CN109679096A - A kind of novel hot imidization method prepares the application of PI and Ultra filtration membrane field - Google Patents
A kind of novel hot imidization method prepares the application of PI and Ultra filtration membrane field Download PDFInfo
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- CN109679096A CN109679096A CN201811560274.0A CN201811560274A CN109679096A CN 109679096 A CN109679096 A CN 109679096A CN 201811560274 A CN201811560274 A CN 201811560274A CN 109679096 A CN109679096 A CN 109679096A
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- Prior art keywords
- hot imidization
- dmmda
- btda
- solution
- imidization method
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2340/00—Filter material
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention utilizes 3,3 '-dimethyl -4,4 '-diaminodiphenylmethane (DMMDA) and 3,3 ', the low temperature poly condensation of 4,4 '-benzophenone tetracid dianhydrides (BTDA) prepares polyamic acid solution, and polyamic acid solution is directly heated and carries out hot imidization reaction, polyimide material is prepared, and then ultrafiltration membrane is prepared into using inversion of phases.Compared to chemical imidization method, hot imidization method greatly reduces the introducing of chemical reagent, simplifies filming technology, opens new approaches and new method for the preparation of polyimides.
Description
Technical field
The present invention relates to the new methods that a kind of novel hot imidization prepares polyimides, suitable for polyimides ultrafiltration membrane
Production.
Background technique
Polyimides (PI) refers to a kind of producing high-molecular platform object in molecular backbone containing imide.Polyamides is sub- in recent years
Amine is increasingly valued by people with its excellent mechanical performance, electrical property, radiation resistance and heat resistance, it is in aviation
Space flight, electrical, communication and automobile and other industries are widely used.
Imidizate is a committed step for preparing polyimides, and the height of degree of imidisation directly influences polyamides
The performance of imines material.Imidization is roughly divided into chemical imidization and two kinds of hot imidization.Chemical imidization method is in polyamide
Imidizing agent is added in acid solution, polyamic acid cyclodehydration is made to form polyimides.Traditional hot imidization method is will to gather
Amic acid coating film forming, then heating makes its imidization paragraph by paragraph by the polyamide acid film progress of preparation.Chemical imidization method introduces sub-
Amination reagent needs that dissolution is precipitated repeatedly during preparing film, causes a large amount of wastes of solvent；Traditional hot imidization method adds
The hot time is longer, and to temperature requirement height.This patent studies the novel hot imidization method of one kind and prepares polyimide material,
And it prepares polyimides ultrafiltration membrane and carries out separating property test.
Summary of the invention
The object of the invention is to study a kind of method that novel hot imidization prepares polyimides, and prepare polyimides
Ultrafiltration membrane is used for separation field.
The present invention specifically adopts the following technical scheme that
A kind of novel hot imidization method prepares polyimide material, it is characterised in that: using DMMDA, BTDA as monomer
During synthesis of polyimides, using by the method for the direct hot imidization of polyamic acid solution, it is molten that polyimides is prepared
Liquid directly coats film forming.Its step are as follows:
In nitrogen atmosphere, DMMDA is dissolved in polar aprotic solvent, BTDA is added into solution, BTDA's adds
Enter the equal molar quantities that amount is DMMDA, solution is purged condition in nitrogen up to polyamic acid solution by stirring 12h under ice-water bath
Lower 160~180 DEG C are heated to reflux 2~4h, obtain polyimide solution, are cooled to room temperature.At 10~30 DEG C, by above-mentioned polyamides
Imide liquor is coated on the porous bottom supporter of non-woven fabrics, and freezing film in coagulating bath is immersed in the control volatilization time 10~150 seconds
Polyimides ultrafiltration membrane is obtained, coagulating bath is water.Obtained polyimides ultrafiltration membrane saves in deionized water.
Diamines is 3,3 '-dimethyl -4, and 4 '-diaminodiphenylmethane (DMMDA) are the aromatic diamines having the following structure
Monomer:
Dianhydride is 3,3 ', 4,4 '-benzophenone tetracid dianhydrides (BTDA), is the aromatic dianhydride monomer having the following structure:
Polar aprotic solvent is N-Methyl pyrrolidone (NMP).
Detailed description of the invention
Fig. 1 is the infrared spectrogram of polyimide material in the embodiment of the present invention.
In figure: the polyimides infrared spectrum of 2h and 4h is reacted at 180 DEG C of hot imidization law article part respectively, it can be in figure
Find out: the absorption peak at 1720cm-1 and 1780cm-1 corresponds respectively in imide group the symmetrical stretching vibration of C=O and not
Symmetrical stretching vibration；And 1380cm-1 and 725cm-1 are attributed to the stretching vibration of C-N and the deformation vibration of imide ring respectively.
This four peaks are the characteristic peaks of PI.Illustrate that this method synthesizes successfully.
Fig. 2 is the separating property figure of polyimides ultrafiltration membrane in the embodiment of the present invention.
In figure: reacting the poly- second of the ultrafiltration membrane of the polyimides preparation of 2h and 4h at 180 DEG C of hot imidization law article part respectively
The retention of glycol (PEG) and flux pattern.It can be seen that the polyimides of reaction time 2h retains the PEG rejection of 500,000 molecular weight
It is 86.08%；The PEG rejection for finding out that the polyimides of reaction time 4h retains 500,000 molecular weight is 83.95%, has retention
Effect.
Specific embodiment
The present invention has the advantage that
1, novel hot imidization method greatly reduces the dosage of solvent, shortens the reaction time, and can successfully make
Standby polyimide material out.
2, the ultrafiltration membrane prepared has excellent separating property.
Embodiment 1:
In nitrogen atmosphere, DMMDA is dissolved in NMP, BTDA is added into solution, the additional amount of BTDA is DMMDA
Equal molar quantities, stirring 12h heats back solution for 180 DEG C up to polyamic acid solution under the conditions of nitrogen purges under ice-water bath
2h is flowed, polyimide solution is obtained, is cooled to room temperature.At 20 DEG C, it is porous that above-mentioned polyimide solution is coated on non-woven fabrics
It on the supporter of bottom, volatilizees the time 10 seconds, immerses freezing film in coagulating bath and obtain polyimides ultrafiltration membrane, coagulating bath is water.?
The polyimides ultrafiltration membrane arrived saves in deionized water.
The retention for testing the polyethylene glycol (PEG) of different molecular weight, wherein the PEG rejection of 500,000 molecular weight is
86.08%.
Embodiment 2:
In nitrogen atmosphere, DMMDA is dissolved in NMP, BTDA is added into solution, the additional amount of BTDA is DMMDA
Equal molar quantities, stirring 12h heats back solution for 180 DEG C up to polyamic acid solution under the conditions of nitrogen purges under ice-water bath
4h is flowed, polyimide solution is obtained, is cooled to room temperature.At 10 DEG C, it is porous that above-mentioned polyimide solution is coated on non-woven fabrics
It on the supporter of bottom, volatilizees the time 10 seconds, immerses freezing film in coagulating bath and obtain polyimides ultrafiltration membrane, coagulating bath is water.?
The polyimides ultrafiltration membrane arrived saves in deionized water.
The retention for testing the polyethylene glycol (PEG) of different molecular weight, wherein the PEG rejection of 500,000 molecular weight is
83.95%.
Embodiment 3:
In nitrogen atmosphere, DMMDA is dissolved in NMP, BTDA is added into solution, the additional amount of BTDA is DMMDA
Equal molar quantities, stirring 12h heats back solution for 160 DEG C up to polyamic acid solution under the conditions of nitrogen purges under ice-water bath
2h is flowed, polyimide solution is obtained, is cooled to room temperature.At 20 DEG C, it is porous that above-mentioned polyimide solution is coated on non-woven fabrics
It on the supporter of bottom, volatilizees the time 20 seconds, immerses freezing film in coagulating bath and obtain polyimides ultrafiltration membrane, coagulating bath is water.?
The polyimides ultrafiltration membrane arrived saves in deionized water.
Polymer molecular weight is low, can not form film.
Embodiment 4:
In nitrogen atmosphere, DMMDA is dissolved in NMP, BTDA is added into solution, the additional amount of BTDA is DMMDA
Equal molar quantities, stirring 12h heats back solution for 160 DEG C up to polyamic acid solution under the conditions of nitrogen purges under ice-water bath
4h is flowed, polyimide solution is obtained, is cooled to room temperature.At 10 DEG C, it is porous that above-mentioned polyimide solution is coated on non-woven fabrics
It on the supporter of bottom, volatilizees the time 10 seconds, immerses freezing film in coagulating bath and obtain polyimides ultrafiltration membrane, coagulating bath is water.?
The polyimides ultrafiltration membrane arrived saves in deionized water.
Polymer molecular weight is low, can not form film.
Claims (5)
1. a kind of novel hot imidization method prepares polyimide material, it is characterised in that: closed by monomer of DMMDA, BTDA
During at polyimides, using by the method for the direct hot imidization of polyamic acid solution, polyimide solution is prepared
Directly coating film forming.Its step are as follows: in nitrogen atmosphere, DMMDA being dissolved in polar aprotic solvent, is added into solution
Enter BTDA, the additional amount of BTDA is the equal molar quantities of DMMDA, and 12h is stirred under ice-water bath up to polyamic acid solution, by solution
2~4h is heated to reflux for 160~180 DEG C under the conditions of nitrogen purging, is obtained polyimide solution, is cooled to room temperature.10~30
At DEG C, above-mentioned polyimide solution is coated on the porous bottom supporter of non-woven fabrics, the control volatilization time 10~150 seconds is immersed
Freezing film obtains polyimides ultrafiltration membrane in coagulating bath, and coagulating bath is water.Obtained polyimides ultrafiltration membrane be stored in from
In sub- water.
2. novel hot imidization method according to claim 1, which is characterized in that diamines is aromatic diamine monomers, such as: 3,
3 '-dimethyl -4,4 '-diaminodiphenylmethane (DMMDA).
3. novel hot imidization method according to claim 1, which is characterized in that dianhydride is aromatic dianhydride monomer, such as: 3,
3 ', 4,4 '-benzophenone tetracid dianhydrides (BTDA).
4. novel hot imidization method according to claim 1, which is characterized in that the molar ratio of DMMDA and both BTDA is
1:1.
5. novel hot imidization method according to claim 1, which is characterized in that polar aprotic solvent is N- methyl pyrrole
Pyrrolidone (NMP).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811560274.0A CN109679096A (en) | 2018-12-20 | 2018-12-20 | A kind of novel hot imidization method prepares the application of PI and Ultra filtration membrane field |
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| CN201811560274.0A CN109679096A (en) | 2018-12-20 | 2018-12-20 | A kind of novel hot imidization method prepares the application of PI and Ultra filtration membrane field |
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| CN109679096A true CN109679096A (en) | 2019-04-26 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3666709A (en) * | 1968-12-14 | 1972-05-30 | Shawa Densen Denran Kk A K A S | Solvent soluble aromatic polymides and production thereof |
| CN1872895A (en) * | 2005-06-03 | 2006-12-06 | 长春人造树脂厂股份有限公司 | Dissoluble polyimide resin, and preparation method |
| CN104151550A (en) * | 2014-08-08 | 2014-11-19 | 上海交通大学 | Soluble polyimide material having short-chain alkyl as side group and preparation method thereof |
| CN107602857A (en) * | 2017-09-11 | 2018-01-19 | 中国石油大学(华东) | The preparation method and application of polyimides |
-
2018
- 2018-12-20 CN CN201811560274.0A patent/CN109679096A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3666709A (en) * | 1968-12-14 | 1972-05-30 | Shawa Densen Denran Kk A K A S | Solvent soluble aromatic polymides and production thereof |
| CN1872895A (en) * | 2005-06-03 | 2006-12-06 | 长春人造树脂厂股份有限公司 | Dissoluble polyimide resin, and preparation method |
| CN104151550A (en) * | 2014-08-08 | 2014-11-19 | 上海交通大学 | Soluble polyimide material having short-chain alkyl as side group and preparation method thereof |
| CN107602857A (en) * | 2017-09-11 | 2018-01-19 | 中国石油大学(华东) | The preparation method and application of polyimides |
Non-Patent Citations (1)
| Title |
|---|
| CHENJIE WEI ET AL.: "One-step fabrication of recyclable polyimide nanofiltration membranes with high selectivity and performance stability by a phase inversion-based process", 《JOURNAL OF MATERIALS SCIENCE》 * |
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Application publication date: 20190426 |