CN107602857A - The preparation method and application of polyimides - Google Patents
The preparation method and application of polyimides Download PDFInfo
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- CN107602857A CN107602857A CN201710812055.6A CN201710812055A CN107602857A CN 107602857 A CN107602857 A CN 107602857A CN 201710812055 A CN201710812055 A CN 201710812055A CN 107602857 A CN107602857 A CN 107602857A
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- polyimides
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Abstract
The present invention proposes a kind of preparation method and applications of polyimides, preparation method：1) under inert gas shielding; by aromatic diamine monomer 3; 3 ' dimethyl 4; 4 ' two amido diphenyl-methanes are dissolved in polar non-solute; obtain aromatic diamine monomer solution; then dianhydride is added portionwise into solution, is reacted in 20 DEG C~40 DEG C, obtains the polyamic acid solution with viscosity；2) chemical imidization reagent is added into the polyamic acid solution of step 1) to be reacted to obtain polyimide solution；The chemical imidization reagent includes dehydrating agent and catalyst.Using polyimides will be obtained as base material, organic solvent-resistant NF membrane is prepared using the method for interfacial polymerization.The polyimides that this method is prepared has the advantages of stability is good, good mechanical property and dissolubility are excellent.
Description
Technical field
The invention belongs to resin technology field, and in particular to a kind of preparation method and application of polyimides.
Background technology
From the Dupont companies invention aromatic polyimide class compound in the nineteen fifty-five U.S. till now, have been developed for
Many kinds have various different structure and the polyimide film and its product of performance.Because polyimides has excellent machine
The advantages of tool performance, electrical property, radiation resistance and heat resistance etc. are unique, thus in Aero-Space, electronics, automobile, communication
Application etc. industry is more and more extensive.Correspondingly, the research also increasingly deeply exhibition on polyimide material and preparation method thereof
Open.
In recent years, the resistance to elevated temperatures to polyimide resin based composites and moulded manufacturability have substantial amounts of research
Report.In general, polyimide resin can be divided into thermoplasticity and the major class of thermosetting two, though wherein thermoplastic polyimide resin
So there is good toughness, but there is melt viscosity is high, poor fluidity, it is difficult to carbon fiber is compound prepares carbon fibre
The shortcomings that dimension/composite polyimide material, although and thermoset polyimide resin glues with higher resistance to elevated temperatures, melt
Spend low, good fluidity, be easy to and carbon fiber is compound prepares carbon fiber/polyamide imines composite, but there is toughness
The shortcomings that poor.
Common polyimides (PI) is due to the knot such as strand regularity is good, rigidity is big, interchain interaction power is strong
Structure feature and infusibility indissoluble, machine-shaping is difficult, using being restricted.Therefore studying a kind of polyimides had both kept PI intrinsic
While heat resistance and other good characteristics, reducing the rigidity of PI materials and increasing its solvability in organic solvent is
The emphasis and focus of industrialization production research.The molecular weight of polyimide prepolymer polyamic acid and polyimides chemical imidization
Program has a great impact to polyimides performance.
The content of the invention
The present invention proposes a kind of preparation method of polyimides, the polyimides that this method is prepared have stability it is good,
The advantages of good mechanical property and excellent dissolubility.
The technical proposal of the invention is realized in this way：
A kind of preparation method of polyimides, comprises the following steps：
1) it is under inert gas shielding, aromatic diamine monomer 3,3 '-dimethyl -4,4 '-two amido diphenyl-methanes are molten
In polar non-solute, obtain aromatic diamine monomer solution, dianhydride be then added portionwise into solution, in -20 DEG C~
40 DEG C are reacted, and obtain the polyamic acid solution with viscosity；
2) chemical imidization reagent is added into the polyamic acid solution of step 1) to be reacted to obtain polyimide solution；
The chemical imidization reagent includes dehydrating agent and catalyst.
Preferably, the solid content of the aromatic diamine monomer solution is 5%~20%.
Preferably, the aromatic diamine monomer and the mol ratio of the dianhydride are 1:0.95~1:1.03.
Preferably, the reaction time of the step 1) is 1~16h.
Preferably, the dianhydride be selected from 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-BPDA, 3,
One or several kinds in 3 ', 4,4 '-two methyl phenyl ethers anisole tetracarboxylic dianhydrides, pyromellitic acid dianhydride.
Preferably, the polar aprotic solvent is selected from DMF, N- vinylpyrrolidones and diformazan
One or more in yl acetamide.
Preferably, one or more of the dehydrating agent in acetic anhydride and propionic andydride, the catalyst are selected from pyrrole
One or more in pyridine, picoline and triethylamine.
Preferably, in addition to by the polyimide solution of step 2) gathered after ethanol water sedimentation, washing, vacuum drying
Acid imide solid.
It is a further object to provide a kind of application of polyimides, using the preparation side of above-mentioned polyimides
Method obtains polyimides as base material, and organic solvent-resistant NF membrane is prepared using the method for interfacial polymerization.
The reaction equation of the preparation method of the present invention is as follows：
Beneficial effects of the present invention：
The stiff chain structure of polyimides is the main reason for influenceing polyimides solubility property.Polyimides main chain introduces
The big side base such as the tert-butyl group, phenyl ring or trifluoromethyl can significantly improve its dissolubility.The introducing of big side base makes molecule interchain
Distance increase, inter-chain action power are reduced, and strand is distorted in itself, and three-dimensional asymmetric state is presented in whole molecule, so that poly-
Imido dissolubility improves.The present invention introduces first using method the simplest, economic on the phenyl ring of diamine monomer
Base, greatly improve the dissolubility of polyimides.
Embodiment
Embodiment 1
Under inert gas shielding and temperature is at -10 DEG C~10 DEG C, by aromatic diamine monomer 3,3 '-dimethyl -4,
4 '-two amido diphenyl-methanes are dissolved in a certain amount of DMF, and it is 10% to control monomer solid content, treats that diamines is complete
After fully dissolved, a certain amount of 3,3 ', 4 are weighed, 4 '-benzophenone tetracarboxylic dianhydride, diamines and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride rubs
You are than being 1:1.01, at 5 DEG C of controlling reaction temperature, 10~13h is reacted, then adds a certain amount of chemical imidization reagent acetic acid
Acid anhydride/pyridine, continue stirring reaction and obtain polyimide solution afterwards for a period of time, after ethanol water sedimentation, washing, vacuum drying
To polyimide solids.
After testing, its weight average molecular weight of polyimides Mw that the present embodiment obtains is 3*106, average chain spacing 0.54nm；
Temperature when thermally decomposing 10% is 500 DEG C；275 DEG C of glass transition temperature；Elongation rate of tensile failure 5%, tensile strength 70.66Mpa；
It is soluble in the organic solvent solvent such as NMP, DMF, chloroform.
Embodiment 2
Under inert gas shielding and temperature is at 5 DEG C~10 DEG C, by aromatic diamine monomer 3,3 '-dimethyl -4,4 ' -
Two amido diphenyl-methanes are dissolved in a certain amount of DMF, and it is 6% to control monomer solid content, treats that diamines is completely molten
Xie Hou, weighs a certain amount of 3,3 ', 4,4 '-two methyl phenyl ethers anisole tetracarboxylic dianhydrides, and diamines and dianhydride mol ratio are 1:0.99, control reaction temperature
At 5 DEG C of degree, 10~13h is reacted.A certain amount of chemical imidization reagent acetic anhydride/picoline is added, continues stirring reaction one
Polyimide solution is obtained after the section time, polyimide solids are obtained after ethanol water sedimentation, washing, vacuum drying.
After testing, its weight average molecular weight of polyimides Mw that the present embodiment obtains is 3.5*106, average chain spacing
0.56nm；Temperature when thermally decomposing 10% is 510 DEG C；290 DEG C of glass transition temperature；Elongation rate of tensile failure 5%, tensile strength
75.6Mpa；It is soluble in the organic solvent solvent such as NMP, DMF, chloroform.
Embodiment 3
The preparation of composite nanometer filtering film：
1) the polyimide solids 10g for taking above-described embodiment 1 to prepare, is dissolved in 85ml polar aprotic solvent at room temperature,
It is uniformly dissolved, after 300 mesh steel wire net filtrations, vacuum outgas bubble is standby.It is dustless, 25 DEG C, under humidity 50~70%, will be above-mentioned
Casting solution is coated on PET non-woven fabrics, and wet-film thickness 250um, inversion of phases film forming is stand-by in water or ethanol, obtains polyimides
Basement membrane.
2) polyimide base film obtained above is immersed in the water remained in alcohol in a period of time exchange of solvent removal film
Point, then it is immersed in certain density diamines/alcoholic solvent and is crosslinked a period of time, the film after crosslinking is stored in alcoholic solvent and prevented
Fenestra, which collapses to be ready to use in, prepares PA/PI composite nanometer filtering films.
3) step 2) is obtained into film and is immersed in 2min in 2% piperazine/aqueous solution, film remained on surface is thoroughly dried up with air knife
Amine aqueous solution, subsequently enter 1min in 1% TMC/ hexane solutions, drying immediately be put into 40 DEG C of -60 DEG C of baking ovens continue it is anti-
4-10min is answered, the composite nanometer filtering film prepared is stored in stand-by in 4 DEG C of deionized water.
Application examples 1：With PEG200-2000/ water separation systems, operating pressure 0.7MPa, 25 DEG C of operation temperature, measure compound
The molecular cut off (MWCO) of film is 400, water flux 60kg/m2h。
Application examples 2：Using Coomassie brilliant blue G (Mn=800g/mol)/methanol as separation system, operating pressure 0.7MPa, behaviour
Make 25 DEG C of temperature, measure Coomassie brilliant blue G rejections 100%, solvent flux 40kg/m2h.Follow-on test 24h, membrane separating property
It is basically unchanged.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.
Claims (9)
1. a kind of preparation method of polyimides, it is characterised in that comprise the following steps：
1) under inert gas shielding, by aromatic diamine monomer 3,3 '-dimethyl -4,4 '-two amido diphenyl-methanes are dissolved in pole
In property aprotic solvent, aromatic diamine monomer solution is obtained, dianhydride is then added portionwise into solution, in -20 DEG C~40 DEG C
Reacted, obtain the polyamic acid solution with viscosity；
2) chemical imidization reagent is added into the polyamic acid solution of step 1) to be reacted to obtain polyimide solution；It is described
Chemical imidization reagent includes dehydrating agent and catalyst.
2. the preparation method of polyimides according to claim 1, it is characterised in that the aromatic diamine monomer solution
Solid content be 5%~20%.
3. the preparation method of polyimides according to claim 2, it is characterised in that the aromatic diamine monomer and institute
The mol ratio for stating dianhydride is 1:0.95~1:1.03.
4. the preparation method of polyimides according to claim 3, it is characterised in that the reaction time of the step 1) is
1~16h.
5. the preparation method of polyimides according to claim 1, it is characterised in that the dianhydride be selected from 3,3 ', 4,4 '-
Benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-BPDA, 3,3 ', 4,4 '-two methyl phenyl ethers anisole tetracarboxylic dianhydrides, pyromellitic acid dianhydride
In one or several kinds.
6. the preparation method of polyimides according to claim 1, it is characterised in that the polar aprotic solvent choosing
From DMF, N- vinylpyrrolidones and the one or more in dimethyl acetamide.
7. the preparation method of polyimides according to claim 1, it is characterised in that the dehydrating agent be selected from acetic anhydride with
One or more in propionic andydride, one or more of the catalyst in pyridine, picoline and triethylamine.
8. the preparation method of the polyimides according to claim 1 to 7 any one, it is characterised in that also including will step
Rapid polyimide solution 2) obtains polyimide solids after ethanol water sedimentation, washing, vacuum drying.
9. a kind of application of polyimides, it is characterised in that using the polyimides as described in claim 1 to 8 any one
Preparation method obtain polyimides as base material, organic solvent-resistant NF membrane is prepared using the method for interfacial polymerization.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108753244A (en) * | 2018-06-27 | 2018-11-06 | 中国地质大学（北京） | A kind of highly filled polyimide coating glue and its preparation method and application |
| CN109337101A (en) * | 2018-08-06 | 2019-02-15 | 安徽国风塑业股份有限公司 | A kind of preparation method of Kapton |
| CN109608648A (en) * | 2018-12-06 | 2019-04-12 | 太原理工大学 | A kind of polyimide material and preparation method thereof with temperature response performance |
| CN109679096A (en) * | 2018-12-20 | 2019-04-26 | 中国石油大学(华东) | A kind of novel hot imidization method prepares the application of PI and Ultra filtration membrane field |
| CN110433672A (en) * | 2018-05-03 | 2019-11-12 | 李保军 | A kind of big steric hindrance polyimide gas separating film of non-co-planar and preparation method thereof |
| CN110713598A (en) * | 2019-11-22 | 2020-01-21 | 哈尔滨工业大学 | Preparation method of soluble low-temperature imidized polyimide |
| CN113019136A (en) * | 2021-03-09 | 2021-06-25 | 华中科技大学 | Polar aprotic organic solvent resistant polyimide separation membrane, preparation and application |
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| CN101338217A (en) * | 2007-07-04 | 2009-01-07 | 中国石油天然气股份有限公司 | Method for manufacturing composite membrane for gasoline desulfurization |
| CN103068476A (en) * | 2010-07-19 | 2013-04-24 | 帝国创新有限公司 | Solvent resistant polyamide nanofiltration membranes |
| CN105566907A (en) * | 2016-03-22 | 2016-05-11 | 天津工业大学 | Polyimide nanofiltration membrane prepared on basis of synergic imidization and method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110433672A (en) * | 2018-05-03 | 2019-11-12 | 李保军 | A kind of big steric hindrance polyimide gas separating film of non-co-planar and preparation method thereof |
| CN110433672B (en) * | 2018-05-03 | 2021-11-19 | 李保军 | Non-coplanar polyimide gas separation membrane with large steric hindrance and preparation method thereof |
| CN108753244A (en) * | 2018-06-27 | 2018-11-06 | 中国地质大学（北京） | A kind of highly filled polyimide coating glue and its preparation method and application |
| CN109337101A (en) * | 2018-08-06 | 2019-02-15 | 安徽国风塑业股份有限公司 | A kind of preparation method of Kapton |
| CN109608648A (en) * | 2018-12-06 | 2019-04-12 | 太原理工大学 | A kind of polyimide material and preparation method thereof with temperature response performance |
| CN109679096A (en) * | 2018-12-20 | 2019-04-26 | 中国石油大学(华东) | A kind of novel hot imidization method prepares the application of PI and Ultra filtration membrane field |
| CN110713598A (en) * | 2019-11-22 | 2020-01-21 | 哈尔滨工业大学 | Preparation method of soluble low-temperature imidized polyimide |
| CN113019136A (en) * | 2021-03-09 | 2021-06-25 | 华中科技大学 | Polar aprotic organic solvent resistant polyimide separation membrane, preparation and application |
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Application publication date: 20180119 |