CN103497335A - High-heat-resistance and high-fluidity polyimide molding powder and preparation method thereof - Google Patents
High-heat-resistance and high-fluidity polyimide molding powder and preparation method thereof Download PDFInfo
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Abstract
The invention discloses high-heat-resistance and high-fluidity polyimide molding powder and a preparation method thereof, belonging to the field of high polymer materials. The molding powder is prepared from dianhydride containing a flexible chain structure and diamine containing a spatial warping structure through high-temperature solution polycondensation. Glass-transition temperature of the molding powder can reach 350 DEG C, and is about 100 DEG C higher than glass-transition temperature of other conventional polyimide molding powder, thus greatly improving heat resistance of the polyimide molding powder. The molding powder, during high-temperature processing, is relatively low in melt viscosity and good in melt fluidity; therefore, the molding powder not only can be shaped by embossing but also is applicable to a resin transfer molding process. The molding powder has potential application value in the aspect of preparing high-performance thermoplastic materials.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of technology of preparing of new type polyimide molding powder.
Background technology
Heat resistance engineering plastics polyimide (PI) is as the exsertile tip materials of a kind of property, excellent electrical insulating property, wear resistance, high temperature resistance radiation and the physical and mechanical properties with it, be widely used in dynamo-electric, electric, instrument, field of petrochemical industry, become one of indispensable materials in hard-core technology field such as global rocket, aerospace.Polyimide (PI), with regard to its chemical structure, has dividing of complete fragrant type and aliphatic type.The former has that equal acid anhydride series, biphenyl are serial, ketone (ether) acid anhydride series, acid anhydride series etc. partially; The latter has bismaleimides etc.They can manufacture the goods such as film, fiber, formed material, matrix material and coating, tackiness agent, to adapt to various purposes.Fully aromatic polyimide (PI) is most important member in special engineering plastics family.Its thermotolerance is the highest, over-all properties is best, consumption is maximum, purposes is the widest.
Polyimide molding powder is mainly used in compression molding and prepares the mold pressing part.Because this material has good mechanical property and thermotolerance, erosion resistance, anti-insulativity etc., be subject to people's great attention, its goods are widely used in the high temperature-resistant part in the fields such as machinery, chemical industry, electric, Nuclear Power Industry, spacecraft and printed electronic circuit material etc.Such as being used as aircraft jet engine part, mechanical component axle sleeve and bearing and sealing-ring, printer elements and junctor etc.Yet the full fragrant polyimide of great majority is insoluble, not molten, and the compression molding condition is high, and the poor toughness of pressing is restricted its range of application.In addition, the excellent specific property of polyimide largely depends on that polyamic acid changes into the factors such as the cyclisation conditions of polyimide, imidization degree, thereby the imidization technique of polyimide is studied, significant to the performance of improving moulding material.
So far the fully aromatic polyimide resin developed, workability is poor, therefore Application Areas is restricted.The emphasis of new product PI exploitation mainly concentrates on exploitation thermoplasticity PI, improve PI self processing characteristics and with the compatibility of other material, to adapt to the active demand of the fields such as aerospace and electronic industry to tip materials.
Summary of the invention
The objective of the invention is thermal characteristics in order to improve conventional polyimide and processing characteristics and prepare a kind of novel high heat resistance with special construction, high workability thermoplastic polyimide molding powder.
In order to obtain the performance more excellent than existing polyimide molding powder, the dianhydride monomer that the present invention's employing contains soft segment and the diamines of special construction make and have higher glass transition temperature by high temperature solution polycondensation, so there is high heat resistance, also there is the new type polyimide molding powder of good flowing property simultaneously.The particular molecule chain structure had due to this molding powder, make the Intermolecular Forces between the polymkeric substance end of the chain reduce, this makes polyimide have good mobility when high-temperature fusion, have the rigid structures such as imide ring, benzoglyoxaline in this polyimide molding powder simultaneously, make again it have the second-order transition temperature higher than general polyimide.Such polyimide molding powder can either meet under hot environment and works, and can possess good thermoplasticity again, has promoted the processing characteristics of itself, has good development prospect.
Polyimide molding powder in the present invention, its general structure is as shown in formula I:
N represents the polymerization degree, is 10～60 integer.
R
1structure is:
R
2structure is:
Use the dianhydride contain special construction and diamines polymerization in this method and obtain polyamic acid, then add end-capping reagent, control it and reach specific molecular weight; Finally use the method refluxed with water to make polyimide resin, and resin is sunk in methyl alcohol (or ethanol), obtain the molding powder and clean drying.
The preparation method of polyimide molding powder of the present invention, its step is as follows:
1) under mechanical stirring and nitrogen protection, diamines and dianhydride are dissolved in organic solvent, the solid content of reaction system is 10～20%;
2) react under room temperature after 2～10 hours and add end-capping reagent, then the continuation reaction obtains polyamic acid solution in 2～10 hours; Then adding band water reagent, is 15～50% of organic solvent volume with the consumption of water reagent, be warmed up to 148～156 ℃ after band water reflux 2～10 hours; After moisture in system is all taken out of, will be with water reagent to steam to the greatest extent, then be warmed up to 160～170 ℃ of backflows 2～10 hours, obtain imide resin;
3) imide resin is washed 2～8 times with methyl alcohol or ethanol, obtained yellow powder after filtration, by yellow powder vacuum-drying under 90～300 ℃ of conditions, obtain polyimide molding powder.
Adopt aniline to do end-capping reagent, the molding powder that preparation amol, the polymerization degree are n, the molar ratio of diamines, dianhydride and aniline is an:a (n+1): 2a; Adopt phthalic anhydride to do end-capping reagent, the molding powder that preparation amol, the polymerization degree are n, the molar ratio of diamines, dianhydride and phthalic anhydride is a (n+1): an:2a; The integer that n is 10～60, a > 0.
Wherein, organic solvent is N-methyl isophthalic acid-pyrrolidone, N, N '-dimethyl formamide, N, and a kind of in N '-N,N-DIMETHYLACETAMIDE, be a kind of in toluene or dimethylbenzene with water reagent.
Characteristics of the present invention
(1) adopt the dianhydride monomer that contains ehter bond to react according to the certain mol proportion example with the diamines of special construction, and add end-capping reagent to control its molecular weight, make new type polyimide molding powder;
(2) simultaneously, control the molecular weight of molding powder with end-capping reagent, by the add-on of regulating end-capping reagent, prepare the new type polyimide molding powder with controllable molecular weight;
(3) the present invention adopts strong aprotic, polar type organic solvent (N-methyl isophthalic acid-pyrrolidone, N, N '-dimethyl formamide, N, a kind of in N '-N,N-DIMETHYLACETAMIDE) and azeotropic band water reagent (in toluene or dimethylbenzene a kind of) as mixed solvent, use, band water makes polyimide molding powder.
The accompanying drawing explanation
Fig. 1: the DSC test curve of polyimide molding powder, can find out from the graph, the second-order transition temperature of this molding powder surpasses 350 ℃, can illustrate that the molding powder has high heat resistance, corresponding embodiment 5.
Fig. 2: the rheometer test curve of polyimide molding powder, minimum melt viscosity can reach 6 * 10
3pas, can illustrate that this molding powder has high workability, corresponding embodiment 5.
Embodiment
Following embodiment gives an example for enforcement of the present invention, is not limitation of the present invention, if no special instructions, is ordinary method.Second-order transition temperature is tested and is drawn by inspection scanning calorimetry (DSC), and molecular weight is tested and drawn by gel permeation chromatography (GPC), and minimum melt viscosity is drawn by the rotational rheometer test.
Embodiment 1:
Load onto mechanical stirring, nitrogen protection, minute water and condensation reflux unit at three neck round-bottomed flasks.Drop into diamines 4 in three-necked bottle, 4 '-diaminodiphenyl oxide 0.0095mol, then add the N after underpressure distillation, and N '-N,N-DIMETHYLACETAMIDE 50mL adds 2,2 after two amine solvents, ' 3,3 '-BPDA 0.01mol.At room temperature react after 4 hours and add end-capping reagent aniline 0.001mol, react and within 2 hours, obtain polyamic acid solution.Then add dimethylbenzene 45mL, be warming up to 152 ℃, band water refluxes 5 hours, after moisture in system is all taken out of, dimethylbenzene is steamed to the greatest extent, continues to be warming up to 168 ℃ and refluxes 3 hours, obtains polyimide resin.Again polyimide resin is sunk in methyl alcohol, with methyl alcohol, wash 3 times, filtration obtains yellow powder, put powder into vacuum drying oven 200 ℃ of dryings, obtain the 0.0005mol polyimide molding powder, second-order transition temperature is 260 ℃, and molecular weight is approximately 9561g/mol, and minimum melt viscosity is about 2 * 10
3pas, n is 19.
Embodiment 2:
Load onto mechanical stirring, nitrogen protection, minute water and condensation reflux unit at three neck round-bottomed flasks.Add diamines 2-(3-aminophenyl)-5-aminobenzimidazole 0.005mol in three-necked bottle, then add the N after underpressure distillation, N '-N,N-DIMETHYLACETAMIDE 34mL, add 2 after two amine solvents, 2, ' 3,3 '-BPDA 0.0055mol, slowly add and guarantee that powder does not lump, at room temperature react after 4 hours and add end-capping reagent aniline 0.001mol reaction within 3 hours, to obtain polyamic acid solution.Then add dimethylbenzene 5mL, be warming up to 150 ℃, band water refluxes 2 hours, after moisture in system is all taken out of, dimethylbenzene is steamed to the greatest extent, continues to be warming up to 167 ℃ and refluxes 2 hours, obtains the 0.0005mol polyimide resin.Subsequent operations, with embodiment 1, finally obtains yellowish polyimide powder.Second-order transition temperature is 255 ℃, and molecular weight is about 9455g/mol, and minimum melt viscosity is about 1.9 * 10
3pas, n is 10.
Embodiment 3:
Load onto mechanical stirring, nitrogen protection, minute water and condensation reflux unit at three neck round-bottomed flasks.Add diamines 1 in three-necked bottle; two (3-amino-benzene oxygen-4 '-benzoyl) the benzene 0.0095mol of 3-; then add the N after underpressure distillation; N '-N,N-DIMETHYLACETAMIDE 35mL slowly adds 3,3 ' after two amine solvents; 4; 4 '-diphenyl ether tetraformic dianhydride 0.01mol, slowly add and guarantee that powder does not lump, and at room temperature reacts after 3 hours and add end-capping reagent aniline 0.001mol reaction within 4 hours, to obtain polyamic acid solution.Then add dimethylbenzene 9mL, be warming up to 150 ℃, band water refluxes 3 hours, after moisture in system is all taken out of, dimethylbenzene is steamed to the greatest extent, continues to be warming up to 166 ℃ and refluxes 3 hours, obtains the 0.0005mol polyimide resin.Subsequent operations, with embodiment 1, finally obtains lurid polyimide powder.Second-order transition temperature is 198 ℃.Molecular weight is about 15587g/mol, and minimum melt viscosity is about 3.3 * 10
3pas, n is 19.
Embodiment 4:
Load onto mechanical stirring, nitrogen protection, minute water and condensation reflux unit at three neck round-bottomed flasks.Drop into diamines 1 in three-necked bottle; two (3-amino-benzene oxygen-4 '-benzoyl) the benzene 0.0095mol of 3-; then add the N after underpressure distillation; N '-N,N-DIMETHYLACETAMIDE 31mL; add pyromellitic acid anhydride 0.01mol after two amine solvents; slowly add and guarantee that powder does not lump, at room temperature react after 3 hours and add end-capping reagent aniline 0.001mol reaction within 2 hours, to obtain polyamic acid solution.Then add dimethylbenzene 9mL, be warming up to 149 ℃, band water refluxes 6 hours, after moisture in system is all taken out of, dimethylbenzene is steamed to the greatest extent, continues to be warming up to 168 ℃ and refluxes 5 hours, obtains the 0.0005mol polyimide resin.Subsequent operations, with embodiment 1, finally obtains lurid polyimide powder, and second-order transition temperature is 225 ℃.Molecular weight is about 13449g/mol, and minimum melt viscosity is about 3 * 10
3pas, n is 19.
Embodiment 5:
Load onto mechanical stirring, nitrogen protection, minute water and condensation reflux unit at three neck round-bottomed flasks.Add diamines 4 in three-necked bottle, 4 '-diaminodiphenyl oxide 0.015mol, then add the N after underpressure distillation, N '-N,N-DIMETHYLACETAMIDE 47mL, add pyromellitic acid anhydride 0.0153mol after two amine solvents, slowly add and guarantee that powder does not lump, at room temperature react after 3 hours and add end-capping reagent aniline 0.001mol reaction within 3 hours, to obtain polyamic acid solution.Then add dimethylbenzene 14mL, be warming up to 150 ℃, band water refluxes 8 hours, after moisture in system is all taken out of, dimethylbenzene is steamed to the greatest extent, continues to be warming up to 168 ℃ and refluxes 7 hours, obtains polyimide resin.Subsequent operations, with embodiment 1, finally obtains the milky polyimide powder of 0.0005mol.Second-order transition temperature is 350 ℃, and molecular weight is about 25313g/mol, and minimum melt viscosity is about 6 * 10
3pas, n is 30.
Embodiment 6:
Load onto mechanical stirring, nitrogen protection, minute water and condensation reflux unit at three neck round-bottomed flasks.Add diamines 1 in three-necked bottle; two (3-amino-benzene oxygen-4 '-benzoyl) the benzene 0.0095mol of 3-; then add the N after underpressure distillation; N '-N,N-DIMETHYLACETAMIDE 35mL slowly adds 3,3 ' after two amine solvents; 4; 4 '-diphenyl ether tetraformic dianhydride 0.01mol, slowly add and guarantee that powder does not lump, and at room temperature reacts after 3 hours and add end-capping reagent aniline 0.001mol reaction within 4 hours, to obtain polyamic acid solution.Then add toluene 15mL, be warming up to 150 ℃, band water refluxes 10 hours, after moisture in system is all taken out of, toluene is steamed to the greatest extent, continues to be warming up to 168 ℃ and refluxes 10 hours, obtains the 0.0005mol polyimide resin.Subsequent operations, with embodiment 1, finally obtains lurid polyimide powder.Second-order transition temperature is 198 ℃.Molecular weight is about 15587g/mol, and minimum melt viscosity is about 3.3 * 10
3pas, n is 19.
Embodiment 7:
Load onto mechanical stirring, nitrogen protection, minute water and condensation reflux unit at three neck round-bottomed flasks.Add diamines 2-(3-aminophenyl)-5-aminobenzimidazole 0.0095mol in three-necked bottle, then add the N after underpressure distillation, N '-N,N-DIMETHYLACETAMIDE 34mL, add 2 after two amine solvents, 2, ' 3,3 '-BPDA 0.01mol, slowly add and guarantee that powder does not lump, at room temperature react after 4 hours and add end-capping reagent aniline 0.001mol reaction within 3 hours, to obtain polyamic acid solution.Then add toluene 10mL, be warming up to 149 ℃, band water refluxes 7 hours, after moisture in system is all taken out of, toluene is steamed to the greatest extent, continues to be warming up to 168 ℃ and refluxes 9 hours, obtains the 0.0005mol polyimide resin.Subsequent operations, with embodiment 1, finally obtains yellowish polyimide powder.Second-order transition temperature is that 216 ℃ of molecular weight are about 15331g/mol, and minimum melt viscosity is about 3.2 * 10
3pas, n is 19.
Embodiment 8:
Load onto mechanical stirring, nitrogen protection, minute water and condensation reflux unit at three neck round-bottomed flasks.Add diamines 2-(4-aminophenyl)-5-aminobenzimidazole 0.0095mol in three-necked bottle, then add the N after underpressure distillation, N '-N,N-DIMETHYLACETAMIDE 41mL, add 4 after two amine solvents, 4 '-hexafluoroisopropyli,ene-Tetra hydro Phthalic anhydride 0.01mol, slowly add and guarantee that powder does not lump, at room temperature react after 2 hours and add end-capping reagent aniline 0.001mol reaction within 4 hours, to obtain polyamic acid solution.Then add toluene 15mL, be warming up to 151 ℃, band water refluxes 5 hours, after moisture in system is all taken out of, toluene is steamed to the greatest extent, continues to be warming up to 167 ℃ and refluxes 3 hours, obtains the 0.0005mol polyimide resin.Subsequent operations, with embodiment 1, finally obtains the polyimide white powder.Second-order transition temperature is that 197 ℃ of molecular weight are about 16503g/mol, and minimum melt viscosity is about 3.5 * 10
3pas, n is 19.
Embodiment 9:
Load onto mechanical stirring, nitrogen protection, minute water and condensation reflux unit at three neck round-bottomed flasks.Add diamines 1 in three-necked bottle, two (3-amino-benzene oxygen-4 '-benzoyl) the benzene 0.0295mol of 3-, then add the N after underpressure distillation, N '-N,N-DIMETHYLACETAMIDE 105mL, slowly add 3 after two amine solvents, 3 ', 4, 4 '-diphenyl ether tetraformic dianhydride 0.03mol, slowly add and guarantee that powder does not lump, at room temperature react after 4 hours and add end-capping reagent aniline 0.001mol reaction within 2 hours, to obtain polyamic acid solution, then add toluene 52mL, be warming up to 152 ℃, band water refluxes 6 hours, after moisture in system is all taken out of, toluene is steamed to the greatest extent, continuing to be warming up to 168 ℃ refluxes 6 hours, obtain the 0.0005mol polyimide resin.Subsequent operations, with embodiment 1, finally obtains the polyimide powder of light brown, and second-order transition temperature is 280 ℃, and molecular weight is approximately 45765g/mol.Minimum melt viscosity is approximately 8.3 * 10
3pas, n is 59.
Embodiment 10:
Load onto mechanical stirring, nitrogen protection, minute water and condensation reflux unit at three neck round-bottomed flasks.Add diamines 1 in three-necked bottle; two (3-amino-benzene oxygen-4 '-benzoyl) the benzene 0.03mol of 3-; then add the N after underpressure distillation; N '-N,N-DIMETHYLACETAMIDE 105mL slowly adds 3,3 ' after two amine solvents; 4; 4 '-diphenyl ether tetraformic dianhydride 0.0295mol, slowly add and guarantee that powder does not lump, and at room temperature reacts after 4 hours and add end-capping reagent aniline 0.001mol reaction within 2 hours, to obtain polyamic acid solution.Then add toluene 45mL, be warming up to 150 ℃, band water refluxes 6 hours, after moisture in system is all taken out of, toluene is steamed to the greatest extent, continues to be warming up to 169 ℃ and refluxes 8 hours, obtains the 0.0005mol polyimide resin.Subsequent operations, with embodiment 1, finally obtains the polyimide powder of light brown, and second-order transition temperature is that 310 ℃ of molecular weight are approximately 47166g/mol.Minimum melt viscosity is approximately 8.6 * 10
3pas, n is 60.
Embodiment 11:
Load onto mechanical stirring, nitrogen protection, minute water and condensation reflux unit at three neck round-bottomed flasks.Add Ursol D 0.0095mol in three-necked bottle, then add the N after underpressure distillation, N '-N,N-DIMETHYLACETAMIDE 34mL, add 2 after two amine solvents, 2, ' 3,3 '-BPDA 0.01mol, slowly add and guarantee that powder does not lump, at room temperature react after 3 hours and add end-capping reagent aniline 0.001mol reaction within 3 hours, to obtain polyamic acid solution.Then add dimethylbenzene 4mL, be warming up to 156 ℃, band water refluxes 5 hours, after moisture in system is all taken out of, dimethylbenzene is steamed to the greatest extent, continues to be warming up to 165 ℃ and refluxes 6 hours, obtains polyimide resin.Subsequent operations, with embodiment 1, finally obtains the yellowish polyimide powder of 0.0005mol.Second-order transition temperature is that 190 ℃ of molecular weight are about 8234g/mol, and minimum melt viscosity is approximately 1.8 * 10
3pas, n is 19.
Embodiment 12:
Load onto mechanical stirring, nitrogen protection, minute water and condensation reflux unit at three neck round-bottomed flasks.Add Ursol D 0.01mol in three-necked bottle, then add the N after underpressure distillation, N '-N,N-DIMETHYLACETAMIDE 34mL, add 2 after two amine solvents, 2, ' 3,3 '-BPDA 0.0095mol, slowly add and guarantee that powder does not lump, at room temperature react after 3 hours and add end-capping reagent phthalic anhydride 0.001mol reaction within 3 hours, to obtain polyamic acid solution.Then add dimethylbenzene 5mL, be warming up to 148 ℃, band water refluxes 4 hours, after moisture in system is all taken out of, dimethylbenzene is steamed to the greatest extent, continues to be warming up to 160 ℃ and refluxes 4 hours, obtains polyimide resin.Subsequent operations, with embodiment 1, finally obtains the yellowish polyimide powder of 0.0005mol.Second-order transition temperature is that 189 ℃ of molecular weight are about 8012g/mol, and minimum melt viscosity is approximately 1.7 * 10
3pas, n is 19.
Claims (4)
1. a polyimide molding powder, its general structure is as shown in formula I:
N represents the polymerization degree, is 10～60 integer,
R
1structure is
R
2structure is
2. the preparation method of polyimide molding powder claimed in claim 1, its step is as follows:
1) under mechanical stirring and nitrogen protection, diamines and dianhydride are dissolved in organic solvent, the solid content of reaction system is 10～20%;
2) react under room temperature after 2～10 hours and add end-capping reagent, two mol ratios that the amount of end-capping reagent is polymkeric substance, then the continuation reaction obtains polyamic acid solution in 2～10 hours; Then adding band water reagent, is 15～50% of organic solvent volume with the consumption of water reagent, be warmed up to 148～156 ℃ after band water reflux 2～10 hours; After moisture in system is all taken out of, will be with water reagent to steam to the greatest extent, then be warmed up to 160～170 ℃ of backflows 2～10 hours, obtain imide resin;
3) imide resin is washed 2～8 times with methyl alcohol or ethanol, obtained yellow powder after filtration, by yellow powder vacuum-drying under 90～300 ℃ of conditions, obtain polyimide molding powder;
Adopt aniline to do end-capping reagent, during molding powder that preparation amol, the polymerization degree are n, the molar ratio of diamines, dianhydride and aniline is an:a (n+1): 2a; Adopt phthalic anhydride to do end-capping reagent, during molding powder that preparation amol, the polymerization degree are n, the molar ratio of diamines, dianhydride and phthalic anhydride is a (n+1): an:2a; The integer that n is 10～60, a > 0.
3. the preparation method of polyimide molding powder as claimed in claim 2, it is characterized in that: organic solvent is N-methyl isophthalic acid-pyrrolidone, N, N '-dimethyl formamide or N, a kind of in N '-N,N-DIMETHYLACETAMIDE.
4. the preparation method of polyimide molding powder as claimed in claim 2 is characterized in that: with water reagent, be a kind of in toluene or dimethylbenzene.
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| CN104710789A (en) * | 2015-03-16 | 2015-06-17 | 吉林大学 | Preparation method of polyimide molding powder |
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| CN101423608A (en) * | 2008-11-12 | 2009-05-06 | 吉林大学 | Method for preparing thermoplastic polyimide molding powder |
| JP2013036021A (en) * | 2011-07-08 | 2013-02-21 | Ube Industries Ltd | Carbon nanotube dispersant including polyamic acid |
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| CN101423608A (en) * | 2008-11-12 | 2009-05-06 | 吉林大学 | Method for preparing thermoplastic polyimide molding powder |
| JP2013036021A (en) * | 2011-07-08 | 2013-02-21 | Ube Industries Ltd | Carbon nanotube dispersant including polyamic acid |
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Application publication date: 20140108 |