CN115594972B - Method for improving processability of polybenzimidazole resin solution - Google Patents
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- 239000004693 Polybenzimidazole Substances 0.000 title claims abstract description 64
- 229920002480 polybenzimidazole Polymers 0.000 title claims abstract description 64
- 239000011347 resin Substances 0.000 title claims abstract description 40
- 229920005989 resin Polymers 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 34
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- -1 4-naphthyl Chemical group 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000002035 prolonged effect Effects 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KSFAWAYSJUPRED-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetramine Chemical compound NC1=C(N)C(N)=CC(C=2C=CC=CC=2)=C1N KSFAWAYSJUPRED-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a method for improving the processability of a polybenzimidazole resin solution. The method of the invention comprises the following steps: the high molecular weight Polybenzimidazole (PBI) and the low molecular weight PBI polymer are mixed and then dissolved in a polar organic solvent, wherein the intrinsic viscosity of the high molecular weight polybenzimidazole resin ranges from 1.5 dL/g to 3.6dL/g, the intrinsic viscosity of the low molecular weight polybenzimidazole resin ranges from 0.5 dL/g to 1.2dL/g, and the content of the high molecular weight polybenzimidazole resin in the polymer ranges from 5wt% to 50wt%. The method has the advantages that the solid content and the fluidity of the solution are obviously improved, the processability of the PBI solution is greatly improved, the storage time and the gel time of the solution are greatly prolonged, and the PBI solution obtained by the method is used for coating films, so that the uniformity and the consistency of the obtained product are improved on the premise of ensuring certain mechanical properties of the product, the production efficiency is improved, and the production energy consumption is reduced.
Description
Technical Field
The invention relates to a method for improving the processability of polybenzimidazole resin solution, belonging to the technical field of resin materials.
Background
Polybenzimidazole (PBI) is the highest performance engineering plastic in the world, is an amorphous linear heterocyclic polymer with benzimidazole as a repeating unit, and has a wholly aromatic main chain which imparts an extremely high glass transition temperature (tg=425-436 ℃) to PBI, and is excellent in chemical stability and mechanical stability. The polybenzimidazole can be used as a high-temperature structural adhesive, and the adhesive strength to stainless steel and titanium alloy is 960.4N/cm at 537 DEG C 2 The fiber can be used as flame-resistant fabric and ablative material, and has good prospect in aerospace, such as heat-resistant films, diaphragms, reinforced plastics, foam materials and the like. PBI was commercialized by Hoechst Selanis in 1983 to produce fibers and textiles for heat insulating and fire resistant applications. Currently PBI is produced mainly by us PBI Performance Products company.
However, PBI has problems of complex preparation process, difficult dissolution and processing and high price, and seriously affects the application and development of the PBI. Aiming at the key technical problems of PBI dissolution and difficult processing, various technical staff put forward different solutions. For example, flexible ether linkages are introduced into the backbone of the PBI Polymer (International Journal of Hydrogen Energy,2013,38 (15): 6494-6502), hexafluoroisopropyl groups are introduced (Journal of Polymer Science Part A Polymer Chemistry,2010,47 (16): 4064-4073), and highly sterically hindered side groups are introduced (Polymer, 2009,50: 3495-3502). However, the introduction of flexible groups often leads to a decrease in the chemical and thermal stability of the polymer, leading to degradation of the film during use, and the synthesis of new polymers and chemical modification of monomers or polymers also lead to complex processes and prolonged production procedures, leading to an extension of the development cycle. In addition, PBI is a strong polar polymer with strong intermolecular forces, and higher solid content is difficult to obtain in the dissolution process of PBI with higher molecular weight, and as the solid content is increased, the fluidity of the solution is poor, which leads to higher engineering difficulties in the stirring, dissolution, filtration, deaeration and film scraping or spinning processes. In addition, PBI has a strong tendency to gel during storage of the solution, and even because the hydrogen bonding forces between the polymers are too strong, the polymers are precipitated from the solution, and LiCl is usually added to the solution as a cosolvent to increase the solubility or increase the solid content, so that the storage time of the solution is prolonged, but the introduction of too much LiCl may cause defects or unstable performance of the finished product. Whereas if only low molecular weight PBI polymers are used to increase the solids content of the solution and to increase the processability, the resulting film or filament has lower mechanical strength.
Disclosure of Invention
The purpose of the invention is that: aiming at the problems and defects of the existing polybenzimidazole solution in the processing, the solubility of the polybenzimidazole and the flowability of the solution are improved by a method of blending polybenzimidazole resins with different molecular weights.
In order to achieve the above object, the present invention provides a method for improving the processability of a polybenzimidazole resin solution, which comprises blending a high molecular weight polybenzimidazole resin with a low molecular weight polybenzimidazole resin and then dissolving the mixture in a polar organic solvent, wherein the high molecular weight polybenzimidazole resin has an intrinsic viscosity ranging from 1.5 to 3.6dL/g, the low molecular weight polybenzimidazole resin has an intrinsic viscosity ranging from 0.5 to 1.2dL/g, and the high molecular weight polybenzimidazole resin has a weight ratio of 5 to 50wt% in a polymer.
Preferably, the polybenzimidazole resin is: one of poly 2,2'- (1, 4-naphthyl) -5,5' -bibenzimidazole NPBI, poly 2,2'- (m-phenyl) -5,5' -bibenzimidazole mPBI, poly 2,2'- (p-phenyl) -5,5' -bibenzimidazole pPBI, and poly 2,2'- (p-diphenyl ether) -5,5' -bibenzimidazole OPBI.
Preferably, the method of blending is mechanical blending and the method of dissolving is: adding an organic solvent into a reaction kettle, adding the blended polybenzimidazole resin in batches, and then mechanically stirring at 50-80 ℃ for dissolution.
Preferably, the polar organic solvent is one or more of N, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), dimethylsulfoxide (DMSO), and N-methylpyrrolidone (NMP).
Preferably, liCl auxiliary is also added during dissolution, and the addition amount of the LiCl auxiliary is less than or equal to 1wt%.
The invention also provides the polybenzimidazole resin solution obtained by the method for improving the processability of the polybenzimidazole resin solution, and the content of the polymer in the polybenzimidazole resin solution is 10-25 wt%.
The invention also provides a polybenzimidazole resin film which is prepared by adopting the polybenzimidazole resin solution to process the polybenzimidazole resin film.
Compared with the prior art, the invention has the beneficial effects that:
(1) The PBI polymer with high and low molecular weight is mixed and dissolved in the organic solvent, wherein the polymer with low molecular weight can play a role in plasticization, the rotational viscosity of the solution is reduced, the solid content of the whole solution is improved, the production efficiency is improved, and the energy consumption is reduced; the polymer with high molecular weight can provide strong mechanical properties, so that the mechanical strength of the finished product is improved, and the structural stability of the product is ensured; the storage time of the solution obtained by the method is greatly prolonged, and the gel time of the solution or the precipitation time of the polymer is obviously prolonged;
(2) The method of the invention obviously improves the solid content and fluidity of the solution, greatly improves the processability of the PBI solution, greatly prolongs the storage time and the gel time of the solution, and can improve the uniformity and consistency of the obtained product and reduce the production energy consumption on the premise of ensuring certain mechanical property of the product when the PBI solution obtained by the method is used for coating.
Drawings
FIG. 1 is a rotational viscosity test of solution 1;
fig. 2 is a rotational viscosity test of solution 6 a.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Example 1
Synthesis of Poly-2, 2'- (1, 4-naphthyl) -5,5' -bibenzimidazole (NPBI):
adding 1, 4-Naphthalene Dicarboxylic Acid (NDA) and biphenyl tetraamine (DAB) monomers into a three-port bottle according to the mol ratio of 1:1, adding polyphosphoric acid into the three-port bottle to enable the mass fraction of the monomers to be 4wt%, introducing nitrogen to remove oxygen, starting the reaction under the condition of mechanical stirring in a staged heating mode, wherein the highest temperature is 140 ℃, obtaining NPBI with different molecular weights by controlling the reaction time at the highest temperature, heat-sinking the reaction solution in water while the reaction solution is hot, obtaining a filamentous polymer, washing with deionized water and sodium carbonate solution for multiple times, and drying to obtain polymer powder. The high molecular weight NPBI intrinsic viscosity was 2.61dL/g and was designated NPBI-H; the low molecular weight NPBI intrinsic viscosity was 0.93dL/g and was designated NPBI-L.
The high molecular weight NPBI-H and the low molecular weight NPBI-L were dissolved in NMP solvent in different proportions, and the compositions of the solutions are shown in Table 1. Solution 1, solution 3 and solution 6 were scraped onto clean glass plates and dried in an oven at 80℃for 12 hours to give NPBI films designated NPBI-1, NPBI-3 and NPBI-6, respectively.
TABLE 1NPBI solution formulation ratio
Example 2
Synthesis of Poly-2, 2'- (m-phenyl) -5,5' -bibenzoimidazole (mPBI):
adding isophthalic acid (IPA) and biphenyltetramine (DAB) monomers into a three-port bottle in a molar ratio of 1:1, adding polyphosphoric acid into the three-port bottle to enable the mass fraction of the monomers to be 4wt%, introducing nitrogen to remove oxygen, starting the reaction under the condition of mechanical stirring in a staged heating mode, obtaining mPBI with different molecular weights at the highest temperature of 180 ℃ by controlling the reaction time, heat-sinking the reaction solution in water while the reaction solution is hot, obtaining a filamentous polymer, washing the reaction solution with deionized water and sodium carbonate solution for multiple times, and drying to obtain polymer powder. The high molecular weight mPBI has an intrinsic viscosity of 2.45dL/g and is designated mPBI-H; the low molecular weight NPBI has an intrinsic viscosity of 0.89dL/g and is designated mPBI-L.
The high molecular weight mPBI-H and the low molecular weight mPBI-L were dissolved in DMAc solvent in varying proportions and the composition of the solutions is shown in Table 2. Solution 10, solution 12 and solution 15 were scraped onto clean glass plates and dried in an oven at 80℃for 12 hours to give mPBI films designated mPBI-10, mPBI-12 and mPBI-15, respectively.
TABLE 2 mPBI solution formulation
Example 3
Synthetic reference to poly 2,2'- (p-diphenyl ether) -5,5' -bibenzoimidazole (OPBI) (Journal of Membrane Science 586 (2019) 231-239): adding diphenyl ether dicarboxylic acid and biphenyltetramine into an Eton reagent (PPMA) solvent, introducing nitrogen to remove oxygen, gradually heating to 140 ℃, controlling the reaction time at the temperature to obtain OPBI with different molecular weights, cooling the reaction liquid in water to obtain a filamentous polymer, washing the filamentous polymer with deionized water and sodium carbonate solution for multiple times, and drying to obtain polymer powder. The high molecular weight OPBI intrinsic viscosity was 2.52dL/g and was designated OPBI-H; the low molecular weight OPBI has an intrinsic viscosity of 0.85dL/g and is designated OPBI-L.
The high molecular weight OPBI-H and the low molecular weight OPBI-L were dissolved in DMSO solvents in different proportions, and the compositions of the solutions are shown in Table 3. Solution 19, solution 21 and solution 24 were scraped onto clean glass plates and dried in an oven at 80℃for 12 hours to give OPBI films designated OPBI-19, OPBI-21 and OPBI-24, respectively.
TABLE 3 OPBI solution formulation
In example 1, by standing the polymer solution and observing the gel time thereof, as shown in table 1, it was found that the gel time of the solution was significantly prolonged with an increase in the NPBI-L content of low molecular weight, and that an increase in the NPBI-L content was advantageous for increasing the solid content of the solution and for increasing the production efficiency. And the solution gel times of example 2 and example 3 exhibited similar results.
As shown in Table 4, the rotational viscosity of the solution decreased with increasing low molecular weight polymer ratio for the different polymers, indicating a significant improvement in flowability and processability. Furthermore, as shown in FIGS. 1 and 2, the rotational viscosity of the solution 1 and the solution 6a show a large difference in the same solid content, also because the NPBI-L content of the low molecular weight in the solution 6a is as high as 95%, making the rotational viscosity thereof very low.
TABLE 4 kinetic viscosity test of different solutions
Although an increase in the content of the low molecular weight polymer can significantly reduce the rotational viscosity of the solution and improve the processability, an excessively high content causes a decrease in the mechanical properties of the finished film, and as shown in Table 5, when the ratio of the low molecular weight polymer reaches 95%, a significant decrease in the tensile strength of the film occurs, so that the solid content of the solution is increased while the mechanical properties of the product are also considered.
TABLE 5 comparison of mechanical Properties of different films
| Film and method for producing the same | Low molecular weight polymer ratio | Tensile Strength [ MPa ]] |
| NPBI-1 | 50％ | 220 |
| NPBI-3 | 70％ | 211 |
| NPBI-6 | 95％ | 153 |
| mPBI-10 | 50％ | 201 |
| mPBI-12 | 70％ | 189 |
| mPBI-15 | 95％ | 142 |
| OPBI-19 | 50％ | 185 |
| OPBI-21 | 70％ | 181 |
| OPBI-24 | 95％ | 136 |
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to be limiting in any way and in nature, and it should be noted that several modifications and additions may be made to those skilled in the art without departing from the invention, which modifications and additions are also intended to be construed as within the scope of the invention.
Claims (7)
1. A method for improving the processability of a solution of a polybenzimidazole resin, which is characterized in that a polybenzimidazole resin having a high molecular weight is dissolved in a polar organic solvent after being blended with a polybenzimidazole resin having a low molecular weight, wherein the polybenzimidazole resin having a high molecular weight has an intrinsic viscosity in the range of 2.45 to 2.61dL/g, the polybenzimidazole resin having a low molecular weight has an intrinsic viscosity in the range of 0.85 to 0.93dL/g, and the polybenzimidazole resin having a high molecular weight has a weight ratio in the polymer of 5 to 50wt%.
2. The method for improving the processability of a polybenzimidazole resin solution according to claim 1, where the polybenzimidazole resin is: one of poly 2,2'- (1, 4-naphthyl) -5,5' -bibenzimidazole NPBI, poly 2,2'- (m-phenyl) -5,5' -bibenzimidazole mPBI, poly 2,2'- (p-phenyl) -5,5' -bibenzimidazole pPBI, and poly 2,2'- (p-diphenyl ether) -5,5' -bibenzimidazole OPBI.
3. The method for improving the processability of a polybenzimidazole resin solution according to claim 1, where said blending method is mechanical blending and said dissolving method is: adding an organic solvent into a reaction kettle, adding the blended polybenzimidazole resin in batches, and then mechanically stirring at 50-80 ℃ for dissolution.
4. The method for improving the processability of a polybenzimidazole resin solution according to claim 1, where the polar organic solvent is one or more of N, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), dimethylsulfoxide (DMSO) and N-methylpyrrolidone (NMP).
5. The method for improving the processability of a polybenzimidazole resin solution according to claim 1, where LiCl aid is added at the time of dissolution, and the added amount of LiCl aid is 1 wt.% or less.
6. The polybenzimidazole resin solution obtained by the process for improving the processability of polybenzimidazole resin solution according to any one of claims 1 to 4 where the content of polymer in polybenzimidazole resin solution is 10 to 25% by weight.
7. A polybenzimidazole resin film prepared by processing the polybenzimidazole resin solution according to claim 6 into a film.
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| CN1845961A (en) * | 2003-07-09 | 2006-10-11 | 江崎格力高株式会社 | Molded object comprising alpha-1,4-glucans and/or modifications thereof and process for producing the same |
| CN112409612A (en) * | 2020-09-30 | 2021-02-26 | 孙利滨 | Preparation method of high-solid-content low-viscosity polyamic acid solution |
| CN113292722A (en) * | 2020-02-24 | 2021-08-24 | 中国科学院上海有机化学研究所 | Preparation method of polybenzimidazole polymer with high molecular weight and high solubility |
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| CN1845961A (en) * | 2003-07-09 | 2006-10-11 | 江崎格力高株式会社 | Molded object comprising alpha-1,4-glucans and/or modifications thereof and process for producing the same |
| CN113292722A (en) * | 2020-02-24 | 2021-08-24 | 中国科学院上海有机化学研究所 | Preparation method of polybenzimidazole polymer with high molecular weight and high solubility |
| CN112409612A (en) * | 2020-09-30 | 2021-02-26 | 孙利滨 | Preparation method of high-solid-content low-viscosity polyamic acid solution |
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