CN102120820B - A kind of method of performing aqueous synthesis of thermosetting polyimide - Google Patents
A kind of method of performing aqueous synthesis of thermosetting polyimide Download PDFInfo
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- CN102120820B CN102120820B CN201110028354.3A CN201110028354A CN102120820B CN 102120820 B CN102120820 B CN 102120820B CN 201110028354 A CN201110028354 A CN 201110028354A CN 102120820 B CN102120820 B CN 102120820B
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- dianhydride
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 38
- 239000004642 Polyimide Substances 0.000 title claims abstract description 37
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 13
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 7
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 18
- 150000004985 diamines Chemical class 0.000 claims abstract description 16
- 238000010792 warming Methods 0.000 claims abstract description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 5
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- -1 allyl group norborneol acid anhydrides Chemical class 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 claims description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- IFSSSYDVRQSDSG-UHFFFAOYSA-N 3-ethenylaniline Chemical compound NC1=CC=CC(C=C)=C1 IFSSSYDVRQSDSG-UHFFFAOYSA-N 0.000 claims description 2
- NNKQLUVBPJEUOR-UHFFFAOYSA-N 3-ethynylaniline Chemical compound NC1=CC=CC(C#C)=C1 NNKQLUVBPJEUOR-UHFFFAOYSA-N 0.000 claims description 2
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001442 methylidyne group Chemical group [H]C#[*] 0.000 claims description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 239000002612 dispersion medium Substances 0.000 abstract 1
- 238000010907 mechanical stirring Methods 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical group C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000004223 radioprotective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a kind of method of performing aqueous synthesis of thermosetting polyimide, belong to the synthesis technical field of polyimide-based polymer, solve the technical problem of Thermocurable polyimide synthetic method length reaction time of the prior art, unstable properties.Method of the present invention with containing the acid anhydrides of a unsaturated link(age) or aniline for end-capping reagent, with water compositing dispersion medium synthesis Thermocurable polyimide; The method comprises one and dianhydride, catalyzer and water is carried out churned mechanically step, comprise a step two anhydride solutions, diamines mixed with end-capping reagent mechanical stirring, comprise one to be warming up to 135 ~ 180 DEG C, 180 ~ 250 DEG C respectively step with the heat-up rate of 1 ~ 5 DEG C/min; Comprise one products therefrom carried out be separated, wash, dry step, namely obtain heat cured polyimide.Present invention process is simple, is easy to industrialization, cost variable range that is low, pollution-free, product performance is wide, controllability good.
Description
Technical field
The present invention relates to chemical field, particularly relate to the synthetic method of Thermocurable polyimide.
Background technology
Polyimide, as a kind of cutting-edge structure material or functional material, has high temperature resistant, rub resistance, corrosion-resistant, radioprotective, an excellent specific property such as anti-oxidant, physical strength is high, electrical insulation capability is good.Thermocurable polyimide is that a class has cancellated crosslinked polymer material, due to the feature such as diversity of synthesis and application processing approach, 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, be all carry out polyreaction formation by diamines and dianhydride main chain on a family macromolecule compound containing imide ring.The difference of monomer whose molecular structure and molecular weight distribution thereof, by imparting its different thermodynamics, optics and mechanical mechanics property.Because any diamines or two compound anhydrides are hydrophobic organism, and polyamic acid very facile hydrolysis, therefore do not use water as the solvent of synthesis of polyimides.Still adopt low temperature in organic solvent to form polyamic acid at present, high temperature imidization obtains polyimide material, as N,N-dimethylacetamide, and the organic solvent such as N-Methyl pyrrolidone or meta-cresol.Not only the cost of raw material is high for this reason, reaction time is long, it is large to pollute, dangerous large, high boiling organic solvent residual in product is difficult to eliminate, and organic solvent and polyimide be separated and recovery derives a lot of technological process, not only consuming time but also consume energy.In recent years find under suitable high pressure and temperature, water also can become the good solvent of some organic compound.The JOHNCHIEFARI etc. of Australia proposes the technology of aqueous phase synthesis of polyimides first, uses water for solvent employing high pressure polycondensation method synthesis of polyimides, but is difficult to repeat to obtain high molecular, the product of stable performance.
Summary of the invention
For the defect existed in above-mentioned prior art, the method providing the stable performing aqueous synthesis of thermosetting polyimide of a kind of product performance of the present invention.
The invention provides a kind of method of performing aqueous synthesis of thermosetting polyimide, it is characterized in that comprising the following steps:
1) take dianhydride respectively, catalyzer is added to the water, dianhydride and catalyst quality are 1:30 ~ 1:50 than the mass ratio for 2000:1 ~ 120:1, dianhydride and water, pass into nitrogen to 0.5 ~ 2.0MPa simultaneously, and constant temperature stirs 0.5 ~ 3h under the condition of 30 ~ 150 DEG C, stirring velocity is 50 ~ 400r/min;
2) 30 ~ 150 DEG C, with 1) in the amount of added dianhydride be benchmark, add diamines and end-capping reagent by a certain percentage, wherein end-capping reagent is the acid anhydrides or the aniline that contain a unsaturated link(age), passes into nitrogen to 0.5 ~ 2.0MPa simultaneously, continues stirring, constant temperature 0.5 ~ 2h at such a temperature;
3) step 2) terminate after, be warming up to 135 ~ 180 DEG C with the heat-up rate of 1 ~ 5 DEG C/min, and with identical speed continue stir, constant temperature 0.5 ~ 2h;
4) step 3) terminate after, be warming up to 180 ~ 250 DEG C with the heat-up rate of 1 ~ 5 DEG C/min, and with identical speed continue stir, constant temperature 0.5 ~ 2h;
5) step 4) terminate after, cooling, is separated gained polyimide/water mixture, washs, dry, obtains Thermocurable polyimide product.
Further, in step 1) in, the particle diameter of dianhydride, diamines is 5 ~ 200 μm.
Further, when the end-capping reagent added is anhydrides material, dianhydride and diamines mol ratio are 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 added is amine substance, diamines and dianhydride mol ratio are 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 anhydride of 4,4 ＇-tetracarboxylic benzophenone dianhydride or 4,4 ＇-oxygen;
Further, described diamines is selected from any one of 3,4-diaminodiphenyl oxide or 4,4-diaminodiphenyl oxide or diaminodiphenylmethane or mphenylenediamine or Ursol D.
Further, described acid anhydrides containing a unsaturated link(age) or aniline end-capping reagent are selected from any one in methylnadic anhydride, inner methylidyne tetrahydric phthalic anhydride, maleic anhydride, allyl group norborneol acid anhydrides or 3-vinyl aniline, 3-acetylenylaniline.
Further, described catalyzer be selected from Tetrabutyl amonium bromide or tetrabutylammonium chloride or benzyltriethylammoinium chloride or tri-n-octyl methyl ammonium chloride any one.
Further, described in step 5), methyl alcohol is adopted to wash.
Principle of work of the present invention: make reaction medium with water, synthesizes Thermocurable polyimide by dianhydride and diamines in 30 ~ 250 DEG C of temperature ranges.The effect of catalyzer improves polyreaction productive rate; By changing end-capping reagent controlling of quality molecular weight, and being cross-linked at curing temperatures by the unsaturated link(age) in end-capping reagent, forming reticulated structure, obtaining the Thermocurable polyimide of different performance.
The invention has the advantages that: 1. technique is simple, and be easy to industrialization, 2. cost is low, 3. pollution-free, and 4. the variable range of product performance is wide, and controllability is good.What is more important, this technology is very easy to realize large-scale industrial and produces.
embodiment:
embodiment 1
At 50 DEG C, by 155.1g4, be placed in the reactor of 5L in the two Tetra hydro Phthalic anhydride of 4 ＇-oxygen, 1.2g Tetrabutyl amonium bromide catalyzer, 1500ml water, pass into nitrogen to 2.0MPa, 100 DEG C are warming up to the heat-up rate of 2 DEG C/min, and with the stirring velocity constant temperature 2h of 400r/min.Then lower the temperature release, add 200.2g4,4-diaminodiphenyl oxide and 178.2g methylnadic anhydride, pass into nitrogen to 1.5MPa, then keep stirring velocity constant, be warming up to 145 DEG C, 210 DEG C respectively and each constant temperature 1h with the heat-up rate of 2 DEG C/min.The mixture of gained polyimide/water is carried out vacuumize separation, methanol wash column three times, again 120 DEG C of dry 2h, obtain the powder Thermocurable polyimide product of 478g beige, this Thermocurable polyimide is through completing solidification at 250 DEG C, obtain its second-order transition temperature of test sample 279 DEG C, shock strength 142MPa.
embodiment 2
At 50 DEG C, by 147.1g3,3 ＇, 4, the reactor of 5L is placed in 4 ＇-bibenzene tetracarboxylic dianhydride, 1.2g benzyltriethylammoinium chloride catalyzer and 2000ml water, directly pass into nitrogen to 2.0MPa, be warming up to 130 DEG C with the heat-up rate of 2 DEG C/min, and with the stirring velocity constant temperature 1h of 400r/min.Then be cooled to 60 DEG C of releases, add 148.7g diaminodiphenylmethane and 49g maleic anhydride, pass into nitrogen to 2.0MPa, then at the uniform velocity stir 1.0h.Then 150 DEG C, 210 DEG C are warming up to respectively and each constant temperature 1.5h with the heat-up rate of 2.5 DEG C/min.The mixture of gained polyimide/water is carried out vacuumize separation, methanol wash column three times, again 120 DEG C of dry 2h, obtain the powder Thermocurable polyimide of 312g yellow, this Thermocurable polyimide and equimolar diallyl bisphenol (DBA) 154.2g are 60
oin C oil bath, stirring and dissolving is to homogeneous, transparent solution, pours rapidly preheated mould into, puts into curing oven (program curing: 160
oc2h+185
oc2h+200
oc2h).Solidified sample second-order transition temperature is 266 DEG C, shock strength 148MPa.
embodiment 3
At 50 DEG C, by 161g3,3 ＇, 4, the reactor of 5L is placed in 4 ＇-tetracarboxylic benzophenone dianhydride, 1.5g benzyltriethylammoinium chloride catalyzer and 1500ml water, directly pass into nitrogen to 1.5MPa, be warming up to 140 DEG C with the heat-up rate of 2 DEG C/min, and with the stirring velocity constant temperature 2h of 400r/min.Then be cooled to 90 DEG C of releases, add 27g mphenylenediamine and 58.5g3-acetylenylaniline, pass into nitrogen to 1.5MPa, then at the uniform velocity stir 0.5h.Then 130 DEG C, 180 DEG C are warming up to respectively and each constant temperature 1.5h with the heat-up rate of 2.5 DEG C/min.Carried out by the mixture of gained polyimide/water vacuumizing separation, methanol wash column three times, again 120 DEG C of dry 2h, obtain the khaki powder Thermocurable polyimide of 218g, this Thermocurable polyimide, through completing solidification at 180-330 DEG C, obtains test sample.Its second-order transition temperature is 268 DEG C, shock strength 145MPa.
embodiment 4
At 50 DEG C, by 147.1g3,3 ＇, be placed in the reactor of 5L in 4,4 ＇-bibenzene tetracarboxylic dianhydride, 1.0g tetrabutylammonium chloride catalyzer, 1500ml water, pass into nitrogen to 1.5MPa, 120 DEG C are warming up to the heat-up rate of 2 DEG C/min, and with the stirring velocity constant temperature 2h of 400r/min.Then lower the temperature release, add 160g3,4-diaminodiphenyl oxide and 115g allyl group norborneol acid anhydrides, pass into nitrogen to 1.5MPa, then keep stirring velocity constant, be warming up to 145 DEG C, 210 DEG C respectively and each constant temperature 1h with the heat-up rate of 2 DEG C/min.The mixture of gained polyimide/water is carried out vacuumize separation, methanol wash column three times, again 120 DEG C of dry 2h, obtain the powder Thermocurable polyimide product of 388g beige, this Thermocurable polyimide is through completing solidification at 250 DEG C, obtain its second-order transition temperature of test sample 283 DEG C, shock strength 152MPa.
Claims (2)
1. a method for performing aqueous synthesis of thermosetting polyimide, is characterized in that comprising the following steps:
1) take dianhydride respectively, catalyzer is added to the water, dianhydride and catalyst quality are 1:30 ~ 1:50 than the mass ratio for 2000:1 ~ 120:1, dianhydride and water, pass into nitrogen to 0.5 ~ 2.0MPa simultaneously, and constant temperature stirs 0.5 ~ 3h under the condition of 30 ~ 150 DEG C, stirring velocity is 50 ~ 400r/min; Described dianhydride is selected from 3,3 ', and 4,4 '-bibenzene tetracarboxylic dianhydride or pyromellitic acid anhydride or 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydride or 4, any one in the two Tetra hydro Phthalic anhydride of 4 '-oxygen; Described catalyzer be selected from Tetrabutyl amonium bromide or tetrabutylammonium chloride or benzyltriethylammoinium chloride or tri-n-octyl methyl ammonium chloride any one;
2) 30 ~ 150 DEG C, with 1) in the amount of added dianhydride be benchmark, add diamines and end-capping reagent by a certain percentage, wherein end-capping reagent is containing the acid anhydrides of a unsaturated link(age) or aniline, above-mentioned containing the acid anhydrides of a unsaturated link(age) or the end-capping reagent of aniline be selected from methylnadic anhydride or inner methylidyne tetrahydric phthalic anhydride or maleic anhydride or allyl group norborneol acid anhydrides or 3-vinyl aniline or 3-acetylenylaniline any one; Pass into nitrogen to 0.5 ~ 2.0MPa simultaneously, continue stirring, constant temperature 0.5 ~ 2h at such a temperature; When the end-capping reagent added is anhydrides material, dianhydride and diamines mol ratio are the mol ratio of 1:2 ~ 1:1.25, dianhydride and end-capping reagent is 1:2 ~ 1:0.5; When the end-capping reagent added is amine substance, diamines and dianhydride mol ratio are the mol ratio of 1:2 ~ 1:1.25, diamines and end-capping reagent is 1:2 ~ 1:0.5; Described diamines is selected from 3,4-diaminodiphenyl oxide or 4, any one in 4 '-diaminodiphenyl oxide or diaminodiphenylmethane or mphenylenediamine or Ursol D;
3) step 2) terminate after, be warming up to 135 ~ 180 DEG C with the heat-up rate of 1 ~ 5 DEG C/min, and with identical speed continue stir, constant temperature 0.5 ~ 2h;
4) step 3) terminate after, be warming up to 180 ~ 250 DEG C with the heat-up rate of 1 ~ 5 DEG C/min, and with identical speed continue stir, constant temperature 0.5 ~ 2h;
5) step 4) terminate after, cooling, gained polyimide/water mixture is separated, methanol wash, drying, obtain Thermocurable polyimide product.
2. the method for a kind of performing aqueous synthesis of thermosetting polyimide as claimed in claim 1, is characterized in that: step 1) in the particle diameter of dianhydride be 5 ~ 200 μm, step 2) in the particle diameter of diamines be 5 ~ 200 μm.
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| 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 |
| CN106459411B (en) * | 2014-06-10 | 2021-01-22 | 延世大学校原州产学协力团 | Method for producing 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 |
| CN117487214B (en) * | 2023-09-28 | 2024-11-01 | 住井科技(深圳)有限公司 | Preparation method of polyimide substrate with high light transmittance and high haze |
| 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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| 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 | A kind of thermosetting polyimide matrix resin and its preparation method and application |
| 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 |
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| JP3544788B2 (en) * | 1995-06-28 | 2004-07-21 | 三井化学株式会社 | 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 |
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2011
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 | A kind of thermosetting polyimide matrix resin and its preparation method and application |
| 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 |
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