CN101412812B - Method for aqueous phase synthesis of polyimides - Google Patents
Method for aqueous phase synthesis of polyimides Download PDFInfo
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- CN101412812B CN101412812B CN2008102018413A CN200810201841A CN101412812B CN 101412812 B CN101412812 B CN 101412812B CN 2008102018413 A CN2008102018413 A CN 2008102018413A CN 200810201841 A CN200810201841 A CN 200810201841A CN 101412812 B CN101412812 B CN 101412812B
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- dianhydride
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Abstract
The invention discloses an aqueous phase synthesis method for polyimide, which belongs to the technical field of synthesis for polyimide polymer. The method comprises the following steps: dianhydride, end-capping reagent, a catalyst and water are mechanically stirred; the dianhydride and diamine are mechanically mixed; at a temperature rise speed of between 1 and 5 DEG C/min, the temperatures rises to between 135 and 180 DEG C and between 180 and 250 DEG C respectively; and the obtained product is separated, washed by acid and dried, and thermoplastic polyimide is obtained. In the steps, if the end-capping reagent is removed, or the end-capping reagent and the catalyst are removed simultaneously, or the ratio of the diamine is adjusted, and other steps are not changed, the thermoplastic polyimide is also obtained. The method has the advantages of simple process, easy industrialization, low cost, no pollution, wide adjustable range of product performance and good controllability.
Description
Technical field:
The present invention relates to the polyimide polymer in the chemical field, especially a kind of water phase synthesis method of polyimide.
Background technology:
Polyimide is as a kind of cutting-edge structure material or functional material,, rub resistance high temperature resistant with it, corrosion-resistant, radioprotective, anti-oxidant, excellent specific property and characteristics such as diversity synthetic, the processing approach such as density is low, physical strength is high, electrical insulation capability is good make it have a wide range of applications in fields such as space flight, aviation, microelectronics, electromechanics, instrument, chemical industry.Polyimide, all be to carry out organic polymer by diamines and dianhydride to react a family macromolecule compound that contains imide ring on the main chain that forms, the difference of monomer whose molecular structure and molecular weight distribution thereof will be given its different thermodynamics, optics and mechanical mechanics property.Because any diamines or two compound anhydrides are hydrophobic organism, nearly all industry or scientific research institutions all adopt organic solvent as reaction medium when synthesis of polyimides at present, as toluene, dimethylbenzene, acetone, ethanol, sherwood oil etc., not only cause the cost height, reaction time of raw material long for this reason, pollute big, dangerous big, and the separating and reclaim a lot of technological process of deriving of organic solvent and polyimide, not only consuming time but also power consumption.To this, Australian JOHN CHIEF ARI etc. proposes the technology of aqueous phase synthesis of polyimides first, but because of its process using one-step synthesis, the physico-chemical property controllability and the poor stability of made polyimide.
Summary of the invention:
The object of the present invention is to provide a kind of method of aqueous phase synthesis of polyimides, the method for described this aqueous phase synthesis of polyimides will solve in the prior art makes dispersion medium with organic solvent and with the controllability of water as solvent single stage method synthesis of polyimides physical and chemical performance and the technical problem of poor stability.
The invention provides a kind of method of water synthetic thermoplastic polyimide, it is characterized in that comprising following process:
1) takes by weighing dianhydride, end-capping reagent, catalyzer, water respectively, wherein, the mol ratio of dianhydride and end-capping reagent is that 50:1～5:1, dianhydride and catalyst quality ratio are 1:5～1:30 for the mass ratio of 2000:1～20:1, dianhydride and water, dianhydride, end-capping reagent, catalyzer, water are added in the reactor, feed nitrogen to 0.5～1.5MPa simultaneously, under 30～100 ℃ condition, carry out constant temperature mechanical stirring 0.5～3h with the speed of 50～400r/min;
2) 30～100 ℃, with 1) in added dianhydride amount be benchmark, in dianhydride and diamines mol ratio is the ratio adding diamines of 0.8:1～1.05:1, feed nitrogen to 0.5～1.5MPa simultaneously, continue under this temperature speed mechanical stirring, constant temperature 0.5～2h with 50～400r/min;
3) step 2) finish after, be warming up to 135～180 ℃ with the heat-up rate of 1～5 ℃/min, and with identical speed continue to stir, constant temperature 0.5～2h;
4) after step 3) finishes, be warming up to 180～250 ℃ with the heat-up rate of 1～5 ℃/min, and with identical speed continue to stir, constant temperature 0.5～2h;
5) after step 4) finishes, cooling, to gained polyimide/water mixture separate, pickling, drying, promptly get the thermoplastic polyimide product.
The invention provides the method for the synthetic Thermocurable polyimide of a kind of water, it is characterized in that comprising following process:
1) with water as solvent, dianhydride or dianhydride and end-capping reagent or dianhydride and catalyzer are added in the entry, feed nitrogen to 0.5～1.5MPa simultaneously, and the speed constant temperature with 50～400r/min stirs 0.5～3h under 30～100 ℃; Wherein, the mol ratio of dianhydride and end-capping reagent is 50:1～5:1, and dianhydride and catalyst quality are than being 2000:1～20:1, and the mass ratio of dianhydride and water is 1:5～1:30;
2) 30～100 ℃, with 1) in added dianhydride amount be benchmark, in dianhydride and diamines mol ratio is the ratio adding diamines of 0.8:1～1.05:1, feed nitrogen to 0.5～1.5MPa simultaneously, continue under this temperature speed mechanical stirring, constant temperature 0.5～2h with 50～400r/min;
3) step 2) finish after, be warming up to 135～180 ℃ with the heat-up rate of 1～5 ℃/min, and under the stirring velocity of 50～400r/min, constant temperature 0.5～2h;
4) after step 3) finishes, be warming up to 180～250 ℃ with the heat-up rate of 1～5 ℃/min, and under the stirring velocity of 50～400r/min, constant temperature 0.5～2h;
5) after step 4) finishes, lower the temperature naturally, to products therefrom filter, pickling, drying, promptly get heat cured polyimide product.
The feature of above-mentioned synthesis technique is: with water as solvent or dispersion medium, adopt two-step approach, synthesis of polyimides in 30～250 ℃ of temperature ranges.
The particle diameter of above-mentioned used dianhydride, diamines and end-capping reagent is 5～200 μ m;
When added dianhydride is two kinds of materials, mol ratio is 10:1～1:5;
When added diamines is two kinds of materials, mol ratio is 20:1～1:10;
Above-mentioned dianhydride is selected from 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, perhaps pyromellitic acid anhydride, perhaps 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydride, perhaps 4,4 '-combination of any one or two kinds in the two Tetra hydro Phthalic anhydrides of oxygen;
Perhaps above-mentioned dianhydride is selected from 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, perhaps pyromellitic acid anhydride, perhaps 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydride, perhaps 4,4 '-combination of any one or two kinds in the dianhydride class material that the two Tetra hydro Phthalic anhydrides of oxygen are molecular structure unit.
Above-mentioned end-capping reagent is selected from any one in diacetyl oxide or MALEIC ANHYDRIDE or the Tetra hydro Phthalic anhydride;
Perhaps above-mentioned end-capping reagent is selected from any one in the anhydrides derivative of diacetyl oxide or MALEIC ANHYDRIDE or Tetra hydro Phthalic anhydride.
Above-mentioned catalyzer is selected from P
d, or P
t, or Ru or Fe or Cu or Co or Ni in any one;
Perhaps above-mentioned catalyzer is selected from P
d, or P
t, or Ru or Fe or Cu or Co or Ni be in the cationic inorganic or organic salt material any one.
Above-mentioned diamines is selected from 3,4-diaminodiphenyl oxide or 4, the combination of any one of 4-diaminodiphenyl oxide or diaminodiphenylmethane or mphenylenediamine or Ursol D or two kinds.
Perhaps above-mentioned diamines is selected from 3, and 4-diaminodiphenyl oxide or 4,4-diaminodiphenyl oxide or diaminodiphenylmethane or mphenylenediamine or Ursol D are the combination of any one or two kinds of two amine materials of molecular structure unit.
Principle of work of the present invention: with water compositing dispersion medium, adopt suspension polymerization, under the effect of catalyzer and end-capping reagent, allow dianhydride and diamines carry out the imidization polyreaction and generate polyimide.By the distribution of preparation technology's regulatory molecule amount, and then the thermoplasticity or the Thermocurable polyimide of acquisition different performance.
The invention has the advantages that: 1. technology is simple, is easy to industrialization, and 2. cost is low, and 3. pollution-free, 4. adjustable range of product performance is wide, and controllability is good.
The present invention is with water as solvent, adopts the new technology of two-step approach at (in 250 ℃) synthesis of polyimides under the lower temperature.Not only cost is low for this technology, technology simple, environmental friendliness, and makes that by the modulation process parameter physico-chemical property of different performance polyimide product is controlled, and what is more important, this technology are very easy to realize large-scale industrial production.
Embodiment:
Embodiment 1
At 30 ℃, with 100g 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 4g Fe (NO
3)
3Catalyzer, 6g MALEIC ANHYDRIDE and 1000ml water place the reactor of 5L, feed nitrogen to 0.5MPa.Under the stirring velocity of 200r/min, be warming up to 80 ℃ and constant temperature 1.5h with the heat-up rate of 2 ℃/min.Be cooled to the room temperature release and add 50g 4,4-diaminodiphenyl oxide and 10g diaminodiphenylmethane feed nitrogen to 0.5MPa, keep then stirring velocity constant, be warming up to 150 ℃, 200 ℃ and each constant temperature 2h respectively with the heat-up rate of 2 ℃/min.The mixture of gained polyimide/water is vacuumized separation, formic acid pickling three times, 100 ℃ of dry 2h again, obtain the block thermoplastic polyimide product of 108g field gray, its second-order transition temperature, melt temperature are respectively 220 ℃ and 380 ℃, and transmittance is 5%.
Embodiment 2
At 60 ℃, with 100g3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 5g Tetra hydro Phthalic anhydride, 4g Fe (NO
3)
3Place the reactor of 5L in catalyzer and the 2000ml water, feed nitrogen, be warming up to 100 ℃ with the heat-up rate of 2 ℃/min to 1.5MPa, and with the stirring velocity constant temperature 2h of 200r/min.Release then adds 10g 3, and 4-diaminodiphenyl oxide and 50g diaminodiphenylmethane feed nitrogen to 1.5MPa, keep then stirring velocity constant, be warming up to 140 ℃, 200 ℃ and each constant temperature 1.5h respectively with the heat-up rate of 3 ℃/min.The mixture of gained polyimide/water is vacuumized separation, formic acid pickling three times, 100 ℃ of dry 2h again, obtain the powder thermoplastic polyimide product of 110g beige, its second-order transition temperature, melt temperature are respectively 210 ℃ and 370 ℃, and transmittance is 65%.
Embodiment 3
At 50 ℃, with 100g 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 4g Fe (NO
3)
3Place the reactor of 5L in catalyzer, 5g diacetyl oxide and the 500ml water, feed nitrogen, be warming up to 80 ℃ with the heat-up rate of 2 ℃/min to 0.5MPa, and with the stirring velocity constant temperature 2h of 400r/min.Release then adds 50g 3,4-diaminodiphenyl oxide or 10g 4, the 4-diaminodiphenyl oxide feeds nitrogen to 0.5MPa, keep then stirring velocity constant, be warming up to 130 ℃, 240 ℃ and each constant temperature 1h respectively with the heat-up rate of 3 ℃/min.The mixture of gained polyimide/water is vacuumized separation, formic acid pickling three times, 100 ℃ of dry 2h again, obtain the powder thermoplastic polyimide product of 97g beige, its second-order transition temperature, melt temperature are respectively 209 ℃ and 375 ℃, and transmittance is 90%.
Embodiment 4
With 100g 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride and 2000ml water places the reactor of 5L, and be warmed up to 100 ℃, under the situation that does not add any end-capping reagent and catalyzer, directly feed nitrogen to 0.5MPa.Under the stirring velocity of 400r/min, 100 ℃ of constant temperature 2h.Release then adds 10g3,4-diaminodiphenyl oxide and 50g4, the 4-diaminodiphenyl oxide feeds nitrogen to 0.5MPa, keep then stirring velocity constant, be warming up to 138 ℃, 230 ℃ and each constant temperature 1h respectively with the heat-up rate of 3 ℃/min.The mixture of gained polyimide/water is vacuumized separation, formic acid pickling three times, 100 ℃ of dry 2h again, obtain the granular Thermocurable polyimide product of 110g beige, its melt temperature is 397 ℃, and cracking temperature is 517 ℃, and transmittance is 0.
Embodiment 5
At 30 ℃, with placing the reactor of 5L in 75g pyromellitic acid anhydride, 5g diacetyl oxide and the 3000ml water, under the situation that does not add catalyzer, directly feed nitrogen to 1.5MPa, heat-up rate with 2 ℃/min is warming up to 80 ℃, and with the stirring velocity constant temperature 2h of 400r/min.Release then adds 60g4, and the 4-diaminodiphenyl oxide feeds nitrogen to 1.0MPa, keep then stirring velocity constant, be warming up to 145 ℃, 190 ℃ and each constant temperature 1h respectively with the heat-up rate of 3 ℃/min.The mixture of gained polyimide/water is vacuumized separation, formic acid pickling three times, 100 ℃ of dry 2h again, obtain the Thermocurable polyimide of 106g field gray, its melt temperature is 525 ℃, and transmittance is 0.
Embodiment 6
At 30 ℃, with 80g 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 15g pyromellitic acid anhydride, 5g diacetyl oxide, 5g Fe (NO
3)
3Place the reactor of 5L in catalyzer and the 2500ml water, directly feed nitrogen, be warming up to 80 ℃ with the heat-up rate of 2 ℃/min to 1.5MPa, and with the stirring velocity constant temperature 2h of 400r/min.Release then adds 20g 3, the 4-diaminodiphenyl oxide, adds 40g 4, and the 4-diaminodiphenyl oxide feeds nitrogen to 1.5MPa, keep then stirring velocity constant, be warming up to 135 ℃, 190 ℃ and each constant temperature 1.5h respectively with the heat-up rate of 1.5 ℃/min.The mixture of gained polyimide/water is vacuumized separation, formic acid pickling three times, 100 ℃ of dry 2h again, obtain the lurid powder thermoplastic polyimide of 136g, its second-order transition temperature, melt temperature are respectively 219 ℃ and 385 ℃, and transmittance is 35%.
Embodiment 7
At 40 ℃, with the two Tetra hydro Phthalic anhydrides of 100g 4,4 '-oxygen, 20g pyromellitic acid anhydride, 5g diacetyl oxide, 8g NiCl
3Place the reactor of 5L in catalyzer and the 1500ml water, directly feed nitrogen, be warming up to 100 ℃ with the heat-up rate of 2 ℃/min to 1.5MPa, and with the stirring velocity constant temperature 1h of 400r/min.Release then adds 55g 3, the 4-diaminodiphenyl oxide, adds 27g 4, and the 4-diaminodiphenyl oxide feeds nitrogen to 1.5MPa, keep then stirring velocity constant, be warming up to 140 ℃, 180 ℃ and each constant temperature 1.5h respectively with the heat-up rate of 2.5 ℃/min.The mixture of gained polyimide/water is vacuumized separation, formic acid pickling three times, 120 ℃ of dry 2h again, obtain the flavous powder thermoplastic polyimide of 170g, its second-order transition temperature, melt temperature are respectively 225 ℃ and 382 ℃, and transmittance is 75%.
Embodiment 8
At 35 ℃, with the two Tetra hydro Phthalic anhydrides of 100g 4,4 '-oxygen, 6g Tetra hydro Phthalic anhydride, 10gNiCl
3Place the reactor of 5L in catalyzer and the 1500ml water, directly feed nitrogen, be warming up to 80 ℃ with the heat-up rate of 2 ℃/min to 2.0MPa, and with the stirring velocity constant temperature 2h of 400r/min.Release then adds 50g 3,4-diaminodiphenyl oxide, 15g 4, the 4-diaminodiphenyl oxide feeds nitrogen to 2.0MPa, keep then stirring velocity constant, be warming up to 130 ℃, 180 ℃ and each constant temperature 1.5h respectively with the heat-up rate of 2.5 ℃/min.The mixture of gained polyimide/water is vacuumized separation, formic acid pickling three times, 120 ℃ of dry 2h again, obtain the flaxen powder thermoplastic polyimide of 140g, its second-order transition temperature, melt temperature are respectively 220 ℃ and 388 ℃, and transmittance is 65%.
Claims (8)
1. the method for a water synthetic thermoplastic polyimide is characterized in that may further comprise the steps:
1) takes by weighing dianhydride, end-capping reagent, catalyzer, water respectively, wherein, the mol ratio of dianhydride and end-capping reagent is that 50: 1～5: 1, dianhydride and catalyst quality ratio are that the mass ratio of 2000: 1～20: 1, dianhydride and water is 1: 5～1: 30, dianhydride, end-capping reagent, catalyzer, water are added in the reactor, feed nitrogen to 0.5～1.5MPa simultaneously, carry out constant temperature mechanical stirring 0.5～3h under 30～100 ℃ condition, described end-capping reagent is a Tetra hydro Phthalic anhydride;
2) 30～100 ℃, with 1) in added dianhydride amount be benchmark, be that 0.8: 1～1.05: 1 ratio adds diamines in dianhydride and diamines mol ratio, feed nitrogen to 0.5～1.5MPa simultaneously, continue mechanical stirring, constant temperature 0.5～2h under this temperature;
3) step 2) finish after, be warming up to 135～180 ℃ with the heat-up rate of 1～5 ℃/min, and with identical speed continue to stir, constant temperature 0.5～2h;
4) after step 3) finishes, be warming up to 180～250 ℃ with the heat-up rate of 1～5 ℃/min, and with identical speed continue to stir, constant temperature 0.5～2h;
5) after step 4) finishes, cooling, to gained polyimide/water mixture separate, pickling, drying, promptly get the thermoplastic polyimide product.
2. by the synthetic method of the described a kind of thermoplastic polyimide of claim 1, it is characterized in that: in step 1), added dianhydride is an one matter.
3. by the synthetic method of the described a kind of thermoplastic polyimide of claim 1, it is characterized in that: in step 1), the particle diameter of dianhydride and end-capping reagent is 5～200 μ m, and stirring velocity is 50～400r/min.
4. by the synthetic method of the described a kind of thermoplastic polyimide of claim 1, it is characterized in that: in step 2) in, added diamines is an one matter.
5. by the synthetic method of the described a kind of thermoplastic polyimide of claim 1, it is characterized in that: in step 2) in, the particle diameter of diamines is 5～200 μ m, and stirring velocity is 50～400r/min.
6. press the synthetic method of the described a kind of thermoplastic polyimide of claim 1, it is characterized in that: described dianhydride is selected from 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride or pyromellitic acid anhydride or 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydride or 4,4 '-in the two Tetra hydro Phthalic anhydrides of oxygen any one.
7. by the synthetic method of the described a kind of thermoplastic polyimide of claim 1, it is characterized in that: described catalyzer is selected from P
d, or P
t, or Ru or Fe or Cu or Co or Ni be in the cationic inorganic or organic salt material any one.
8. press the synthetic method of the described a kind of thermoplastic polyimide of claim 1, it is characterized in that: described diamines is selected from 3,4-diaminodiphenyl oxide or 4, any one in 4-diaminodiphenyl oxide or diaminodiphenylmethane or mphenylenediamine or the Ursol D.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102120820B (en) * | 2011-01-26 | 2016-03-30 | 上海三普化工有限公司 | A kind of method of performing aqueous synthesis of thermosetting polyimide |
| CN102766260B (en) * | 2012-07-18 | 2014-08-13 | 杭州塑盟特科技有限公司 | Method for preparing polyimide in supercritical carbon dioxide |
| EP3259302B1 (en) | 2015-02-20 | 2024-07-24 | SHPP Global Technologies B.V. | Poly(amic acid) synthesis and conversion to high molecular weight polyimide |
| CN118344591A (en) * | 2024-06-03 | 2024-07-16 | 江苏海洋大学 | Preparation method of thermosetting polyimide material using water as solvent |
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| JP2002212287A (en) * | 2001-01-22 | 2002-07-31 | Hitachi Cable Ltd | Method for producing polyimide |
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Address after: 200000 China (Shanghai) free trade zone, 1388 Tung Chang Road, building 201, room 9 Patentee after: Shanghai Sanpu water Mstar Technology Ltd Address before: 201611 Shanghai City, Songjiang District new town Frestech road 1500 Lane 69 Patentee before: Shanghai Sanpu Chemical Co.,Ltd. |