CN104710789A - Preparation method of polyimide molding powder - Google Patents
Preparation method of polyimide molding powder Download PDFInfo
- Publication number
- CN104710789A CN104710789A CN201510113931.7A CN201510113931A CN104710789A CN 104710789 A CN104710789 A CN 104710789A CN 201510113931 A CN201510113931 A CN 201510113931A CN 104710789 A CN104710789 A CN 104710789A
- Authority
- CN
- China
- Prior art keywords
- powder
- preparation
- solvent
- molding powder
- polyimide molding
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C08G73/1067—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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
Abstract
The invention discloses a preparation method of polyimide molding powder, and belongs to the technical field of high polymer materials. The preparation method comprises the following steps: under conditions of mechanical stirring and inert gas shielding, dissolving a diamine monomer and a dianhydride monomer into an organic solvent, performing a reaction for 3-8 hours at the room temperature, then adding an end-capping reagent, and then continuing to perform the reaction for 4-10 hours to obtain a polyamide acid solution (PAA); in an emulsifying machine, preparing yellow imide resin powder; washing the yellow imide resin powder with a solvent for 3-5 times, filtering, removing the solvent at 160-180 DEG C, and performing vacuum drying at the temperature of 200-300 DEG C, so as to obtain the polyimide molding powder. According to the preparation method disclosed by the invention, the high-speed stirring step of the emulsifying machine is simple, convenient and feasible; most of the used solvent can be recycled; in the preparation process, the hazardous substance cannot be released into atmosphere; compared with the molding powder prepared by the conventional thermal imidization method, under the situation that the thermal stability is basically remained to be unchanged, the processing windows of the two kinds of molding powder are identical, but the lowest viscosity of the molding powder is reduced to a certain extent.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of preparation method of polyimide molding powder.
Background technology
Polyimide molding powder is that a class has significant application value, more typical engineering plastics, it can injection moulding, extrude or be placed in mould, compression moulding under High Temperature High Pressure, not only convenient transport, and do not have solvent to discharge at final molding stage, can manufacture comparatively complicated component, therefore market demand increases day by day.
Polyimide molding powder be widely used in Aeronautics and Astronautics, electrically, the field such as machinery, chemical industry, microelectronics: such as aircraft jet engine part and tagblock and deceleration transmission gear; Mechanical component axle sleeve and bearing and seal washer; Printer elements and junctor.According to estimates polyimide molding product from now on by with annual 8% speed increase.
Polyimide molding powder can adopt melt-polycondensation or solution polycondensation preparation usually.
Unit heating is polymerized to very high temperature by melt phase polycondensation usually, usually more than 250 DEG C.Because different monomers has different volatility, melt-polycondensation is therefore adopted to be difficult to the actual effective level ratio accurately controlling reactant.In addition, the polyimide molecule amount be obtained by reacting in melt phase polycondensation is all very large, not easily a step processing.
Solution polycondensation be first by organic dianhydride and organic diamine monomer in DMAc, DMF, NMP polar aprotic solvent, room temperature is carried out polycondensation and is generated polyamic acid PAA, then polyamic acid cyclodehydration is made the process of polyimide.Reaction is main adopts following several method to carry out:
1) first method: adopt chemical dehydrator make polyamic acid generation cyclodehydration and carry out the process of imidization.Chemical imidization is at room temperature carried out usually, adds dewatering agent acetic anhydride and catalyst pyridine in polyamic acid, and at room temperature reaction prepares polyimide in more than 15 hours.The chemical imidization of polyimide, except formation imide ring, also may generate different imide.Because polyisoimide is soluble in the aprotic dipolar solvents such as DMAc, NMP than corresponding polyimide, therefore under low temperature, different imide is difficult to be converted into imide completely, the molecular weight of product distribution that thoroughly can not cause of imidization broadens, and has a negative impact to the performance of polyimide.
2) second method: polyamic acid solution is carried out heating and concentrate, then concentrated solution is poured in methyl alcohol or water, again intensification is carried out to the powder obtained dry, polyamic acid changes into polyimide in the process of heating, because the method needs a large amount of solvents equally, and solvent can not easily clean up by a large amount of parcels in the powder, this is very disadvantageous to final mold pressing processing.
3) the third method is single stage method: organic dianhydride and organic diamine monomer are dissolved in high boiling point (180 ~ 220 DEG C) organic solvent (comprising oil of mirbane, meta-cresol, polar aprotic solvent etc.), simultaneously, also usually add the zinc salt of catalyzer as quinoline, tertiary amine, basic metal and carboxylic acid in this preparation process, be beneficial to normally carrying out of reaction.The water generated in polymerization process takes reaction system out of by azeotropic solvent, to impel polyreaction to carry out to the direction forming polymkeric substance, obtains the polyimide resin of high molecular.Because the meta-cresol toxicity that uses in this reaction process is very large, very large harm can be caused to environment, and solvent very easily wraps up and not easily cleaning up in the powder, affects the final course of processing.
4) the 4th kind of method is band water law: first by organic dianhydride and organic diamine monomer in DMAc, DMF, NMP polar aprotic solvent, room temperature is carried out polycondensation and is generated polyamic acid PAA; Then in polyamic acid solution, add toluene or dimethylbenzene as water entrainer, solution is heated to about 150 DEG C, form azeotropic solution, the water that imidization is formed is taken away by water trap, and final powder is separated out from solvent, filters, wash 2 ~ 3 times with ethanol, dry.The method is simple to operate, and saves solvent, does not wrap up solvent, for partial crystallization material, because molecular weight is too concentrated, cause melt viscosity too high, be unfavorable for processing in obtained powder.
The preparation method passing through mulser high-speed stirring used by the present invention is simple and easy to do, and used most of solvent can be recycled, and in preparation process, unharmful substance is discharged into the atmosphere.Obtained Moulding powder is compared with traditional hot imidization method (band water law), and thermostability remains unchanged substantially, and process window is identical, and minimum viscosity decrease to some degree.
Summary of the invention
The object of this invention is to provide a kind of preparation method of thermoplastic polyimide molding powder, be intended to the processing characteristics improving polyimide molding powder.
Polyimide molding powder of the present invention, its general structure is as shown in formula I:
N represents the polymerization degree, is the integer of 10 ~ 80,
R
1structure is
R
2structure is
The preparation method of polyimide molding powder of the present invention, its step is as follows:
(1) under mechanical stirring and protection of inert gas, be dissolved in organic solvent by diamine monomer and dianhydride monomer, the solid content of reaction system is 10% ~ 20%; Add end-capping reagent after reacting 3 ~ 8h under room temperature, continue reaction 4 ~ 10h and obtain polyamic acid solution (PAA);
(2) in mulser, add mixed solvent A, B, C, adjustment mulser with certain rotating speed stirred solution, and drips PAA solution wherein, is precipitated after reaction 15min ~ 2h;
(3) precipitation leached, be placed in solvent C, backflow 8 ~ 16h, obtains yellow imide resin powder after filtration;
(4) the imide resin powder of yellow step (3) obtained uses solvent D to wash 3 ~ 5 times, obtains yellow powder after filtration;
(5) by the yellow powder that step (4) obtains, except desolventizing at 160 ~ 180 DEG C, then vacuum-drying under 200 ~ 300 DEG C of conditions, namely obtains polyimide molding powder.
Adopt aniline to do end-capping reagent, when preparation a mol, the polymerization degree are the Moulding powder of n, the molar ratio of diamines, dianhydride and aniline is an:a (n+1): 2a; Adopt phthalic anhydride to do end-capping reagent, when preparation amol, the polymerization degree are the Moulding powder of n, the molar ratio of diamines, dianhydride and phthalic anhydride is a (n+1): an:2a; N is the integer of 10 ~ 80, a>0.
Wherein, organic solvent described in step (1) can be N, the aprotic polar solvents such as N-N,N-DIMETHYLACETAMIDE (DMAc), DMF (DMF), N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO).
Described in step (2), the volume ratio of mixed solvent A, B, C is 10 ~ 20:2 ~ 4:1, and the rotating speed of mulser is 2500 ~ 4500r/min, and preferred rotating speed is 3000 ~ 4000r/min; The volume total amount of mixed solvent is 6 ~ 10 times that drip PAA amount; The speed dripping PAA is 0.1 ~ 2mL/s, and solvent orange 2 A can select toluene, dimethylbenzene, sym-trimethylbenzene; Solvent B can select pyridine, triethylamine, picoline; Solvent C can select the anhydrides such as diacetyl oxide, propionic anhydride material, Acetyl Chloride 98Min., sulfur oxychloride, Dicyclohexylcarbodiimide (DCC).
Return time described in step (3) is preferably 10 ~ 12h.Solvent D described in step (4) can select ethanol, methyl alcohol, acetone.
The preparation method passing through mulser high-speed stirring used by the present invention is simple and easy to do, and used most of solvent can be recycled, and in preparation process, unharmful substance is discharged into the atmosphere.Obtained Moulding powder is compared with traditional hot imidization method, and when thermostability remains unchanged substantially, process window is identical, and minimum viscosity decrease to some degree.
Accompanying drawing explanation
The infrared test curve of the Moulding powder that Fig. 1 embodiment 1 is obtained, as can be seen from the figure 1720,1780 and 1380cm
-1there is the charateristic avsorption band (in figure arrow indication) of polyimide in wave number place, explanation present method has successfully obtained the higher Moulding powder of imidization degree.
The thermogravimetric curve comparison diagram of the Moulding powder that Fig. 2 embodiment 2 is obtained and the obtained Moulding powder of traditional hot imidization method (band water law), as can be seen from the figure, the obtained Moulding powder 5% thermal weight loss temperature of two kinds of methods, all more than 500 DEG C, illustrates that the thermostability of the Moulding powder that use the inventive method obtains is higher.
390 ~ 450 DEG C of alternating temperature flow curve figure of the Moulding powder that Fig. 3 embodiment 5 is obtained and the obtained Moulding powder of traditional hot imidization method (band water law), as can be seen from the figure, the process window of two kinds of methods is identical (410 ~ 430 DEG C), and the minimum melt viscosity of the inventive method will lower than band water law.
Embodiment
Be further described method of the present invention below by specific embodiment, the specific descriptions of described embodiment just to claim of the present invention, claim includes but not limited to described embodiment content.
Embodiment 1:
Take 92.0843g1, two (4-amino-benzene oxygen) benzene of 3-, 7.0084g 4,4 '-diaminodiphenyl oxide is placed in flask, put into a certain amount of N, N-N,N-DIMETHYLACETAMIDE (DMAc) dissolves to monomer, then in system, 101.2606g 3 is slowly added, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, add DMAc (total amount is 1.9L) subsequently, at room temperature react after 5 hours and add end-capping reagent phthalic anhydride 1.7283g, and then room temperature reaction 8h under an inert atmosphere, obtain PAA solution.
In mulser, add 250mL toluene, 52mL triethylamine and 13mL diacetyl oxide afterwards, adjustment mulser rotating speed is 4000r/min, drips the PAA solution of above-mentioned synthesis wherein, adds 50mL altogether, control rotating speed with the speed of 0.5mL/s, continues to stir 1h.After 1h, throw out is leached, pour in 200mL solution of acetic anhydride, backflow 10h.Then throw out is leached, with methanol wash column 5 times, filter and obtain yellow powder, yellow powder is put into convection oven 170 DEG C and dry 5h, then proceed to vacuum drying oven 300 DEG C and dry 1h, obtain polyimide molding powder, productive rate 92%.Second-order transition temperature is 212 DEG C, and minimum melt viscosity is about 13000Pa.s.
Embodiment 2:
In mulser, add 300mL toluene, 31mL pyridine and 13mL diacetyl oxide, adjustment mulser rotating speed is 4500r/min, drips the PAA solution of synthesis in embodiment 1 wherein, adds 50mL altogether, control rotating speed with the speed of 0.1mL/s, continues to stir 15min.After 15min, throw out is leached, pour in 300mL solution of acetic anhydride, backflow 12h.Then throw out is leached, wash 3 times with ethanol, filter and obtain yellow powder, Moulding powder is put into convection oven 170 DEG C and dry 5h, then proceed to vacuum drying oven 250 DEG C and dry 1h, obtain polyimide molding powder, productive rate 96%.Second-order transition temperature is 212 DEG C, and minimum melt viscosity is about 12600Pa.s.
Embodiment 3:
In mulser, add 250mL toluene, 52mL pyridine and 13mL diacetyl oxide, adjustment mulser rotating speed is 3000r/min, drips the PAA solution of synthesis in embodiment 1 wherein, adds 50mL altogether, control rotating speed with the speed of 2mL/s, continues to stir 1h.After 1h, throw out is leached, pour in 150mL solution of acetic anhydride, backflow 12h.Then throw out is leached, with methanol wash column 3 times, filter and obtain yellow powder, Moulding powder is put into convection oven 160 DEG C and dry 5h, then proceed to vacuum drying oven 280 DEG C and dry 1h, obtain polyimide molding powder, productive rate 93%.Second-order transition temperature is 212 DEG C, and minimum melt viscosity is about 13000Pa.s.
Embodiment 4:
In mulser, add 250mL dimethylbenzene, 52mL pyridine and 13mL propionic anhydride, adjustment mulser rotating speed is 2500r/min, drips the PAA solution of synthesis in embodiment 1 wherein, adds 50mL altogether, control rotating speed with the speed of 0.1mL/s, continues to stir 2h.After 2h, throw out is leached, pour in 200mL propionic anhydride solution, backflow 10h.Then throw out is leached, wash 3 times with ethanol, filter and obtain yellow powder, Moulding powder is put into convection oven 180 DEG C and dry 5h, then proceed to vacuum drying oven 280 DEG C and dry 1h, obtain polyimide molding powder, productive rate 94%.Second-order transition temperature is 211 DEG C, and minimum melt viscosity is about 13400Pa.s.
Embodiment 5:
Take 92.0843g 1, two (4-amino-benzene oxygen) benzene of 3-, 7.0084g 4,4 '-diaminodiphenyl oxide is placed in flask, put into a certain amount of N, N-N,N-DIMETHYLACETAMIDE (DMAc) dissolves to monomer, then in system, 101.2606g 3 is slowly added, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, add DMAc (total amount is 1.9L) subsequently, at room temperature react after 5 hours and add end-capping reagent phthalic anhydride 1.7283g, and then room temperature reaction 8h under an inert atmosphere, obtain PAA solution.
In mulser, add 156mL toluene, 31mL pyridine and 13mL diacetyl oxide afterwards, adjustment mulser rotating speed is 3000r/min, drips the PAA solution of above-mentioned synthesis wherein, adds 50mL altogether, control rotating speed with the speed of 0.3mL/s, continues to stir 1h.After 1h, throw out is leached, pour in 150mL solution of acetic anhydride, backflow 10h.Then throw out is leached, wash 5 times with ethanol, filter and obtain yellow powder, Moulding powder is put into convection oven 170 DEG C and dry 5h, then proceed to vacuum drying oven 300 DEG C and dry 1h, obtain polyimide molding powder, productive rate 96%.Second-order transition temperature is 212 DEG C, and minimum melt viscosity is about 12700Pa.s.
Embodiment 6:
In mulser, add 156mL toluene, 31mL pyridine and 13mL Acetyl Chloride 98Min., adjustment mulser rotating speed is 4000r/min, drips the PAA solution of synthesis in embodiment 5 wherein, adds 50mL altogether, control rotating speed with the speed of 1mL/s, continues to stir 1h.After 1h, throw out is leached, pour in 200mL chloride solution, backflow 12h.Then throw out is leached, wash 5 times with ethanol, Moulding powder is put into convection oven 170 DEG C and dry 5h, then proceed to vacuum drying oven 300 DEG C and dry 1h, filter and obtain yellow powder, imines Moulding powder, productive rate 93%.Second-order transition temperature is 211 DEG C, and minimum melt viscosity is about 13500Pa.s.
Embodiment 7:
Take 4,4 '-diaminodiphenyl oxide 0.0095mol, is placed in flask, put into a certain amount of N, N-N,N-DIMETHYLACETAMIDE (DMAc) dissolves to monomer, then in system, slowly adds 2,2, ' 3,3 '-BPDA 0.01mol, adds DMAc (total amount is 50mL) subsequently, at room temperature reacts after 3 hours and adds end-capping reagent aniline 0.001mol, and then room temperature reaction 10h under an inert atmosphere, obtain PAA solution.
In mulser, add 250mL toluene, 52mL triethylamine and 13mL diacetyl oxide afterwards, adjustment mulser rotating speed is 4100r/min, drips the PAA solution of above-mentioned synthesis wherein, adds 50mL altogether, control rotating speed with the speed of 0.5ml/s, continues to stir 1h.After 1h, throw out is leached, pour in 200mL solution of acetic anhydride, backflow 10h.Then throw out is leached, with methanol wash column 5 times, filtration obtains yellow powder, Moulding powder is put into convection oven 170 DEG C and dry 5h, then proceed to vacuum drying oven 250 DEG C and dry 1h, obtain polyimide molding powder, productive rate 92%, second-order transition temperature is 261 DEG C, and minimum melt viscosity is about 1600Pa.s.
Embodiment 8:
Take 4,4 '-diaminodiphenyl oxide 0.015mol, be placed in flask, put into a certain amount of N,N-dimethylacetamide (DMAc) to dissolve to monomer, then in system, slowly add pyromellitic acid anhydride 0.0153mol, add DMAc (total amount is 47mL) subsequently, at room temperature react after 8 hours and add end-capping reagent aniline 0.001mol, and then room temperature reaction 8h under an inert atmosphere, obtain PAA solution.
In mulser, add 252mL toluene, 53mL triethylamine and 13mL diacetyl oxide afterwards, adjustment mulser rotating speed is 4500r/min, drips the PAA solution of above-mentioned synthesis wherein, adds 40mL altogether, control rotating speed with the speed of 1mL/s, continues to stir 1h.After 1h, throw out is leached, pour in 200mL solution of acetic anhydride, backflow 10h.Then throw out is leached, 5 times are washed with ethanol, filtration obtains yellow powder, Moulding powder is put into convection oven 180 DEG C and dry 5h, then proceed to vacuum drying oven 300 DEG C and dry 1h, obtain polyimide molding powder, productive rate 93%, second-order transition temperature is 350 DEG C, and minimum melt viscosity is about 5600Pa.s.
Embodiment 9:
Take 2-(3-aminophenyl)-5-aminobenzimidazole 0.0095mol, be placed in flask, put into a certain amount of N,N-dimethylacetamide (DMAc) and dissolve to monomer, then in system, slowly 2 are added, 2, ' 3,3 '-BPDA 0.01mol, add DMAc (total amount is 34mL) subsequently, at room temperature react after 3 hours and add end-capping reagent aniline 0.001mol, and then room temperature reaction 4h under an inert atmosphere, obtain PAA solution.
In mulser, add 255mL toluene, 55mL triethylamine and 13mL propionic anhydride afterwards, adjustment mulser rotating speed is 4500r/min, drips the PAA solution of above-mentioned synthesis wherein, adds 30mL altogether, control rotating speed with the speed of 0.5mL/s, continues to stir 1h.After 1h, throw out is leached, pour in 170mL propionic anhydride solution, backflow 12h.Then throw out is leached, 5 times are washed with ethanol, filtration obtains yellow powder, Moulding powder is put into convection oven 180 DEG C and dry 5h, then proceed to vacuum drying oven 250 DEG C and dry 1h, obtain polyimide molding powder, productive rate 93%, second-order transition temperature is 216 DEG C, and minimum melt viscosity is about 2900Pa.s.
Embodiment 10:
Take 2-(3-aminophenyl)-5-aminobenzimidazole 0.005mol, be placed in flask, put into a certain amount of N,N-dimethylacetamide (DMAc) and dissolve to monomer, then in system, slowly 2 are added, 2, ' 3,3 '-BPDA 0.0055mol, add DMAc (total amount is 34mL) subsequently, at room temperature react after 5 hours and add end-capping reagent aniline 0.001mol, and then room temperature reaction 10h under an inert atmosphere, obtain PAA solution.
In mulser, add 250mL dimethylbenzene, 55mL triethylamine and 13mL diacetyl oxide afterwards, adjustment mulser rotating speed is 4200r/min, drips the PAA solution of above-mentioned synthesis wherein, adds 30mL altogether, control rotating speed with the speed of 0.5mL/s, continues to stir 1h.After 1h, throw out is leached, pour in 160mL solution of acetic anhydride, backflow 10h.Then throw out is leached, with methanol wash column 5 times, filtration obtains yellow powder, Moulding powder is put into convection oven 180 DEG C and dry 5h, then proceed to vacuum drying oven 250 DEG C and dry 2h, obtain polyimide molding powder, productive rate 95%, second-order transition temperature is 255 DEG C, and minimum melt viscosity is about 1600Pa.s.
Embodiment 11:
Take 1,3-two (3-amino-benzene oxygen-4 '-benzoyl) benzene 0.0095mol, be placed in flask; put into a certain amount of N; N-N,N-DIMETHYLACETAMIDE (DMAc) dissolves to monomer, then in system, slowly adds 3,3 '; 4; 4 '-diphenyl ether tetraformic dianhydride 0.01mol, adds DMAc (total amount is 35mL) subsequently, at room temperature reacts after 3 hours and adds end-capping reagent aniline 0.001mol; and then room temperature reaction 10h under an inert atmosphere, obtain PAA solution.
In mulser, add 250mL dimethylbenzene, 50mL triethylamine and 13mL diacetyl oxide afterwards, adjustment mulser rotating speed is 4000r/min, drips the PAA solution of above-mentioned synthesis wherein, adds 30mL altogether, control rotating speed with the speed of 1mL/s, continues to stir 50min.After 50min, throw out is leached, pour in 150mL solution of acetic anhydride, backflow 8h.Then throw out is leached, with methanol wash column 5 times, filtration obtains yellow powder, Moulding powder is put into convection oven 180 DEG C and dry 5h, then proceed to vacuum drying oven 200 DEG C and dry 4h, obtain polyimide molding powder, productive rate 94%, second-order transition temperature is 198 DEG C, and minimum melt viscosity is about 3100Pa.s.
Embodiment 12:
Take Ursol D 0.01mol, be placed in flask, put into a certain amount of N,N-dimethylacetamide (DMAc) and dissolve to monomer, then in system, slowly 2 are added, 2, ' 3,3 '-BPDA 0.0095mol, add DMAc (total amount is 34mL) subsequently, at room temperature react after 3 hours and add end-capping reagent phthalic anhydride 0.001mol, then room temperature reaction 7h under an inert atmosphere, obtain PAA solution.
In mulser, add 250mL dimethylbenzene, 55mL triethylamine and 13mL diacetyl oxide afterwards, adjustment mulser rotating speed is 2500r/min, drips the PAA solution of above-mentioned synthesis wherein, adds 30mL altogether, control rotating speed with the speed of 1.5mL/s, continues to stir 1h.After 1h, throw out is leached, pour in 150mL solution of acetic anhydride, backflow 11h.Then throw out is leached, with methanol wash column 5 times, filtration obtains yellow powder, Moulding powder is put into convection oven 180 DEG C and dry 5h, then proceed to vacuum drying oven 200 DEG C and dry 1h, obtain polyimide molding powder, productive rate 95%, second-order transition temperature is 189 DEG C, and minimum melt viscosity is about 1200Pa.s.
Embodiment 13:
Take 1,3-two (3-amino-benzene oxygen-4 '-benzoyl) benzene 0.0295mol, be placed in flask; put into a certain amount of N; N-N,N-DIMETHYLACETAMIDE (DMAc) dissolves to monomer, then in system, slowly adds 3,3 '; 4; 4 '-diphenyl ether tetraformic dianhydride 0.03mol, adds DMAc (total amount is 105mL) subsequently, at room temperature reacts after 3 hours and adds end-capping reagent aniline 0.001mol; then room temperature reaction 8h under an inert atmosphere, obtains PAA solution.
In mulser, add 250mL dimethylbenzene, 55mL triethylamine and 13mL diacetyl oxide afterwards, adjustment mulser rotating speed is 4500r/min, drips the PAA solution of above-mentioned synthesis wherein, adds 50mL altogether, control rotating speed with the speed of 0.5mL/s, continues to stir 1h.After 1h, throw out is leached, pour in 200mL solution of acetic anhydride, backflow 12h.Then throw out is leached, with methanol wash column 5 times, filtration obtains yellow powder, Moulding powder is put into convection oven 180 DEG C and dry 5h, then proceed to vacuum drying oven 260 DEG C and dry 1h, obtain polyimide molding powder, productive rate 92%, second-order transition temperature is 280 DEG C, and minimum melt viscosity is about 7400Pa.s.
Embodiment 14:
Take 1,3-two (3-amino-benzene oxygen-4 '-benzoyl) benzene 0.03mol, be placed in flask; put into a certain amount of N,N-dimethylacetamide (DMAc) to dissolve to monomer, then in system, slowly add 3; 3 '; 4,4 '-diphenyl ether tetraformic dianhydride 0.0295mol, add DMAc (total amount is 105mL) subsequently; at room temperature react after 4 hours and add end-capping reagent aniline 0.001mol, then room temperature reaction 8h under an inert atmosphere, obtain PAA solution.In mulser, add 250mL dimethylbenzene, 55mL triethylamine and 13mL diacetyl oxide afterwards, adjustment mulser rotating speed is 4100r/min, drips the PAA solution of above-mentioned synthesis wherein, adds 50mL altogether, control rotating speed with the speed of 0.5mL/s, continues to stir 1h.After 1h, throw out is leached, pour in 200mL solution of acetic anhydride, backflow 12h.Then throw out is leached, 5 times are washed with acetone, filtration obtains yellow powder, Moulding powder is put into convection oven 180 DEG C and dry 5h, then proceed to vacuum drying oven 260 DEG C and dry 1h, obtain polyimide molding powder, productive rate 92%, second-order transition temperature is 310 DEG C, and minimum melt viscosity is about 7600Pa.s.
Embodiment 15:
Take 1; 3-pair (3-amino-benzene oxygen-4 '-benzoyl) benzene 0.0095mol; be placed in flask; put into a certain amount of N,N-dimethylacetamide (DMAc) to dissolve to monomer, then in system, slowly add pyromellitic acid anhydride 0.01mol; add DMAc (total amount is 31mL) subsequently; at room temperature react after 4 hours and add end-capping reagent aniline 0.001mol, then room temperature reaction 8h under an inert atmosphere, obtain PAA solution.
In mulser, add 250mL dimethylbenzene, 50mL triethylamine and 13mL diacetyl oxide afterwards, adjustment mulser rotating speed is 4000r/min, drips the PAA solution of above-mentioned synthesis wherein, adds 30mL altogether, control rotating speed with the speed of 0.5mL/s, continues to stir 1h..After 1h, throw out is leached, pour in 150mL solution of acetic anhydride, backflow 10h.Then throw out is leached, 3 times are washed with ethanol, filtration obtains yellow powder, Moulding powder is put into convection oven 180 DEG C and dry 5h, then proceed to vacuum drying oven 260 DEG C and dry 1h, obtain polyimide molding powder, productive rate 91%, second-order transition temperature is 225 DEG C, and minimum melt viscosity is about 2500Pa.s.
Claims (8)
1. a preparation method for polyimide molding powder, its step is as follows:
1) under mechanical stirring and protection of inert gas, be dissolved in organic solvent by diamine monomer and dianhydride monomer, the solid content of reaction system is 10% ~ 20%; Add end-capping reagent after reacting 3 ~ 8h under room temperature, continue reaction 4 ~ 10h and obtain polyamic acid solution;
2) in mulser, add mixed solvent A, B, C, adjustment mulser with certain rotating speed stirred solution, and drips PAA solution wherein, is precipitated after reaction 15min ~ 2h; Solvent orange 2 A is toluene, dimethylbenzene or sym-trimethylbenzene; Solvent B is pyridine, triethylamine or picoline; Solvent C is diacetyl oxide, propionic anhydride, Acetyl Chloride 98Min., sulfur oxychloride or Dicyclohexylcarbodiimide;
3) precipitation leached, be placed in solvent C, backflow 8 ~ 16h, obtains yellow imide resin powder after filtration;
4) the imide resin powder of yellow step (3) obtained uses solvent D to wash 3 ~ 5 times, obtains yellow powder after filtration; Solvent D is ethanol, methyl alcohol or acetone;
5) by the yellow powder that step (4) obtains, except desolventizing at 160 ~ 180 DEG C, then vacuum-drying under 200 ~ 300 DEG C of conditions, namely obtains polyimide molding powder, and its structural formula is as follows,
N represents the polymerization degree, is the integer of 10 ~ 80,
R
1structure is
R
2structure is
2. the preparation method of a kind of polyimide molding powder as claimed in claim 1, it is characterized in that: adopt aniline to do end-capping reagent, when preparation amol, the polymerization degree are the Moulding powder of n, the molar ratio of diamines, dianhydride and aniline is an:a (n+1): 2a; N is the integer of 10 ~ 80, a>0.
3. the preparation method of a kind of polyimide molding powder as claimed in claim 1, it is characterized in that: adopt phthalic anhydride to do end-capping reagent, when preparation amol, the polymerization degree are the Moulding powder of n, the molar ratio of diamines, dianhydride and phthalic anhydride is a (n+1): an:2a; N is the integer of 10 ~ 80, a>0.
4. the preparation method of a kind of polyimide molding powder as claimed in claim 1, is characterized in that: the organic solvent described in step (1) is N,N-dimethylacetamide, DMF, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO).
5. the preparation method of a kind of polyimide molding powder as claimed in claim 1, is characterized in that: described in step (2), the volume ratio of mixed solvent A, B, C is 10 ~ 20:2 ~ 4:1.
6. the preparation method of a kind of polyimide molding powder as claimed in claim 1, is characterized in that: described in step (2), the rotating speed of mulser is 2500 ~ 4500r/min, and preferred rotating speed is 3000 ~ 4000r/min.
7. the preparation method of a kind of polyimide molding powder as claimed in claim 1, is characterized in that: in step (2), the volume total amount of mixed solvent is 6 ~ 10 times that drip PAA amount; The speed dripping PAA is 0.1 ~ 2mL/s.
8. the preparation method of a kind of polyimide molding powder as claimed in claim 1, is characterized in that: the return time described in step (3) is 10 ~ 12h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510113931.7A CN104710789A (en) | 2015-03-16 | 2015-03-16 | Preparation method of polyimide molding powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510113931.7A CN104710789A (en) | 2015-03-16 | 2015-03-16 | Preparation method of polyimide molding powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104710789A true CN104710789A (en) | 2015-06-17 |
Family
ID=53410531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510113931.7A Pending CN104710789A (en) | 2015-03-16 | 2015-03-16 | Preparation method of polyimide molding powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104710789A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085281A (en) * | 2015-08-07 | 2015-11-25 | 吉林大学 | Diamine monomer containing diphenylamine-fluorene, preparation method and application of same in polyimide preparation |
| CN105175721A (en) * | 2015-08-17 | 2015-12-23 | 吉林大学 | Method for preparing polyimide moulding powder with uniform molecular weight distribution |
| CN106167547A (en) * | 2016-08-11 | 2016-11-30 | 中国科学院宁波材料技术与工程研究所 | The crystallinity copolyimide resin of the easy melt-processed of a kind of low melt viscosity and application |
| CN114008139A (en) * | 2019-06-20 | 2022-02-01 | 住友电气工业株式会社 | Resin composition, method for producing resin composition, and insulated wire |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6335418B1 (en) * | 1999-02-26 | 2002-01-01 | Osaka Prefectural Government | Functional polyamic acid microfine particles, functional polyimide microfine particles, and processes for their production |
| CN101392057A (en) * | 2008-11-03 | 2009-03-25 | 吉林大学 | Method for preparing crystalline thermoplastic polyimide moulding powder |
| CN101423608A (en) * | 2008-11-12 | 2009-05-06 | 吉林大学 | Method for preparing thermoplastic polyimide molding powder |
| CN101703913A (en) * | 2010-01-16 | 2010-05-12 | 太原理工大学 | Method for preparing polyimide microspheres |
| CN102690415A (en) * | 2012-06-05 | 2012-09-26 | 中国科学院化学研究所 | Polyimide microspheres and preparation method and application thereof |
| CN103113585A (en) * | 2013-03-08 | 2013-05-22 | 哈尔滨工业大学 | Preparation method of solid polyimide microspheres |
| CN103497335A (en) * | 2013-10-11 | 2014-01-08 | 吉林大学 | High-heat-resistance and high-fluidity polyimide molding powder and preparation method thereof |
| CN103570946A (en) * | 2013-11-19 | 2014-02-12 | 武汉理工大学 | Preparation method of polyimide microsphere |
-
2015
- 2015-03-16 CN CN201510113931.7A patent/CN104710789A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6335418B1 (en) * | 1999-02-26 | 2002-01-01 | Osaka Prefectural Government | Functional polyamic acid microfine particles, functional polyimide microfine particles, and processes for their production |
| CN101392057A (en) * | 2008-11-03 | 2009-03-25 | 吉林大学 | Method for preparing crystalline thermoplastic polyimide moulding powder |
| CN101423608A (en) * | 2008-11-12 | 2009-05-06 | 吉林大学 | Method for preparing thermoplastic polyimide molding powder |
| CN101703913A (en) * | 2010-01-16 | 2010-05-12 | 太原理工大学 | Method for preparing polyimide microspheres |
| CN102690415A (en) * | 2012-06-05 | 2012-09-26 | 中国科学院化学研究所 | Polyimide microspheres and preparation method and application thereof |
| CN103113585A (en) * | 2013-03-08 | 2013-05-22 | 哈尔滨工业大学 | Preparation method of solid polyimide microspheres |
| CN103497335A (en) * | 2013-10-11 | 2014-01-08 | 吉林大学 | High-heat-resistance and high-fluidity polyimide molding powder and preparation method thereof |
| CN103570946A (en) * | 2013-11-19 | 2014-02-12 | 武汉理工大学 | Preparation method of polyimide microsphere |
Non-Patent Citations (1)
| Title |
|---|
| 贾赫: ""一种简单的方法合成聚酰亚胺纳米微球"", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085281A (en) * | 2015-08-07 | 2015-11-25 | 吉林大学 | Diamine monomer containing diphenylamine-fluorene, preparation method and application of same in polyimide preparation |
| CN105175721A (en) * | 2015-08-17 | 2015-12-23 | 吉林大学 | Method for preparing polyimide moulding powder with uniform molecular weight distribution |
| CN106167547A (en) * | 2016-08-11 | 2016-11-30 | 中国科学院宁波材料技术与工程研究所 | The crystallinity copolyimide resin of the easy melt-processed of a kind of low melt viscosity and application |
| CN106167547B (en) * | 2016-08-11 | 2018-10-02 | 中国科学院宁波材料技术与工程研究所 | A kind of crystallinity copolyimide resin of the easy melt-processed of low melt viscosity and application |
| CN114008139A (en) * | 2019-06-20 | 2022-02-01 | 住友电气工业株式会社 | Resin composition, method for producing resin composition, and insulated wire |
| CN114008139B (en) * | 2019-06-20 | 2023-10-20 | 住友电气工业株式会社 | Resin composition, method for producing resin composition, and insulated wire |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102604091B (en) | Polyimide containing benzimidazole unit and preparation method thereof | |
| CN101307013B (en) | Aromatic diamine with phthalonitrile pendant group, preparation method thereof and polyimides or polyamide prepared therefrom | |
| CN108641082B (en) | Thermosetting polyimide prepolymer and preparation method and application thereof | |
| CN101880389B (en) | Phthalonitrile-terminated polyimide resin containing phthalazinone structure, cured product and preparation method thereof | |
| CN100569833C (en) | A kind of fluorine-containing thermoplastic polyimide polymer and preparation method thereof | |
| CN103788650A (en) | Colorless and transparent polyimide film and preparation method thereof | |
| CN102492141B (en) | Soluble polyimide molded plastic and preparation method thereof | |
| CN104710789A (en) | Preparation method of polyimide molding powder | |
| CN105461922B (en) | A kind of low viscosity thermoset polyimide resin and its preparation method and application | |
| CN107793566B (en) | Thermoplastic polybenzimidazole imide and preparation method thereof | |
| CN107602857A (en) | The preparation method and application of polyimides | |
| CN111019129A (en) | Low-thermal expansion coefficient soluble polyimide resin powder and preparation method thereof | |
| CN105504282A (en) | Fluorenyl Cardo type polymide diluting agent and preparing method and application thereof | |
| CN104530429B (en) | High-fluidity wide-processing-widow polyimide pre-polymer and preparation method thereof | |
| CN102120820B (en) | A kind of method of performing aqueous synthesis of thermosetting polyimide | |
| US20130292873A1 (en) | Method for preparing polyimide film | |
| CN105348551A (en) | Polyimide porous membrane and preparation method thereof | |
| CN111533907A (en) | Preparation method of heat-resistant polyimide molding powder containing benzimidazole structure | |
| CN111303426B (en) | Polyimide film and method for preparing polyimide film by click chemistry | |
| CN105175721A (en) | Method for preparing polyimide moulding powder with uniform molecular weight distribution | |
| CN107892745B (en) | Thermoplastic polybenzoxazole imide and preparation method thereof | |
| CN101392057A (en) | Method for preparing crystalline thermoplastic polyimide moulding powder | |
| CN101225169B (en) | Sulfur fluoro self-crosslinkable polyimide material and preparation method thereof | |
| CN103483240A (en) | Soluble benzocyclobutene-terminated imide monomer as well as preparation method and curing method thereof | |
| CN109735917A (en) | A kind of ternary copolymerization polyimide spinning solution and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150617 |
|
| WD01 | Invention patent application deemed withdrawn after publication |