CN102120820A - Method for performing aqueous synthesis of thermosetting polyimide - Google Patents
Method for performing aqueous synthesis of thermosetting polyimide Download PDFInfo
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- CN102120820A CN102120820A CN2011100283543A CN201110028354A CN102120820A CN 102120820 A CN102120820 A CN 102120820A CN 2011100283543 A CN2011100283543 A CN 2011100283543A CN 201110028354 A CN201110028354 A CN 201110028354A CN 102120820 A CN102120820 A CN 102120820A
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- dianhydride
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- thermocurable polyimide
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Abstract
The invention discloses a method for performing the aqueous synthesis of thermosetting polyimide, belonging to the technical field of the synthesis of the polyimide polymer and solving the technical problem of the prior art that the synthesis method of thermosetting polyimide has long reaction period and unstable performance. The method uses anhydride with a unsaturated bond or aniline as blocking agent and water as dispersion medium to synthesize thermosetting polyimide. The method comprises the following steps: using dianhydride, catalyst and water to perform mechanical agitation; using dianhydride solution, diamine and blocking agent to perform mechanical agitation; heating to 135-180 DEG C and 180-250 DEG C respectively in a heating speed of 1-5 DEG C/min; and separating the obtained product, washing and drying to obtain thermosetting polyimide. The method has simple process, low cost, no pollution, wide adjustable range of the product performance and good controllability, and is easy to realize industrialization.
Description
Technical field
The present invention relates to chemical field, relate in particular to the synthetic method of Thermocurable polyimide.
Background technology
Polyimide is as a kind of cutting-edge structure material or functional material, has high temperature resistant, rub resistance, corrosion-resistant, radioprotective, anti-oxidant, excellent specific property such as physical strength is high, electrical insulation capability is good.Thermocurable polyimide is that a class has cancellated crosslinked polymer material, because synthetic and use processing approach characteristics such as diversity, they are widely used in the technical fields such as machinery, electric, space flight and aviation with forms such as tackiness agent, coating, Embedding Material and matrix materials.
Polyimide all is family macromolecule compounds that carry out containing on the main chain that polyreaction forms imide ring by diamines and dianhydride.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, and polyamic acid ten minutes facile hydrolysis, therefore do not make the solvent of water as synthesis of polyimides.Still adopt low temperature formation polyamic acid in organic solvent at present, the high-temperature sub amination obtains polyimide material, as N,N-dimethylacetamide, and organic solvents such as N-Methyl pyrrolidone or meta-cresol.For this reason not only the cost height of raw material, reaction time long, pollute big, dangerous greatly, residual high boiling organic solvent is difficult to eliminate in the product, and organic solvent and polyimide separate and recovery derives a lot of technological processs, not only consuming time but also power consumption.In recent years find that water also can become the good solvent of some organic compound under suitable high pressure and temperature.Australian JOHN CHIEF ARI etc. proposes the technology of aqueous phase synthesis of polyimides first, and making water is that solvent adopts high pressure polycondensation method synthesis of polyimides, yet is difficult to repeat to obtain high molecular, the product of stable performance.
Summary of the invention
At the defective that exists in the above-mentioned prior art, the method that the synthetic Thermocurable polyimide of the stable water of a kind of product performance is provided of the present invention.
The invention provides the method for the synthetic Thermocurable polyimide of a kind of water, it is characterized in that may further comprise the steps:
1) take by weighing dianhydride respectively, catalyzer adds in the entry, dianhydride and catalyst quality ratio are 1:30～1:50 for the mass ratio of 2000:1～120:1, dianhydride and water, feed nitrogen to 0.5～2.0MPa simultaneously, and constant temperature stirs 0.5～3h under 30～150 ℃ condition, and stirring velocity is 50～400r/min;
2) 30～150 ℃, with 1) in added dianhydride amount be benchmark, add diamines and end-capping reagent by a certain percentage, wherein end-capping reagent is acid anhydrides or the aniline that contains a unsaturated link(age), feeds nitrogen to 0.5～2.0MPa simultaneously, continues 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, washing, drying, promptly get the Thermocurable polyimide product.
Further, in step 1), the particle diameter of dianhydride, diamines is 5～200 μ m.
Further, when the end-capping reagent that adds was the anhydrides material, dianhydride and diamines mol ratio were that the mol ratio of 1:2～1:1.25, dianhydride and end-capping reagent is 1:2～1:0.5.
Further, when the end-capping reagent that adds was amine substance, diamines and dianhydride mol ratio were that the mol ratio of 1:2～1:1.25, diamines and end-capping reagent is 1:2～1:0.5.
Further, described dianhydride is selected from 3,3 ＇, 4,4 ＇-bibenzene tetracarboxylic dianhydride or pyromellitic acid anhydride or 3,3 ＇, any one in the two Tetra hydro Phthalic anhydrides of 4,4 ＇-tetracarboxylic benzophenone dianhydride or 4,4 ＇-oxygen;
Further, described diamines is selected from 3,4-diaminodiphenyl oxide or 4, any one of 4-diaminodiphenyl oxide or diaminodiphenylmethane or mphenylenediamine or Ursol D.
Further, described acid anhydrides that contains a unsaturated link(age) or aniline end-capping reagent are selected from any one in methyl carbic anhydride, inner methylidyne tetrahydric phthalic anhydride, maleic anhydride, allyl group norborneol acid anhydrides or 3-vinyl aniline, the 3-ethynyl aniline.
Further, described catalyzer is selected from any one in Tetrabutyl amonium bromide or tetrabutylammonium chloride or benzyltriethylammoinium chloride or the tri-n-octyl methyl ammonium chloride.
Further, in step 5), adopt methyl alcohol to wash described.
Principle of work of the present invention: make reaction medium with water, in 30～250 ℃ of temperature ranges, synthesize Thermocurable polyimide by dianhydride and diamines.The effect of catalyzer is to improve the polyreaction productive rate; By changing end-capping reagent controlling of quality molecular weight, and under solidification value, takes place crosslinkedly by the unsaturated link(age) in the end-capping reagent, form reticulated structure, 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.What is more important, this technology are very easy to realize large-scale industrial production.
Embodiment:
Embodiment 1
At 50 ℃, with placing the reactor of 5L in the two Tetra hydro Phthalic anhydrides of 155.1g 4,4 ＇-oxygen, 1.2g Tetrabutyl amonium bromide catalyzer, the 1500ml water, feed nitrogen to 2.0MPa, heat-up rate with 2 ℃/min is warming up to 100 ℃, and with the stirring velocity constant temperature 2h of 400r/min.The release of lowering the temperature then adds 200.2g 4, and 4-diaminodiphenyl oxide and 178.2g methyl carbic anhydride feed nitrogen to 1.5MPa, keep then stirring velocity constant, be warming up to 145 ℃, 210 ℃ and each constant temperature 1h respectively with the heat-up rate of 2 ℃/min.The mixture of gained polyimide/water vacuumized separation, methyl alcohol are given a baby a bath on the third day after its birth time, 120 ℃ of dry 2h again, obtain the powder Thermocurable polyimide product of 478g beige, this Thermocurable polyimide is through finishing curing at 250 ℃, obtain 279 ℃ of its second-order transition temperatures of specimen, shock strength 142MPa.
Embodiment 2
At 50 ℃, with 147.1g 3,3 ＇, 4, place the reactor of 5L in 4 ＇-bibenzene tetracarboxylic dianhydride, 1.2g benzyltriethylammoinium chloride catalyzer and the 2000ml water, directly feed nitrogen to 2.0MPa, be warming up to 130 ℃ with the heat-up rate of 2 ℃/min, and with the stirring velocity constant temperature 1h of 400r/min.Be cooled to 60 ℃ of releases then, add 148.7g diaminodiphenylmethane and 49g maleic anhydride, feed nitrogen, at the uniform velocity stir 1.0h then to 2.0MPa.Heat-up rate with 2.5 ℃/min is warming up to 150 ℃, 210 ℃ and each constant temperature 1.5h respectively then.The mixture of gained polyimide/water vacuumized separation, methyl alcohol are given a baby a bath on the third day after its birth time, 120 ℃ of dry 2h again, obtain 312g xanchromatic powder Thermocurable polyimide, this Thermocurable polyimide and equimolar diallyl bisphenol (DBA) 154.2g are 60
oStirring and dissolving is poured the good mould of preheating rapidly into to homogeneous, transparent solution in the C oil bath, puts into curing oven (program curing: 160
oC 2h+185
oC 2h+200
oC 2h).The solidified sample second-order transition temperature is 266 ℃, shock strength 148MPa.
Embodiment 3
At 50 ℃, with 161g 3,3 ＇, 4, place the reactor of 5L in 4 ＇-tetracarboxylic benzophenone dianhydride, 1.5 g benzyltriethylammoinium chloride catalyzer and the 1500ml water, directly feed nitrogen to 1.5MPa, be warming up to 140 ℃ with the heat-up rate of 2 ℃/min, and with the stirring velocity constant temperature 2h of 400r/min.Be cooled to 90 ℃ of releases then, add 27g mphenylenediamine and 58.5g 3-ethynyl aniline, feed nitrogen, at the uniform velocity stir 0.5h then to 1.5MPa.Heat-up rate with 2.5 ℃/min is warming up to 130 ℃, 180 ℃ and each constant temperature 1.5h respectively then.The mixture of gained polyimide/water vacuumized separation, methyl alcohol are given a baby a bath on the third day after its birth time, 120 ℃ of dry 2h again, obtain the khaki powder Thermocurable polyimide of 218g, this Thermocurable polyimide obtains specimen through finishing curing at 180-330 ℃.Its second-order transition temperature is 268 ℃, shock strength 145MPa.
Embodiment 4
At 50 ℃, with 147.1g 3,3 ＇, place the reactor of 5L in 4,4 ＇-bibenzene tetracarboxylic dianhydride, 1.0g tetrabutylammonium chloride catalyzer, the 1500ml water, feed nitrogen to 1.5MPa, heat-up rate with 2 ℃/min is warming up to 120 ℃, and with the stirring velocity constant temperature 2h of 400r/min.The release of lowering the temperature then adds 160g 3, and 4-diaminodiphenyl oxide and 115g allyl group norborneol acid anhydrides feed nitrogen to 1.5MPa, keep then stirring velocity constant, be warming up to 145 ℃, 210 ℃ and each constant temperature 1h respectively with the heat-up rate of 2 ℃/min.The mixture of gained polyimide/water vacuumized separation, methyl alcohol are given a baby a bath on the third day after its birth time, 120 ℃ of dry 2h again, obtain the powder Thermocurable polyimide product of 388g beige, this Thermocurable polyimide is through finishing curing at 250 ℃, obtain 283 ℃ of its second-order transition temperatures of specimen, shock strength 152MPa.
Claims (9)
1. the method for the synthetic Thermocurable polyimide of a water is characterized in that may further comprise the steps:
Take by weighing dianhydride respectively, catalyzer adds in the entry, dianhydride and catalyst quality ratio are 1:30～1:50 for the mass ratio of 2000:1～120:1, dianhydride and water, feed nitrogen to 0.5～2.0MPa simultaneously, and constant temperature stirs 0.5～3h under 30～150 ℃ condition, and stirring velocity is 50～400r/min;
30～150 ℃, with 1) in added dianhydride amount be benchmark, add diamines and end-capping reagent by a certain percentage, wherein end-capping reagent is acid anhydrides or the aniline that contains a unsaturated link(age), feeds nitrogen to 0.5～2.0MPa simultaneously, continues stirring, constant temperature 0.5～2h under this temperature;
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;
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;
After step 4) finishes, cooling, to gained polyimide/water mixture separate, washing, drying, promptly get the Thermocurable polyimide product.
2. the method for the synthetic Thermocurable polyimide of a kind of water as claimed in claim 1, it is characterized in that: in step 1), the particle diameter of dianhydride, diamines is 5～200 μ m.
3. the method for the synthetic Thermocurable polyimide of a kind of water as claimed in claim 1, it is characterized in that: in step 2) in, when the end-capping reagent that adds was the anhydrides material, dianhydride and diamines mol ratio were that the mol ratio of 1:2～1:1.25, dianhydride and end-capping reagent is 1:2～1:0.5.
4. the method for the synthetic Thermocurable polyimide of a kind of water as claimed in claim 1, it is characterized in that: in step 2) in, when the end-capping reagent that adds was amine substance, diamines and dianhydride mol ratio were that the mol ratio of 1:2～1:1.25, diamines and end-capping reagent is 1:2～1:0.5.
5. the method for the synthetic Thermocurable polyimide of a kind of water as claimed in 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, in the two Tetra hydro Phthalic anhydrides of 4 ＇-tetracarboxylic benzophenone dianhydride or 4,4 ＇-oxygen any one.
6. the method for the synthetic Thermocurable polyimide of a kind of water as claimed in 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.
7. the method for the synthetic Thermocurable polyimide of a kind of water as claimed in claim 1, it is characterized in that: the above-mentioned acid anhydrides that contains a unsaturated link(age) or the end-capping reagent of aniline be selected from methyl carbic anhydride or inner methylidyne tetrahydric phthalic anhydride or maleic anhydride or allyl group norborneol acid anhydrides or, perhaps any one in 3-vinyl aniline or the 3-ethynyl aniline.
8. the method for the synthetic Thermocurable polyimide of a kind of water as claimed in claim 1, it is characterized in that: described catalyzer is selected from any one in Tetrabutyl amonium bromide or tetrabutylammonium chloride or benzyltriethylammoinium chloride or the tri-n-octyl methyl ammonium chloride.
9. the method for the synthetic Thermocurable polyimide of a kind of water as claimed in claim 1 is characterized in that: in step 5), adopt methyl alcohol to wash described.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724624A (en) * | 2013-12-30 | 2014-04-16 | 深圳市惠程电气股份有限公司 | High-dielectric-constant polyimide film, preparation method and application thereof |
| CN106459411A (en) * | 2014-06-10 | 2017-02-22 | 延世大学校原州产学协力团 | Method for preparing polyimide using water as dispersion medium and method for recovering water |
| CN108395534A (en) * | 2018-01-16 | 2018-08-14 | 常州杰铭新材料科技有限公司 | A kind of solubility height and the good bismaleimide performed polymer and its preparation method and application of temperature tolerance |
| CN108948352A (en) * | 2018-07-18 | 2018-12-07 | 上海三普水相材料科技有限公司 | A method of preparing polyimides |
| CN109135552A (en) * | 2018-07-05 | 2019-01-04 | 常州思宇知识产权运营有限公司 | A kind of preparation method of high-strength high temperature-resistant type impregnating varnish |
| CN111072963A (en) * | 2019-12-27 | 2020-04-28 | 江门市优巨新材料有限公司 | Method for synthesizing polyimide in aqueous phase |
| CN111978725A (en) * | 2020-07-28 | 2020-11-24 | 凯正包装科技(广东)有限公司 | Antibacterial high-temperature-aging-resistant polyimide film and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0971651A (en) * | 1995-06-28 | 1997-03-18 | Mitsui Toatsu Chem Inc | Linear polyamic acid, linear polyimide and thermosetting polyimide |
| JPH11292966A (en) * | 1998-04-13 | 1999-10-26 | Mitsui Chem Inc | Linear polymamic acid, linear polyimide and thermosetting polyimide |
| CN1389494A (en) * | 2001-06-04 | 2003-01-08 | 中国科学院化学研究所 | Thermosetting polyimide base resin and its prepn. |
| CN1680465A (en) * | 2004-04-05 | 2005-10-12 | 中国科学院化学研究所 | Thermosetting polyimide matrix resin, preparation and use thereof |
| CN101412812A (en) * | 2008-10-28 | 2009-04-22 | 上海三普化工有限公司 | Method for aqueous phase synthesis of polyimides |
-
2011
- 2011-01-26 CN CN201110028354.3A patent/CN102120820B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0971651A (en) * | 1995-06-28 | 1997-03-18 | Mitsui Toatsu Chem Inc | Linear polyamic acid, linear polyimide and thermosetting polyimide |
| JPH11292966A (en) * | 1998-04-13 | 1999-10-26 | Mitsui Chem Inc | Linear polymamic acid, linear polyimide and thermosetting polyimide |
| CN1389494A (en) * | 2001-06-04 | 2003-01-08 | 中国科学院化学研究所 | Thermosetting polyimide base resin and its prepn. |
| CN1680465A (en) * | 2004-04-05 | 2005-10-12 | 中国科学院化学研究所 | Thermosetting polyimide matrix resin, preparation and use thereof |
| CN101412812A (en) * | 2008-10-28 | 2009-04-22 | 上海三普化工有限公司 | Method for aqueous phase synthesis of polyimides |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724624A (en) * | 2013-12-30 | 2014-04-16 | 深圳市惠程电气股份有限公司 | High-dielectric-constant polyimide film, preparation method and application thereof |
| CN103724624B (en) * | 2013-12-30 | 2016-03-30 | 深圳市惠程电气股份有限公司 | high dielectric constant polyimide film and its preparation method and application |
| CN106459411A (en) * | 2014-06-10 | 2017-02-22 | 延世大学校原州产学协力团 | Method for preparing polyimide using water as dispersion medium and method for recovering water |
| CN108395534A (en) * | 2018-01-16 | 2018-08-14 | 常州杰铭新材料科技有限公司 | A kind of solubility height and the good bismaleimide performed polymer and its preparation method and application of temperature tolerance |
| CN109135552A (en) * | 2018-07-05 | 2019-01-04 | 常州思宇知识产权运营有限公司 | A kind of preparation method of high-strength high temperature-resistant type impregnating varnish |
| CN108948352A (en) * | 2018-07-18 | 2018-12-07 | 上海三普水相材料科技有限公司 | A method of preparing polyimides |
| CN111072963A (en) * | 2019-12-27 | 2020-04-28 | 江门市优巨新材料有限公司 | Method for synthesizing polyimide in aqueous phase |
| CN111978725A (en) * | 2020-07-28 | 2020-11-24 | 凯正包装科技(广东)有限公司 | Antibacterial high-temperature-aging-resistant polyimide film and preparation method thereof |
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| CN102120820B (en) | 2016-03-30 |
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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: 200122 No. 357 pinewood Road, Shanghai, Pudong New Area 2711-2713 Patentee before: Shanghai Sanpu Chemical Co.,Ltd. |