CN108192097A - A kind of solvable thermoplastic polyimide and its ultra-fine powder, preparation method thereof - Google Patents
A kind of solvable thermoplastic polyimide and its ultra-fine powder, preparation method thereof Download PDFInfo
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- CN108192097A CN108192097A CN201711257191.XA CN201711257191A CN108192097A CN 108192097 A CN108192097 A CN 108192097A CN 201711257191 A CN201711257191 A CN 201711257191A CN 108192097 A CN108192097 A CN 108192097A
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Classifications
-
- 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
- C08G73/1046—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
- C08G73/1003—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
- C08G73/1067—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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention belongs to field of polymer material preparing technology, are related to the preparation method of a kind of solvable thermoplastic polyimide and its superfine powder.The solvable polyimides of the present invention is by asymmetric ether dianhydride (a ODPA) and ether diamine (1,3,4 APB) it is polymerized, using aprotic polar solvent as reaction dissolvent, cyclization process is completed using chemical imines method, it is precipitated under high-pressure atomization and high-speed stirred effect, washed, dry, superfreeze, which crushes, obtains solvable thermoplastic polyimide superfines.The solvable thermoplastic polyimide of the present invention has excellent dissolubility in the organic solvents such as DMAC, DMF, NMP, available for fields such as resin modified, high-temperature resistant membrane, High-performance adhesive, thermoplastic fibre, thermoplastic composites.
Description
Technical field
The invention belongs to field of polymer material preparing technology, are related to a kind of solvable thermoplastic polyimide and its superfine powder
Preparation method.
Background technology
Polyimides is a kind of high temperature polymeric materials with Good All-around Property, and wherein thermoplastic polyimide has
There are excellent heat resistance, mechanical property, dielectric properties, flame retardant property etc..Most of thermoplastic polyimide have indissoluble hardly possible
The characteristics of molten, although hot property, mechanical property requirements can be met, its processing performance is affected, it is further wide to limit it
General application.Therefore, under the premise of the original hot property of polyimides is ensured, soluble polyimide is found and application has weight
Meaning is wanted, available for resin modified, high-temperature resistant membrane, High-performance adhesive, coating, thermoplastic fibre, thermoplastic composite
The fields of grade.
In order to improve the processing performance of polyimides, it will usually the molecular structure of synthesis of polyimides is designed, it will
Flexible structure unit or the larger side group of volume etc., which introduce molecular chain structure, passes through copolyreaction improves dissolubility, reduces polyamides
The methods of symmetry of imines chain structure, destroys the upright and outspoken chain structure of main chain and the intermolecular interaction force of reduction to reach,
It is the means for improving polyimides solubility property.CN 101085833 discloses soluble fluorine-containing aromatic polyimide and its conjunction
Into method, CN101456954 is disclosed prepares polyimides containing double miscellaneous naphthalenone structures and trifluoromethyl substituted aroma diamine monomer
Method, CN104356386 discloses a kind of soluble polyimides of fluorine-containing and isopropyl based structures and preparation method thereof, and obtains
Obtained the fibrous polyimides of favorable solubility.Multinomial patent discloses the solvable thermoplastic polyimide of various structures and its system
Preparation Method, the product form that these patents obtain is mostly film, resin solution, ordinary resin powder, mainly or for gluing
The application of agent, coating, film etc..
Soluble polyimide is due to good dissolubility energy, dissolving in or being slightly soluble in a variety of organic solvents or mixing
Solvent, therefore the preparation difficulty of its superfine powder is larger.Thermoplastic polymer superfine powder is in high-performance thermosetting resin and its compound
Material modification field has obtained extensive use, and for example the superfine powders such as polyether-ether-ketone, polyether sulphone are in terms of epoxy resin modification
With more report, but for the modification of temperature resistant grade higher bismaleimide, thermoset polyimide resin, often
Since heat resistance deficiency and matching effect are bad and be unable to reach the purpose of toughening modifying.Solvable thermoplastic polyimide is ultra-fine
Powder due to good dissolubility energy and toughness properties, high performance resin and its composite modification field have compared with
Good application prospect, available for epoxy resin, bimaleimide resin, polyimide resin toughening modifying.It is in addition, solvable
Thermoplastic polyimide superfine powder can realize quick dissolving in organic solvent, it may also be used for high-temperature resistant membrane, high-performance glue
The multiple fields such as glutinous agent, thermoplastic fibre, thermoplastic composite.
Invention content
The purpose of the present invention is：It is proposed the preparation method of a kind of solvable thermoplastic polyimide and its superfine powder, it would be desirable to
The dissolubility of polyimide resin is enough improved, and can realize the preparation of superfine powder, it is made to can be used for resin modified, high temperature resistant thin
The fields such as film, High-performance adhesive, thermoplastic fibre, thermoplastic composite.
The technical scheme is that：
The solvable thermoplastic polyimide has following molecular structure：
Dianhydride monomer is a-OPDA used by the solvable thermoplastic polyimide resin, has following molecule knot
Structure：
Diamine monomer is 1,3,4-APB used by the solvable thermoplastic polyimide resin, has following molecule
Structure：
The dianhydride monomer a-OPDA and the molar ratio of diamine monomer 1,3,4-APB are：1.0~1.03：1.0.
The solvable thermoplastic polyimide superfine powder is prepared in accordance with the following methods：
(1) under room temperature condition (25 DEG C), by 1,3,4-APB powder monomer add in mechanical stirring device, condensing unit,
In reaction vessel under nitrogen atmosphere, organic solvent is then added in, consumption of organic solvent is the 70%~95% of solution gross weight, is stirred
Mixing makes it be dissolved to solution in clear state, and it is -10 DEG C~30 DEG C to control diamine solution temperature.
(2) α-ODPA monomer powders are directly added into above-mentioned diamine solution, it is stirring while adding, treat that reaction monomers are complete
After dissolving, control temperature of reaction system is -10 DEG C~30 DEG C, persistently stirs 2h~12h and obtains polyamic acid solution.
(3) polyamic acid solution that above-mentioned reaction obtains is slowly added to be made of organic solvent, dehydrating agent and catalyst
Catalyst system and catalyzing in, consumption of organic solvent be catalyst system and catalyzing weight 20%-50%, dehydrating agent dosage be 1-4 times of diamine monomer
(mole dosage), catalyst amount are the 30%-60% (mole dosage) of dehydrating agent, and 2h- is stirred to react at 0 DEG C -50 DEG C
For 24 hours, the polyimide solution of chemical imidization is obtained.
(4) it by polyimide solution concentration dilution to 1%-10%, is subsequently poured into high-pressure atomization spray gun, and with 0.05-
Solid is precipitated in the cleaning solvent that the pressure of 0.2MPa is spurted into resin solution under high-speed stirred, is removed using centrifuge dripping method
Solvent is removed, washs 1-6 times repeatedly, half dry solid after washing is placed into 12h-48h at room temperature, obtains solid powder.
(5) obtained solid powder is placed in vacuum drying oven, 6h-48h is handled at 100 DEG C -260 DEG C, obtain polyamides Asia
Polyimide resin powder, and it is crushed using low-temperature grinding method, it is -100 DEG C -0 DEG C to crush temperature, and acquisition can compatible thermoplastic
Polyimides superfines.
The organic solvent is dioxane, pyridine, n,N-dimethylacetamide, n,N-Dimethylformamide, N- first
One or more of base pyrrolidones, metacresol.
The catalyst is：Triethylamine, pyridine；Dehydrating agent is acetic anhydride；Catalyst system and catalyzing is combined as：(triethylamine+acetic acid
Acid anhydride) or (pyridine+acetic anhydride).
The cleaning solvent is resin for methanol or ethyl alcohol or acetone or tetrahydrofuran or distilled water, cleaning solvent dosage
3-10 times of solution weight.
The breaking method is mechanical crushing or air-flow crushing.
The present invention has the advantage that is with advantageous effect：
The present invention is using non-title ether dianhydride (a-ODPA) and ether diamine (1,3,4-APB) as reaction monomers, chemistry knot
The solvable thermoplastic polyimide of structure has good dissolubility energy, and it is a variety of organic molten to be dissolvable in water DMAC, DMF, NMP, THF etc.
In agent, and with excellent toughness properties, mechanical property and heat resistance；It is molten as reaction using aprotic polar solvent
Agent completes cyclization process using chemical imines method, and synthesis technology is stable and easy to control, and molecular weight control accuracy is higher, gained
Resin property is stably and controllable；It is precipitated under high-speed stirred shear action into powder using high-pressure atomization method, and with reference to ultra-low temperature cold
The broken method of agar can realize the preparation of solvable thermoplastic polyimide superfines, the superfine powder grain size of acquisition up to 1 micron-
50 microns.The solvable thermoplastic polyimide superfine powder obtained can be used for high-temperature resistant membrane, High-performance adhesive, thermoplasticity fine
The multiple fields such as dimension, thermoplastic composite especially have preferable in high performance resin and its composite modification field
Application prospect, available for epoxy resin, bimaleimide resin, polyimide resin toughening modifying.
Specific embodiment
The present invention is described in further details below.A kind of solvable thermoplastic polyimide and preparation method thereof, it is special
Sign is that using asymmetric ether dianhydride (a-ODPA) and ether diamine (1,3,4-APB) be monomer, is made using aprotic polar solvent
For reaction dissolvent, cyclization process is completed using chemical imines method, is precipitated under high-pressure atomization and high-speed stirred effect, through washing
It washs, dry, superfreeze crushes and obtains solvable thermoplastic polyimide superfines.
(1) dianhydride monomer is selected as a-OPDA, diamine monomer 1,3,4-APB controls a-OPDA and 1, and 3,4-APB rub
You are at ratio：1.0~1.03：1.0.
(2) under room temperature condition (25 DEG C), by 1,3,4-APB powder monomer add in mechanical stirring device, condensing unit,
In reaction vessel under nitrogen atmosphere, organic solvent is then added in, consumption of organic solvent is the 70%~95% of solution gross weight, is stirred
Mixing makes it be dissolved to solution in clear state, and it is -10 DEG C~30 DEG C to control diamine solution temperature.
(3) α-ODPA monomer powders are directly added into above-mentioned diamine solution, it is stirring while adding, treat that reaction monomers are complete
After dissolving, control temperature of reaction system is -10 DEG C~30 DEG C, persistently stirs 2h~12h and obtains polyamic acid solution.
(4) polyamic acid solution that above-mentioned reaction obtains is slowly added to be made of organic solvent, dehydrating agent and catalyst
Catalyst system and catalyzing in, consumption of organic solvent be catalyst system and catalyzing weight 20%-50%, dehydrating agent dosage be 1-4 times of diamine monomer
(mole dosage), catalyst amount are the 30%-60% (mole dosage) of dehydrating agent, and consumption of organic solvent, dehydrating agent dosage is,
Catalyst amount is to be stirred to react 2h-24h at 0 DEG C -50 DEG C, obtains the polyimide solution of chemical imidization.
(5) it by polyimide solution concentration dilution to 1%-10%, is subsequently poured into high-pressure atomization spray gun, and with 0.05-
Solid is precipitated in the cleaning solvent that the pressure of 0.2MPa is spurted into resin solution under high-speed stirred, is removed using centrifuge dripping method
Solvent is removed, washs 1-6 times repeatedly, half dry solid after washing is placed into 12h-48h at room temperature, obtains solid powder.
(6) obtained solid powder is placed in vacuum drying oven, 6h-48h is handled at 100 DEG C -260 DEG C, obtain polyamides Asia
Polyimide resin powder, and it is crushed using low-temperature grinding method, it is -100 DEG C -0 DEG C to crush temperature, and acquisition can compatible thermoplastic
Polyimides superfines.
Specific embodiment 1
Under room temperature condition (25 DEG C), 1,3,4-APB powder monomers of 292.33g (1mol), which are added in, has mechanical agitation dress
It puts, in the reaction vessel under condensing unit, nitrogen atmosphere, then adds in 3362gDMAc, stir to dissolve to solution in clarification
State, and it is 20 DEG C to control diamine solution temperature.316.41g (1.02mol) α-ODPA monomer powders are directly added into above-mentioned two
Stirring while adding in amine aqueous solution, after reaction monomers are completely dissolved, control temperature of reaction system is 20 DEG C, persistently stirs 6h
Obtain polyamic acid solution.The polyamic acid solution that above-mentioned reaction obtains is slowly added to by 305.37gDMAc, 204.18g
In the catalyst system and catalyzing of (2mol) acetic anhydride and 101.19g (1mol) triethylamine composition, 12h is stirred to react at 20 DEG C, is changed
Learn the polyimide solution of imidization.Polyimide solution concentration dilution to 10% is subsequently poured into high-pressure atomization spray gun, and
Solid is precipitated in the ethyl alcohol for spurting into resin solution under high-speed stirred with the pressure of 0.1MPa, then using centrifuge dripping method
It washs 4 times repeatedly, half dry solid after washing is placed for 24 hours at room temperature.Obtained solid powder is placed in vacuum drying oven,
12h is handled at 260 DEG C, obtains polyimide resin powder end.By toner at -50 DEG C its carry out air-flow crushing, pass through control
The flow of liquid nitrogen processed controls crushing temperature, and the solvable thermoplastic polyimide superfines particle diameter distribution of acquisition is at 5 micron -15
In micron range.The superfine powder of acquisition is hot-forming under 320 DEG C, the pressure of 5MPa, obtain thermoplastic polyimide resin
Sample.
1 solvable polyimides solubility property of table
Note：++ dissolving；+ be partly dissolved；It is insoluble
The physicochemical property and mechanical property of 2 solvable polyimide resin of table
| Serial number | Test event | Test result | Test method |
| 1 | Number-average molecular weight (Mn), g/mol | 2.68×104 | GPC |
| 2 | Glass transition temperature (Tg), DEG C | 236 | DMA methods |
| 3 | Heat decomposition temperature (5%), DEG C | 545 | TGA methods |
| 4 | Impact strength, MPa | 103 | GB/T 2567-2008 |
| 5 | Tensile strength, MPa | 100 | GB/T 16421-1996 |
| 6 | Elongation at break, % | 9.68 | GB/T 16421-1996 |
Specific embodiment 2
Under room temperature condition (25 DEG C), 1,3,4-APB powder monomers of 292.33g (1mol), which are added in, has mechanical agitation dress
It puts, in the reaction vessel under condensing unit, nitrogen atmosphere, then adds in 3362gDMAc, stir to dissolve to solution in clarification
State, and it is 20 DEG C to control diamine solution temperature.316.41g (1.02mol) α-ODPA monomer powders are directly added into above-mentioned two
Stirring while adding in amine aqueous solution, after reaction monomers are completely dissolved, control temperature of reaction system is 20 DEG C, persistently stirs 6h
Obtain polyamic acid solution.The polyamic acid solution that above-mentioned reaction obtains is slowly added to by 305.37gDMAc, 204.18g
In the catalyst system and catalyzing of (2mol) acetic anhydride and 101.19g (1mol) triethylamine composition, 12h is stirred to react at 20 DEG C, is changed
Learn the polyimide solution of imidization.Polyimide solution concentration dilution to 5% is subsequently poured into high-pressure atomization spray gun, and
Solid is precipitated in the ethyl alcohol for spurting into resin solution under high-speed stirred with the pressure of 0.1MPa, then using centrifuge dripping method
It washs 4 times repeatedly, half dry solid after washing is placed for 24 hours at room temperature.Obtained solid powder is placed in vacuum drying oven,
12h is handled at 260 DEG C, obtains polyimide resin powder end.By toner at -70 DEG C its carry out air-flow crushing, pass through control
The flow of liquid nitrogen processed controls crushing temperature, and the solvable thermoplastic polyimide superfines particle diameter distribution of acquisition is at 2 micron -10
In micron range.The superfine powder of acquisition is hot-forming under 320 DEG C, the pressure of 5MPa, obtain thermoplastic polyimide resin
Sample.
3 solvable polyimides solubility property of table
Note：++ dissolving；+ be partly dissolved；It is insoluble
The physicochemical property and mechanical property of 4 solvable polyimide resin of table
| Serial number | Test event | Test result | Test method |
| 1 | Number-average molecular weight (Mn), g/mol | 2.72×104 | GPC |
| 2 | Glass transition temperature (Tg), DEG C | 238 | DMA methods |
| 3 | Heat decomposition temperature (5%), DEG C | 549 | TGA methods |
| 4 | Impact strength, MPa | 106 | GB/T 2567-2008 |
| 5 | Tensile strength, MPa | 110 | GB/T 16421-1996 |
| 6 | Elongation at break, % | 12.56 | GB/T 16421-1996 |
Specific embodiment 3
Under room temperature condition (25 DEG C), 1,3,4-APB powder monomers of 292.33g (1mol), which are added in, has mechanical agitation dress
It puts, in the reaction vessel under condensing unit, nitrogen atmosphere, then adds in 5554gNMP, stir to dissolve to solution in clarification
State, and it is 0 DEG C to control diamine solution temperature.313.31g (1.01mol) α-ODPA monomer powders are directly added into above-mentioned diamines
Stirring while adding in solution, after reaction monomers are completely dissolved, control temperature of reaction system is 20 DEG C, persistently stirs 12h and obtains
To polyamic acid solution.The polyamic acid solution that above-mentioned reaction obtains is slowly added to by 305.37gNMP, 306.27g (3mol)
It in the catalyst system and catalyzing of acetic anhydride and 151.79g (1.5mol) triethylamine composition, is stirred to react at 20 DEG C for 24 hours, obtains chemical Asia
The polyimide solution of amination.Polyimide solution concentration dilution to 8% is subsequently poured into high-pressure atomization spray gun, and with
Solid is precipitated in the ethyl alcohol that the pressure of 0.15MPa is spurted into resin solution under high-speed stirred, then using centrifuge dripping method
It washs 4 times repeatedly, half dry solid after washing is placed into 36h at room temperature.Obtained solid powder is placed in vacuum drying oven,
18h is handled at 260 DEG C, obtains polyimide resin powder end.By toner at -50 DEG C its carry out air-flow crushing, pass through control
The flow of liquid nitrogen processed controls crushing temperature, and the solvable thermoplastic polyimide superfines particle diameter distribution of acquisition is at 5 micron -20
In micron range.The superfine powder of acquisition is hot-forming under 330 DEG C, the pressure of 5MPa, obtain thermoplastic polyimide resin
Sample.
1 solvable polyimides solubility property of table
Note：++ dissolving；+ be partly dissolved；It is insoluble
The physicochemical property and mechanical property of 2 solvable polyimide resin of table
Specific embodiment 4
Under room temperature condition (25 DEG C), 1,3,4-APB powder monomers of 292.33g (1mol), which are added in, has mechanical agitation dress
It puts, in the reaction vessel under condensing unit, nitrogen atmosphere, then adds in 7016gNMP, stir to dissolve to solution in clarification
State, and it is 0 DEG C to control diamine solution temperature.312.278g (1.01mol) α-ODPA monomer powders are directly added into above-mentioned two
Stirring while adding in amine aqueous solution, after reaction monomers are completely dissolved, control temperature of reaction system is 20 DEG C, persistently stirs 15h
Obtain polyamic acid solution.The polyamic acid solution that above-mentioned reaction obtains is slowly added to by 283.28gNMP, 306.27g
In the catalyst system and catalyzing of (3mol) acetic anhydride and 118.65g (1.5mol) pyridine composition, 36h is stirred to react at 20 DEG C, is changed
Learn the polyimide solution of imidization.Polyimide solution concentration dilution to 6% is subsequently poured into high-pressure atomization spray gun, and
Solid is precipitated in the ethyl alcohol for spurting into resin solution under high-speed stirred with the pressure of 0.2MPa, then using centrifuge dripping method
It washs 5 times repeatedly, half dry solid after washing is placed into 40h at room temperature.Obtained solid powder is placed in vacuum drying oven,
It is handled at 260 DEG C for 24 hours, obtains polyimide resin powder end.By toner at -80 DEG C its carry out air-flow crushing, pass through control
The flow of liquid nitrogen processed controls crushing temperature, and the solvable thermoplastic polyimide superfines particle diameter distribution of acquisition is at 5 micron -15
In micron range.The superfine powder of acquisition is hot-forming under 330 DEG C, the pressure of 5MPa, obtain thermoplastic polyimide resin
Sample.
1 solvable polyimides solubility property of table
Note：++ dissolving；+ be partly dissolved；It is insoluble
The physicochemical property and mechanical property of 2 solvable polyimide resin of table
| Serial number | Test event | Test result | Test method |
| 1 | Number-average molecular weight (Mn), g/mol | 9.26×104 | GPC |
| 2 | Glass transition temperature (Tg), DEG C | 252 | DMA methods |
| 3 | Heat decomposition temperature (5%), DEG C | 576 | TGA methods |
| 4 | Impact strength, MPa | 135 | GB/T 2567-2008 |
| 5 | Tensile strength, MPa | 106 | GB/T 16421-1996 |
| 6 | Elongation at break, % | 36.5% | GB/T 16421-1996 |
Claims (5)
1. the preparation method of a kind of solvable thermoplastic polyimide and its superfine powder, which is characterized in that described can compatible thermoplastic
Polyimides has following molecular structure：
Wherein, used dianhydride monomer is a-OPDA, has following molecular structure：
Used diamine monomer is 1,3,4-APB, has following molecular structure：
The molar ratio of used dianhydride monomer a-OPDA and diamine monomer 1,3,4-APB is：1.0~1.03：1.0；
The preparation method of solvable thermoplastic polyimide and its superfine powder is prepared according to following steps：
(1) at 25 DEG C of room temperature, 1,3,4-APB monomer powders are added in under mechanical stirring device, condensing unit, nitrogen atmosphere
Reaction vessel in, then add in organic solvent, consumption of organic solvent is the 70%~95% of solution gross weight, is stirred to dissolve
To solution in clear state, and it is -10 DEG C~30 DEG C to control diamine solution temperature；
(2) α-ODPA monomer powders are directly added into above-mentioned diamine solution, it is stirring while adding, treat that reaction monomers are completely dissolved
Afterwards, control temperature of reaction system is -10 DEG C~30 DEG C, persistently stirs 2h~12h and obtains polyamic acid solution；
(3) polyamic acid solution that above-mentioned reaction obtains is slowly added to be urged by what organic solvent, dehydrating agent and catalyst formed
In change system, consumption of organic solvent is the 20%-50% of catalyst system and catalyzing weight, and the mole dosage of dehydrating agent is 1-4 times of diamines list
Body 1,3,4-APB, the mole dosage of catalyst are the 30%-60% of dehydrating agent, are stirred to react 2h-24h at 0 DEG C -50 DEG C, obtain
To the polyimide solution of chemical imidization；
(4) it by polyimide solution concentration dilution to 1%-10%, is subsequently poured into high-pressure atomization spray gun, and with 0.05-
Solid is precipitated in the cleaning solvent that the pressure of 0.2MPa is spurted into resin solution under high-speed stirred, is removed using centrifuge dripping method
Solvent is removed, washs 1-6 times repeatedly, half dry solid after washing is placed into 12h-48h at room temperature, obtains solid powder；
(5) obtained solid powder is placed in vacuum drying oven, 6h-48h is handled at 100 DEG C -260 DEG C, obtain polyimides tree
Cosmetics end, and it is crushed using low-temperature grinding method, it is -100 DEG C -0 DEG C to crush temperature, obtains solvable thermoplasticity polyamides
Imines superfines.
2. according to a kind of solvable thermoplastic polyimide and its preparation method of superfine powder described in claim 1, feature
It is, the organic solvent is dioxane, pyridine, n,N-dimethylacetamide, n,N-Dimethylformamide, N- methyl pyrroles
One or more of pyrrolidone, metacresol.
3. according to a kind of solvable thermoplastic polyimide and its preparation method of superfine powder described in claim 1, feature
It is, the catalyst is：Triethylamine, pyridine etc.；Dehydrating agent is acetic anhydride；Catalyst system and catalyzing is combined as：Triethylamine and acetic acid
Acid anhydride or pyridine and acetic anhydride.
4. according to a kind of solvable thermoplastic polyimide and its preparation method of superfine powder described in claim 1, feature
It is, the cleaning solvent is molten for resin for methanol or ethyl alcohol or acetone or tetrahydrofuran or distilled water, cleaning solvent dosage
3-10 times of liquid weight.
5. according to a kind of solvable thermoplastic polyimide and its preparation method of superfine powder described in claim 1, feature
It is, the breaking method is mechanical crushing or air-flow crushing.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256670A (en) * | 2019-05-24 | 2019-09-20 | 东南大学 | One kind thermoplastic polyimide containing fluorene group and its preparation method and application |
| CN110713598A (en) * | 2019-11-22 | 2020-01-21 | 哈尔滨工业大学 | Preparation method of soluble low-temperature imidized polyimide |
| CN112552513A (en) * | 2020-12-08 | 2021-03-26 | 珠海长先新材料科技股份有限公司 | Synthesis process of nano polyimide micro powder |
| CN112592475A (en) * | 2020-12-20 | 2021-04-02 | 武汉市美克亚胺科技有限责任公司 | Preparation method and application of polyimide micropowder |
| CN113402709A (en) * | 2021-05-07 | 2021-09-17 | 苏州予信天材新材料应用技术有限公司 | High-temperature-resistant polyimide soluble in o-diallyl bisphenol A and preparation method thereof |
| CN113698601A (en) * | 2021-09-06 | 2021-11-26 | 黄山金石木塑料科技有限公司 | Method for synthesizing high-performance polyimide resin with assistance of ultrasonic microwave method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108124A (en) * | 2010-12-30 | 2011-06-29 | 上海市合成树脂研究所 | Preparation method of meltable polyimide moulding compound |
| CN102219902A (en) * | 2011-05-19 | 2011-10-19 | 中国科学院长春应用化学研究所 | Polymide molding powder and preparation method thereof |
| CN104098772A (en) * | 2014-07-29 | 2014-10-15 | 上海华谊（集团）公司 | Novel polyamide-imide preparation method |
| CN105111469A (en) * | 2015-09-08 | 2015-12-02 | 上海华谊（集团）公司 | Preparation method of polyamideimide fine powder |
| CN105175721A (en) * | 2015-08-17 | 2015-12-23 | 吉林大学 | Method for preparing polyimide moulding powder with uniform molecular weight distribution |
-
2017
- 2017-12-01 CN CN201711257191.XA patent/CN108192097A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108124A (en) * | 2010-12-30 | 2011-06-29 | 上海市合成树脂研究所 | Preparation method of meltable polyimide moulding compound |
| CN102492141A (en) * | 2010-12-30 | 2012-06-13 | 上海市合成树脂研究所 | Soluble polyimide molded plastic and preparation method thereof |
| CN102219902A (en) * | 2011-05-19 | 2011-10-19 | 中国科学院长春应用化学研究所 | Polymide molding powder and preparation method thereof |
| CN104098772A (en) * | 2014-07-29 | 2014-10-15 | 上海华谊（集团）公司 | Novel polyamide-imide preparation method |
| CN105175721A (en) * | 2015-08-17 | 2015-12-23 | 吉林大学 | Method for preparing polyimide moulding powder with uniform molecular weight distribution |
| CN105111469A (en) * | 2015-09-08 | 2015-12-02 | 上海华谊（集团）公司 | Preparation method of polyamideimide fine powder |
Non-Patent Citations (4)
| Title |
|---|
| HAI-WANG SONG,ET AL.: "Synthesis and Properties of Organic Soluble Polyimide Derived from 2,3,3",4"-Oxydiphthalic Anhydride and Various Aromatic Diamines", 《7TH INTERNATIONAL SYMPOSIUM ON HIGH-TECH POLYMER MATERIALS》 * |
| HAI-WANG SONG,ET AL.: "Synthesis and Properties of Organic Soluble Polyimide Derived from 2,3,3’,4’-Oxydiphthalic Anhydride and Various Aromatic Diamines", 《7TH INTERNATIONAL SYMPOSIUM ON HIGH-TECH POLYMER MATERIALS》 * |
| 李凤生: "《超细粉体技术》", 31 July 2000, 国防工业出版社 * |
| 藏雨等: "《气体分离膜材料科学》", 31 January 2017, 哈尔滨工业大学出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256670A (en) * | 2019-05-24 | 2019-09-20 | 东南大学 | One kind thermoplastic polyimide containing fluorene group and its preparation method and application |
| CN110256670B (en) * | 2019-05-24 | 2021-06-01 | 东南大学 | Thermoplastic polyimide containing fluorene group and preparation method and application thereof |
| CN110713598A (en) * | 2019-11-22 | 2020-01-21 | 哈尔滨工业大学 | Preparation method of soluble low-temperature imidized polyimide |
| CN112552513A (en) * | 2020-12-08 | 2021-03-26 | 珠海长先新材料科技股份有限公司 | Synthesis process of nano polyimide micro powder |
| CN112592475A (en) * | 2020-12-20 | 2021-04-02 | 武汉市美克亚胺科技有限责任公司 | Preparation method and application of polyimide micropowder |
| CN113402709A (en) * | 2021-05-07 | 2021-09-17 | 苏州予信天材新材料应用技术有限公司 | High-temperature-resistant polyimide soluble in o-diallyl bisphenol A and preparation method thereof |
| CN113402709B (en) * | 2021-05-07 | 2022-09-16 | 苏州予信天材新材料应用技术有限公司 | High-temperature-resistant polyimide soluble in o-diallyl bisphenol A and preparation method thereof |
| CN113698601A (en) * | 2021-09-06 | 2021-11-26 | 黄山金石木塑料科技有限公司 | Method for synthesizing high-performance polyimide resin with assistance of ultrasonic microwave method |
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