyl oxide, pyridine, triethylamine in a large number, and course of processing damage ratio is comparatively large, cost is high, and the method rarely has use in the industry.Thus, in novel green solvent, prepare the polyimide powder meeting selective laser sintering and moulding processing requirement and there is extremely important economic benefit and marketable value.
Summary of the invention
Object of the present invention will provide a kind of alternative laser sintering and moulding polyimide powder and preparation method thereof exactly, the method adopts diamines step imidization in ion solvent, the polyimide powder not only imidization degree of preparation is high, heat-resistant stability is high, and the parameter such as its size distribution, apparent density, pattern meets selective laser sintering and moulding processing requirement.
For achieving the above object, the alternative laser sintering and moulding polyimide powder of one provided by the present invention, the general structure of described alternative laser sintering and moulding polyimide powder is as follows:
In formula, n is 100 ~ 10 5interior integer.
Further, the particle diameter of described alternative laser sintering and moulding polyimide powder is 5 ~ 100 μm, and its apparent density is 0.2 ~ 0.5g/cm 3.
Preferably, the particle diameter of described alternative laser sintering and moulding polyimide powder is 5 ~ 40 μm, and its apparent density is 0.3 ~ 0.4g/cm 3.
Prepare a method for alternative laser sintering and moulding polyimide powder, comprise the steps:
1) under nitrogen or argon shield, diamines is added in ion solvent, be warming up to after 25 ~ 60 DEG C of stirrings make it fully to dissolve, be cooled to normal temperature for subsequent use;
2) dianhydride is added step 1 in batches) in gained solution, every batch of interval time is 20 ~ 40min, is more progressively warming up to 120 ~ 260 DEG C, and sustained reaction is after 2 ~ 24 hours, successively through washing, drying treatment, obtain alternative laser sintering and moulding polyimide powder.
Further, described step 1) in, the mass ratio of diamines and ion solvent is 1:10 ~ 60.
Preferably, described step 1) in, the mass ratio of diamines and ion solvent is 1:15 ~ 45.
Further, described step 1) in, diamines is one or more in aromatic diamine, fats diamines, alicyclic diamine.
Further, described diamines is Ursol D, 4, 4 '-diaminodiphenyl-methane, 4, 4 '-diaminodiphenyl oxide, 4, 4 '-diaminodiphenylsulfone(DDS), 3, 4 '-diaminodiphenylsulfone(DDS), 3, 3 '-diaminodiphenylsulfone(DDS), 3, 4 '-diamino-diphenyl ether, O-Phenylene Diamine, 2, 6-diaminotoluene, 2, 4-diaminochlorobenzene, 3, 3 '-dimethyl-4, 4 '-benzidine, 4, 4 '-diaminodiphenyl sulfide, 1, 4-diaminobutane, 1, 4-diamino-cyclohexane, 1, 2-diamino-cyclohexane, 3, 4-diamino-pyridine or 1, one or more in 4-diamino-2-butanone.
Preferably; described diamines is the purifying Ursol D through high-temperature pressure-reduction distillation; the purifying concrete steps of described Ursol D are: under nitrogen protection effect; add 5 ~ 10g reddish-brown Ursol D in 500mL volume apophorometer, set temperature 125 ~ 133 DEG C, heat up and open water of condensation simultaneously; and adopt oil pump to vacuumize; vacuum tightness 0.01 ~ 5mmHg, sublimation time 4 ~ 6 hours, faint yellow nearly water white transparency Ursol D crystal.
Further, described step 1) in, ion solvent is 1-butyl-3-methyl imidazolium bromide, chlorination 1,3-bis-(2-methoxyl group-2-oxygen ethyl) imidazoles, 1, one in 3-bis-(2-methoxyl group-2-oxygen ethyl) limidazolium hexafluorophosphate, 1,3-bis-(2-methoxyl group-2-oxygen ethyl) imidazoles acetate, tetramethyl guanidine tetrafluoroborate ion liquid.
Preferably, described ion solvent is 1-butyl-3-methyl imidazolium bromide solvent.
Further, described step 2) in, the mol ratio of dianhydride and diamines is 1:1, and wherein, dianhydride is one or more in aromatic series tetracarboxylic acid acid anhydride, aliphatics tetracarboxylic anhydride, Alicyclic tetracarboxylic acid acid anhydride, heterocycle race tetracarboxylic anhydride.
Preferably, described dianhydride is 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, pyromellitic acid dianhydride, 2,3,3 ', 4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 6,6 '-biphenyl tetracarboxylic dianhydride, butane-1, one in 2,3,4-tetracarboxylic dianhydride.
Again further, described step 2) in, be progressively first warming up to 100 DEG C with the speed of 5 ~ 20 DEG C/min by normal temperature in temperature-rise period, the 20 DEG C of insulation 20min that then often heat up are until temperature reaches 120 ~ 260 DEG C.
Further, described step 2) in, washing, drying treatment process are first add appropriate methyl alcohol and deionized water wash, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, then repeat above-mentioned steps number all over after, dry under temperature is 50 ~ 120 DEG C of conditions.
Compared with prior art, tool of the present invention has the following advantages:
One, the present invention adopts diamines step imidization in ion solvent, and gained polyimide powder imidization degree is high;
Its two, the present invention adopts the ionic liquid of pollution-free, easy recovery to be solvent, has not only widened the solvent system preparing polyimide, and avoid a step pyroprocess use in synthesis of polyimides process band toxicity aprotic polar solvent;
Its three, the present invention adopts symmetrical stiff chain reaction monomers, and by introducing bibenzene tetracarboxylic dianhydride and contraposition diamine structures, the polyimide powder of preparation has higher temperature classification;
Its four, the particle diameter of the polyimide powder that the present invention obtains is 5 ~ 100 μm, and Average Particle Diameters about 10 ~ 30 μm, its apparent density is 0.2 ~ 0.5g/cm 3, pattern is homogeneous, even particle size distribution, excellent heat stability, meets selective laser sintering and moulding processing requirement;
Its five, present invention process is simple, and energy-conserving and environment-protective, are beneficial to stably stored, and solvent is easy to reclaim, and has higher marketable value.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of obtained alternative laser sintering and moulding polyimide powder;
Fig. 2 is the thermogravimetric analysis figure of obtained alternative laser sintering and moulding polyimide powder;
Fig. 3 is the thermogravimetric analysis figure of the polyimide that conventional two-step obtains;
Fig. 4 is the means of differential scanning calorimetry figure of obtained alternative laser sintering and moulding polyimide powder;
Fig. 5 is the means of differential scanning calorimetry figure of the polyimide that conventional two-step obtains;
Fig. 6 is the scanning electron microscope (SEM) photograph that obtained alternative laser sintering and moulding polyimide powder amplifies 12000 times;
Fig. 7 is the scanning electron microscope (SEM) photograph that obtained alternative laser sintering and moulding polyimide powder amplifies 500 times;
Fig. 8 is the grain size distribution of obtained alternative laser sintering and moulding polyimide powder.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1:
A preparation method for alternative laser sintering and moulding polyimide powder, comprises the steps:
1) under nitrogen or argon shield, 1.0814g (10mmol) Ursol D is added in 23g1-butyl-3-methyl imidazolium bromide solvent (solid content 15%), be warming up to after 50 DEG C of stirrings make it fully to dissolve, be cooled to normal temperature for subsequent use;
2) by 2.9422g (10mmol) 3, 3 ', 4, 4 '-biphenyl tetracarboxylic dianhydride adds step 1 in batches) in gained solution, every batch of interval time is 30min, progressively be warming up to 180 DEG C again, progressively first be warming up to 100 DEG C with the speed of 20 DEG C/min by normal temperature in temperature-rise period, then 20 DEG C of insulation 20min are often heated up until temperature reaches 180 DEG C, sustained reaction is after 8 hours, successively through washing, drying treatment, wherein, washing, appropriate methyl alcohol and deionized water wash is first added in drying treatment process, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, repeat again above-mentioned steps number all over after, dry under temperature is 80 DEG C of conditions, obtain flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 2:
A preparation method for alternative laser sintering and moulding polyimide powder, comprises the steps:
1) under nitrogen or argon shield, 2.1628g (20mmol) Ursol D is added in 45g1-butyl-3-methyl imidazolium bromide solvent (solid content 5%), be warming up to after 50 DEG C of stirrings make it fully to dissolve, be cooled to normal temperature for subsequent use;
2) by 5.8844g (20mmol) 3, 3 ', 4, 4 '-biphenyl tetracarboxylic dianhydride adds step 1 in batches) in gained solution, every batch of interval time is 20min, progressively be warming up to 180 DEG C again, progressively first be warming up to 100 DEG C with the speed of 20 DEG C/min by normal temperature in temperature-rise period, then 20 DEG C of insulation 20min are often heated up until temperature reaches 180 DEG C, sustained reaction is after 8 hours, successively through washing, drying treatment, wherein, washing, appropriate methyl alcohol and deionized water wash is first added in drying treatment process, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, repeat again above-mentioned steps number all over after, dry under temperature is 80 DEG C of conditions, obtain flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 3:
A preparation method for alternative laser sintering and moulding polyimide powder, comprises the steps:
1) under nitrogen or argon shield, by 1.2415g (5mmol) 3,4 '-diaminodiphenylsulfone(DDS) and 1.2415g (5mmol) 4,4 '-diaminodiphenylsulfone(DDS) adds in 25.2977g1-butyl-3-methyl imidazolium bromide solvent (solid content 15%), be warming up to after 50 DEG C of stirrings make it fully to dissolve, be cooled to normal temperature for subsequent use;
2) by 1.9813g (10mmol) butane-1, 2, 3, 4-tetracarboxylic dianhydride adds step 1 in batches) in gained solution, every batch of interval time is 40min, progressively be warming up to 180 DEG C again, progressively first be warming up to 100 DEG C with the speed of 20 DEG C/min by normal temperature in temperature-rise period, then 20 DEG C of insulation 20min are often heated up until temperature reaches 180 DEG C, sustained reaction is after 12 hours, successively through washing, drying treatment, wherein, washing, appropriate methyl alcohol and deionized water wash is first added in drying treatment process, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, repeat again above-mentioned steps number all over after, dry under temperature is 120 DEG C of conditions, obtain flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 4:
A preparation method for alternative laser sintering and moulding polyimide powder, comprises the steps:
1) under nitrogen or argon shield, 1.6221g (15mmol) Ursol D is added in 32g1-butyl-3-methyl imidazolium bromide solvent (solid content about 5%), be warming up to after 50 DEG C of stirrings make it fully to dissolve, be cooled to normal temperature for subsequent use;
2) by 4.4133g (15mmol) 2, 3, 3 ', 4 '-biphenyl tetracarboxylic dianhydride adds step 1 in batches) in gained solution, every batch of interval time is 30min, progressively be warming up to 180 DEG C again, progressively first be warming up to 100 DEG C with the speed of 20 DEG C/min by normal temperature in temperature-rise period, then 20 DEG C of insulation 20min are often heated up until temperature reaches 180 DEG C, sustained reaction is after 8 hours, successively through washing, drying treatment, wherein, washing, appropriate methyl alcohol and deionized water wash is first added in drying treatment process, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, repeat again above-mentioned steps number all over after, dry under temperature is 120 DEG C of conditions, obtain flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 5:
A preparation method for alternative laser sintering and moulding polyimide powder, comprises the steps:
1) under nitrogen or argon shield, 2.7035g (25mmol) Ursol D is added in 157.6g1-butyl-3-methyl imidazolium bromide solvent (solid content 6%), be warming up to after 50 DEG C of stirrings make it fully to dissolve, be cooled to normal temperature for subsequent use;
2) by 7.3555g (25mmol) 3, 3 ', 4, 4 '-biphenyl tetracarboxylic dianhydride adds step 1 in batches) in gained solution, every batch of interval time is 30min, progressively be warming up to 180 DEG C again, progressively first be warming up to 100 DEG C with the speed of 20 DEG C/min by normal temperature in temperature-rise period, then 20 DEG C of insulation 20min are often heated up until temperature reaches 180 DEG C, react after 14 hours, successively through washing, drying treatment, washing, appropriate methyl alcohol and deionized water wash is first added in drying treatment process, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, repeat again above-mentioned steps number all over after, dry under temperature is 120 DEG C of conditions, obtain flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 6:
A preparation method for alternative laser sintering and moulding polyimide powder, comprises the steps:
1) under nitrogen or argon shield, by 4 of 1.7763g (9mmol), 4 of 4 '-diaminodiphenyl-methane and 0.2002g (1mmol), 4 '-diaminodiphenyl oxide adds in 46.7892g1-butyl-3-methyl imidazolium bromide solvent (solid content 10%), be warming up to after 30 DEG C of stirrings make it fully to dissolve, be cooled to normal temperature for subsequent use;
2) by 3.2223g (10mmol) 3, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride adds step 1 in batches) in gained solution, every batch of interval time is 30min, progressively be warming up to 180 DEG C again, progressively first be warming up to 100 DEG C with the speed of 20 DEG C/min by normal temperature in temperature-rise period, then 20 DEG C of insulation 20min are often heated up until temperature reaches 180 DEG C, react after 20 hours, successively through washing, drying treatment, washing, appropriate methyl alcohol and deionized water wash is first added in drying treatment process, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, repeat again above-mentioned steps number all over after, dry under temperature is 120 DEG C of conditions, obtain flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 7:
A preparation method for alternative laser sintering and moulding polyimide powder, comprises the steps:
1) under nitrogen or argon shield, by 4 of 1.2415g (5mmol), 4 of 4 '-diaminodiphenylsulfone(DDS) and 1.0815g (5mmol), 4 '-diaminodiphenyl sulfide adds in 49.9077g1-butyl-3-methyl imidazolium bromide solvent (solid content 10%), be warming up to after 30 DEG C of stirrings make it fully to dissolve, be cooled to normal temperature for subsequent use;
2) by 3.2223g (10mmol) 2, 2 ', 3, 3 '-benzophenone tetracarboxylic dianhydride adds step 1 in batches) in gained solution, every batch of interval time is 20min, progressively be warming up to 180 DEG C again, progressively first be warming up to 100 DEG C with the speed of 20 DEG C/min by normal temperature in temperature-rise period, then 20 DEG C of insulation 20min are often heated up until temperature reaches 180 DEG C, react after 18 hours, successively through washing, drying treatment, washing, appropriate methyl alcohol and deionized water wash is first added in drying treatment process, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, repeat again above-mentioned steps number all over after, dry under temperature is 120 DEG C of conditions, obtain flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 8:
A preparation method for alternative laser sintering and moulding polyimide powder, comprises the steps:
1) under nitrogen or argon shield, by 3 of 0.6579g (3mmol), 3 '-dimethyl-4,1 of 4 '-benzidine and 0.7993g (7mmol), 4-diamino-cyclohexane adds in 42.1155g1-butyl-3-methyl imidazolium bromide solvent (solid content 10%), be warming up to after 50 DEG C of stirrings make it fully to dissolve, be cooled to normal temperature for subsequent use;
2) by 3.2223g (10mmol) 2, 3 ', 3, 4 '-benzophenone tetracarboxylic dianhydride adds step 1 in batches) in gained solution, every batch of interval time is 40min, progressively be warming up to 220 DEG C again, progressively first be warming up to 100 DEG C with the speed of 20 DEG C/min by normal temperature in temperature-rise period, then 20 DEG C of insulation 20min are often heated up until temperature reaches 220 DEG C, react after 16 hours, successively through washing, drying treatment, washing, appropriate methyl alcohol and deionized water wash is first added in drying treatment process, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, repeat again above-mentioned steps number all over after, dry under temperature is 120 DEG C of conditions, obtain flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 9:
A preparation method for alternative laser sintering and moulding polyimide powder, comprises the steps:
1) under nitrogen or argon shield, by 1 of the O-Phenylene Diamine of 0.5407 (5mmol) and 0.5710g (5mmol), 2-diamino-cyclohexane adds in 36.4851g1-butyl-3-methyl imidazolium bromide solvent (solid content 10%), be warming up to after 60 DEG C of stirrings make it fully to dissolve, be cooled to normal temperature for subsequent use;
2) by 2.9422g (10mmol) 2, 2 ', 6, 6 '-biphenyl tetracarboxylic dianhydride adds step 1 in batches) in gained solution, every batch of interval time is 40min, progressively be warming up to 240 DEG C again, progressively first be warming up to 100 DEG C with the speed of 20 DEG C/min by normal temperature in temperature-rise period, then 20 DEG C of insulation 20min are often heated up until temperature reaches 240 DEG C, react after 12 hours, successively through washing, drying treatment, washing, appropriate methyl alcohol and deionized water wash is first added in drying treatment process, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, repeat again above-mentioned steps number all over after, dry under temperature is 120 DEG C of conditions, obtain flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 10:
A preparation method for alternative laser sintering and moulding polyimide powder, comprises the steps:
1) under nitrogen or argon shield, by 1 of 0.7002 (4mmol), 1 of 4-diamino-2-butanone and 0.9664g (6mmol), 4-diaminobutane adds in 34.6302g1-butyl-3-methyl imidazolium bromide solvent (solid content 10%), be warming up to after 60 DEG C of stirrings make it fully to dissolve, be cooled to normal temperature for subsequent use;
2) 2.1812g (10mmol) pyromellitic acid dianhydride is added step 1 in batches) in gained solution, every batch of interval time is 40min, progressively be warming up to 260 DEG C again, progressively first be warming up to 100 DEG C with the speed of 20 DEG C/min by normal temperature in temperature-rise period, then 20 DEG C of insulation 20min are often heated up until temperature reaches 260 DEG C, react after 18 hours, successively through washing, drying treatment, washing, appropriate methyl alcohol and deionized water wash is first added in drying treatment process, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, repeat again above-mentioned steps number all over after, dry under temperature is 120 DEG C of conditions, obtain flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 11:
A preparation method for alternative laser sintering and moulding polyimide powder, comprises the steps:
1) under nitrogen or argon shield, by 2 of 0.2443g (2mmol), 2 of 6-diaminotoluene and 1.1407g (8mmol), 4-diaminochlorobenzene adds in 32.0958g1-butyl-3-methyl imidazolium bromide solvent (solid content 10%), be warming up to after 40 DEG C of stirrings make it fully to dissolve, be cooled to normal temperature for subsequent use;
2) 2.1812g (10mmol) pyromellitic acid dianhydride is added step 1 in batches) in gained solution, every batch of interval time is 40min, progressively be warming up to 200 DEG C again, progressively first be warming up to 100 DEG C with the speed of 20 DEG C/min by normal temperature in temperature-rise period, then 20 DEG C of insulation 20min are often heated up until temperature reaches 200 DEG C, react after 12 hours, successively through washing, drying treatment, washing, appropriate methyl alcohol and deionized water wash is first added in drying treatment process, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, repeat again above-mentioned steps number all over after, dry under temperature is 120 DEG C of conditions, obtain flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 12:
A preparation method for alternative laser sintering and moulding polyimide powder, comprises the steps:
1) under nitrogen or argon shield, by 3 of 1.0913 (10mmol), 4-diamino-pyridine adds in 36.3015g1-butyl-3-methyl imidazolium bromide solvent (solid content 10%), is warming up to after 60 DEG C of stirrings make it fully to dissolve, is cooled to normal temperature for subsequent use;
2) by 2.9422g (10mmol) 3, 3 ', 4, 4 '-biphenyl tetracarboxylic dianhydride adds step 1 in batches) in gained solution, every batch of interval time is 40min, progressively be warming up to 200 DEG C again, progressively first be warming up to 100 DEG C with the speed of 20 DEG C/min by normal temperature in temperature-rise period, then 20 DEG C of insulation 20min are often heated up until temperature reaches 200 DEG C, react after 6 hours, successively through washing, drying treatment, washing, appropriate methyl alcohol and deionized water wash is first added in drying treatment process, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, repeat again above-mentioned steps number all over after, dry under temperature is 120 DEG C of conditions, obtain flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 13:
A preparation method for alternative laser sintering and moulding polyimide powder, comprises the steps:
1) under nitrogen or argon shield, by 3 of 1.2415g (5mmol), 3 of 3 '-diaminodiphenylsulfone(DDS) and 1.2415g (5mmol), 4 '-diamino-diphenyl ether add in 48.8268g1-butyl-3-methyl imidazolium bromide solvent (solid content 10%), be warming up to after 60 DEG C of stirrings make it fully to dissolve, be cooled to normal temperature for subsequent use;
2) by 2.9422g (10mmol) 2, 2 ', 6, 6 '-biphenyl tetracarboxylic dianhydride adds step 1 in batches) in gained solution, every batch of interval time is 40min, progressively be warming up to 200 DEG C again, progressively first be warming up to 100 DEG C with the speed of 20 DEG C/min by normal temperature in temperature-rise period, then 20 DEG C of insulation 20min are often heated up until temperature reaches 220 DEG C, react after 24 hours, successively through washing, drying treatment, washing, appropriate methyl alcohol and deionized water wash is first added in drying treatment process, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, repeat again above-mentioned steps number all over after, dry under temperature is 120 DEG C of conditions, obtain flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 14:
A preparation method for alternative laser sintering and moulding polyimide powder, comprises the steps:
1) under nitrogen or argon shield, 1.0814g (10mmol) Ursol D is added in 23g1-butyl-3-methyl imidazolium tetrafluoroborate solvent (solid content 15%), be warming up to after 50 DEG C of stirrings make it fully to dissolve, be cooled to normal temperature for subsequent use;
2) by 2.9422g (10mmol) 3, 3 ', 4, 4 '-biphenyl tetracarboxylic dianhydride adds step 1 in batches) in gained solution, every batch of interval time is 30min, progressively be warming up to 200 DEG C again, progressively first be warming up to 100 DEG C with the speed of 20 DEG C/min by normal temperature in temperature-rise period, then 20 DEG C of insulation 20min are often heated up until temperature reaches 200 DEG C, sustained reaction is after 14 hours, successively through washing, drying treatment, wherein, washing, appropriate methyl alcohol and deionized water wash is first added in drying treatment process, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, repeat again above-mentioned steps number all over after, dry under temperature is 120 DEG C of conditions, obtain flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 15:
A preparation method for alternative laser sintering and moulding polyimide powder, comprises the steps:
1) under nitrogen or argon shield, 1.0814g (10mmol) Ursol D is added in 23g tetramethyl guanidine a tetrafluoro borate (solid content 15%), be warming up to after 60 DEG C of stirrings make it fully to dissolve, be cooled to normal temperature for subsequent use;
2) by 2.9422g (10mmol) 3, 3 ', 4, 4 '-bibenzene tetracarboxylic dianhydride adds step 1 in batches) in gained solution, every batch of interval time is 30min, progressively be warming up to 240 DEG C again, progressively first be warming up to 100 DEG C with the speed of 20 DEG C/min by normal temperature in temperature-rise period, then 20 DEG C of insulation 20min are often heated up until temperature reaches 240 DEG C, sustained reaction is after 20 hours, successively through washing, drying treatment, wherein, washing, appropriate methyl alcohol and deionized water wash is first added in drying treatment process, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, repeat again above-mentioned steps number all over after, dry under temperature is 100 DEG C of conditions, obtain flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 16:
A preparation method for alternative laser sintering and moulding polyimide powder, comprises the steps:
1) under nitrogen or argon shield, by 2.0024g (10mmol) 4,4 '-diaminodiphenyl oxide adds in 23.7070g1-butyl-3-methyl imidazolium bromide solvent (solid content 15%), is warming up to after 60 DEG C of stirrings make it fully to dissolve, is cooled to normal temperature for subsequent use;
2) 2.1812g (10mmol) pyromellitic acid dianhydride is added step 1 in batches) in gained solution, every batch of interval time is 20min, progressively be warming up to 200 DEG C again, progressively first be warming up to 100 DEG C with the speed of 20 DEG C/min by normal temperature in temperature-rise period, then 20 DEG C of insulation 20min are often heated up until temperature reaches 200 DEG C, sustained reaction is after 20 hours, successively through washing, drying treatment, wherein, washing, appropriate methyl alcohol and deionized water wash is first added in drying treatment process, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, repeat again above-mentioned steps number all over after, dry under temperature is 100 DEG C of conditions, obtain flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 17:
A preparation method for alternative laser sintering and moulding polyimide powder, comprises the steps:
1) under nitrogen or argon shield, by 2.0024g (10mmol) 4,4 '-diaminodiphenyl oxide adds 23.7070g chlorination 1, in 3-bis-(2-methoxyl group-2-oxygen ethyl) imidazoles (solid content 15%), be warming up to after 60 DEG C of stirrings make it fully to dissolve, be cooled to normal temperature for subsequent use;
2) 2.1812g (10mmol) pyromellitic acid dianhydride is added step 1 in batches) in gained solution, every batch of interval time is 20min, progressively be warming up to 200 DEG C again, progressively first be warming up to 100 DEG C with the speed of 20 DEG C/min by normal temperature in temperature-rise period, then 20 DEG C of insulation 20min are often heated up until temperature reaches 200 DEG C, sustained reaction is after 20 hours, successively through washing, drying treatment, wherein, washing, appropriate methyl alcohol and deionized water wash is first added in drying treatment process, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, repeat again above-mentioned steps number all over after, dry under temperature is 100 DEG C of conditions, obtain flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 18:
A preparation method for alternative laser sintering and moulding polyimide powder, comprises the steps:
1) under nitrogen or argon shield, by 4 of 1.2415g (5mmol), 4 of 4 '-diaminodiphenylsulfone(DDS) and 1.0815g (5mmol), 4 '-diaminodiphenyl sulfide adds 49.9077g1, in 3-bis-(2-methoxyl group-2-oxygen ethyl) limidazolium hexafluorophosphate (solid content 10%), be warming up to after 50 DEG C of stirrings make it fully to dissolve, be cooled to normal temperature for subsequent use;
2) by 3.2223g (10mmol) 2, 2 ', 3, 3 '-benzophenone tetracarboxylic dianhydride adds step 1 in batches) in gained solution, every batch of interval time is 20min, progressively be warming up to 180 DEG C again, progressively first be warming up to 100 DEG C with the speed of 20 DEG C/min by normal temperature in temperature-rise period, then 20 DEG C of insulation 20min are often heated up until temperature reaches 180 DEG C, react after 18 hours, successively through washing, drying treatment, washing, appropriate methyl alcohol and deionized water wash is first added in drying treatment process, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, repeat again above-mentioned steps number all over after, dry under temperature is 120 DEG C of conditions, obtain flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 19:
A preparation method for alternative laser sintering and moulding polyimide powder, comprises the steps:
1) under nitrogen or argon shield, 2.1628g (20mmol) Ursol D is added 45g1, in 3-bis-(2-methoxyl group-2-oxygen ethyl) imidazoles acetate (solid content 5%), be warming up to after 40 DEG C of stirrings make it fully to dissolve, be cooled to normal temperature for subsequent use;
2) by 5.8844g (20mmol) 3, 3 ', 4, 4 '-biphenyl tetracarboxylic dianhydride adds step 1 in batches) in gained solution, every batch of interval time is 20min, progressively be warming up to 180 DEG C again, progressively first be warming up to 100 DEG C with the speed of 20 DEG C/min by normal temperature in temperature-rise period, then 20 DEG C of insulation 20min are often heated up until temperature reaches 180 DEG C, sustained reaction is after 8 hours, successively through washing, drying treatment, wherein, washing, appropriate methyl alcohol and deionized water wash is first added in drying treatment process, Keep agitation, treat that powder is all separated out, by the powdered mixture decompress filter of gained, repeat again above-mentioned steps number all over after, dry under temperature is 80 DEG C of conditions, obtain flaxen alternative laser sintering and moulding polyimide powder.
Embodiment 20: effect example
The polyimide powder of gained is carried out performance test, and Fig. 1 is infrared spectrogram, from Fig. 1, and 1708cm -1and 1354cm -1the symmetrical stretching vibration of C=O and the stretching vibration of C-N in corresponding imide group respectively, 1074cm -1and 733cm -1the respectively flexural vibration peak of C-O and C=O in corresponding imide ring, the powder of known preparation is polyimide, simultaneously stretching vibration peak (the 1855cm of carbonyl in fragrant monomer -1and 1770cm -1), diamine groups (3400-3500cm -1), secondary amide group (1640cm -1and 1540cm -1) vibration peak is all invisible, illustrates that the imidization degree of complete and prepared polyimide powder is carried out in reaction high.
Fig. 2 is the thermogravimetric analysis figure of obtained alternative laser sintering and moulding polyimide powder, and rate of weight loss is that the temperature of 1%, 5%, 10% correspondence is respectively 447.37 DEG C, 609.15 DEG C, 625.7 DEG C.Fig. 3 is the obtained polyimide thermogravimetric analysis figure of conventional two-step (first synthesizing polyamides acid high temperature curing of coating again), and rate of weight loss is that the temperature of 1%, 5%, 10% correspondence is respectively 412 DEG C, 561.67 DEG C, 601.37 DEG C.By contrast, the polyimide prepared by the present invention has more excellent thermostability.
Fig. 4 is the means of differential scanning calorimetry figure of obtained alternative laser sintering and moulding polyimide powder, be the means of differential scanning calorimetry figure that conventional two-step prepares polyimide compared to Fig. 5, as can be seen from the figure there is obvious crosslinking curing peak, illustrate that polyimide prepared by the present invention possesses better machine-shaping property;
Fig. 6 is the scanning electron microscope (SEM) photograph that obtained alternative laser sintering and moulding polyimide powder amplifies 12000 times, Fig. 7 is the scanning electron microscope (SEM) photograph that embodiment 1 obtains alternative laser sintering and moulding polyimide powder and amplifies 500 times, gained polyimide powder disperses better, uniform particle diameter as we know from the figure, and amount of powder presents the spherical morphology of rule.
Fig. 8 is the grain size distribution of obtained alternative laser sintering and moulding polyimide powder, and powder diameter is normal distribution, and particle diameter is 5 ~ 100 μm, and its apparent density is 0.2 ~ 0.5g/cm 3.Table 1 obtains alternative laser sintering and moulding polyimide powder granularity and scope internal volume percentage ratio table for embodiment 1, and particle diameter is mainly distributed in 5 ~ 60 μm.
Table 1
Granularity (μm) Scope internal volume % Granularity (μm) Scope internal volume % Granularity (μm) Scope internal 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, be only the specific embodiment of the present invention, it should be pointed out that any those of ordinary skill in the art are in the technical scope disclosed by the present invention, the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.

Claims (10)

1. an alternative laser sintering and moulding polyimide powder, is characterized in that, the general structure of described alternative laser sintering and moulding polyimide powder is as follows:
In formula, n is 100 ~ 10 5interior integer.
2. alternative laser sintering and moulding polyimide powder according to claim 1, is characterized in that, the particle diameter of described alternative laser sintering and moulding polyimide powder is 5 ~ 100 μm, and its apparent density is 0.2 ~ 0.5g/cm 3.
3. prepare a method for the alternative laser sintering and moulding polyimide powder described in claim 1 or 2, it is characterized in that, comprise the steps:
1) under nitrogen or argon shield, diamines is added in ion solvent, be warming up to after 25 ~ 60 DEG C of stirrings make it fully to dissolve, be cooled to normal temperature for subsequent use;
2) dianhydride is added step 1 in batches) in gained solution, every batch of interval time is 20 ~ 40min, is more progressively warming up to 120 ~ 260 DEG C, and sustained reaction is after 2 ~ 24 hours, successively through washing, drying treatment, obtain alternative laser sintering and moulding polyimide powder.
4. the preparation method of alternative laser sintering and moulding polyimide powder according to claim 3, is characterized in that, described step 1) in, the mass ratio of diamines and ion solvent is 1:10 ~ 60.
5. the preparation method of alternative laser sintering and moulding polyimide powder according to claim 3, is characterized in that, described step 1) in, diamines is one or more in aromatic diamine, fats diamines, alicyclic diamine.
6. the preparation method of alternative laser sintering and moulding polyimide powder according to claim 5, it is characterized in that, described diamines is Ursol D, 4, 4 '-diaminodiphenyl-methane, 4, 4 '-diaminodiphenyl oxide, 4, 4 '-diaminodiphenylsulfone(DDS), 3, 4 '-diaminodiphenylsulfone(DDS), 3, 3 '-diaminodiphenylsulfone(DDS), 3, 4 '-diamino-diphenyl ether, O-Phenylene Diamine, 2, 6 '-diaminotoluene, 2, 4-diaminochlorobenzene, 3, 3 '-dimethyl-4, 4 '-benzidine, 4, 4 '-diaminodiphenyl sulfide, 1, 4-diaminobutane, 1, 4-diamino-cyclohexane, 1, 2-diamino-cyclohexane, 3, 4-diamino-pyridine, 1, one or more in 4-diamino-2-butanone.
7. the preparation method of alternative laser sintering and moulding polyimide powder according to claim 3, it is characterized in that, described step 1) in, ion solvent is 1-butyl-3-methyl imidazolium bromide, chlorination 1,3-bis-(2-methoxyl group-2-oxygen ethyl) imidazoles, 1, one in 3-bis-(2-methoxyl group-2-oxygen ethyl) limidazolium hexafluorophosphate, 1,3-bis-(2-methoxyl group-2-oxygen ethyl) imidazoles acetate, tetramethyl guanidine tetrafluoroborate ion liquid.
8. the preparation method of alternative laser sintering and moulding polyimide powder according to claim 3, it is characterized in that, described step 2) in, the mol ratio of dianhydride and diamines is 1:1, wherein, dianhydride is the one in aromatic series tetracarboxylic acid acid anhydride, aliphatics tetracarboxylic anhydride, Alicyclic tetracarboxylic acid acid anhydride, heterocycle race tetracarboxylic anhydride.
9. the preparation method of alternative laser sintering and moulding polyimide powder according to claim 8, is characterized in that, described dianhydride is 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, pyromellitic acid dianhydride, 2,3,3 ', 4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 2,2 ' 6,6 '-biphenyl tetracarboxylic dianhydride, butane-1,2, one in 3,4-tetracarboxylic dianhydride.
10. the preparation method of alternative laser sintering and moulding polyimide powder according to claim 3, it is characterized in that, described step 2) in, progressively first be warming up to 100 DEG C with the speed of 5 ~ 20 DEG C/min by normal temperature in temperature-rise period, the 20 DEG C of insulation 20min that then often heat up are until temperature reaches 120 ~ 260 DEG C.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106380610A (en) * 2016-09-23 2017-02-08 江西师范大学 Method for preparing polyether sulfone powder consumable item for 3D printing of laser sintering and molding
CN113072703A (en) * 2021-04-19 2021-07-06 中国科学院化学研究所 Thermoplastic polyimide with excellent comprehensive performance and preparation method and application thereof
CN117548622A (en) * 2024-01-05 2024-02-13 中国机械总院集团沈阳铸造研究所有限公司 Precoated sand for selective laser sintering and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006249166A (en) * 2005-03-09 2006-09-21 Nippon Synthetic Chem Ind Co Ltd:The Manufacturing process of aromatic polyimide
CN102219900A (en) * 2011-04-12 2011-10-19 北京市射线应用研究中心 Synthesizing method of polyimide
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
WO2015120430A1 (en) * 2014-02-10 2015-08-13 President And Fellows Of Harvard College 3d-printed polishing pad for chemical-mechanical planarization (cmp)

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006249166A (en) * 2005-03-09 2006-09-21 Nippon Synthetic Chem Ind Co Ltd:The Manufacturing process of aromatic polyimide
CN102219900A (en) * 2011-04-12 2011-10-19 北京市射线应用研究中心 Synthesizing method of polyimide
WO2015120430A1 (en) * 2014-02-10 2015-08-13 President And Fellows Of Harvard College 3d-printed polishing pad for chemical-mechanical planarization (cmp)
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

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106380610A (en) * 2016-09-23 2017-02-08 江西师范大学 Method for preparing polyether sulfone powder consumable item for 3D printing of laser sintering and molding
CN106380610B (en) * 2016-09-23 2018-08-21 江西师范大学 The preparation method of laser sintering (SLS) 3D printing polyether sulfone powder supplies
CN113072703A (en) * 2021-04-19 2021-07-06 中国科学院化学研究所 Thermoplastic polyimide with excellent comprehensive performance and preparation method and application thereof
CN117548622A (en) * 2024-01-05 2024-02-13 中国机械总院集团沈阳铸造研究所有限公司 Precoated sand for selective laser sintering and preparation method thereof
CN117548622B (en) * 2024-01-05 2024-03-12 中国机械总院集团沈阳铸造研究所有限公司 Precoated sand for selective laser sintering and preparation method thereof

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