CN115160565A - Polyimide film material containing sulfonyl structure between imide rings and preparation method thereof - Google Patents

Polyimide film material containing sulfonyl structure between imide rings and preparation method thereof Download PDF

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CN115160565A
CN115160565A CN202210713882.0A CN202210713882A CN115160565A CN 115160565 A CN115160565 A CN 115160565A CN 202210713882 A CN202210713882 A CN 202210713882A CN 115160565 A CN115160565 A CN 115160565A
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polyimide film
film material
preparing
polyimide
monomer
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薛立新
黄菲
罗伶萍
高从堦
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Zhejiang University of Technology ZJUT
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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
    • 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
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • 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
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

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Abstract

The invention discloses a polyimide film material containing sulfuryl structure among imide rings and a preparation method thereof, the film material takes 3,3', 4' -diphenyl sulfone tetracarboxylic dianhydride as dianhydride monomer, and adopts a solution copolycondensation method with diamine monomer to synthesize a flexible transparent polyimide film, and the intermediate product polyamide acid can be dissolved in N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the method for preparing the sulfonyl-containing polyimide has the characteristics of simple synthesis route, mild reaction conditions, few organic solvent usage types, capability of reducing environmental pollution to the maximum extent and the like, and the prepared membrane material has application potential in the fields of gas separation, high transparency, high refractive index material development and the like;

Description

Polyimide film material containing sulfonyl structure between imide rings and preparation method thereof
Technical Field
The invention relates to the technical field of polymer film materials, in particular to a polyimide film material containing a sulfone group structure among imide rings and a preparation method thereof.
Background
Aromatic Polyimide (PI) is an important high molecular material, and the synthesis process is most commonly a two-step method, wherein in the first step, dicarboxylic anhydride and diamine are subjected to polycondensation at a low temperature to obtain polyamic acid, and in the second step, the polyamic acid is cyclized into polyimide by a chemical imidization method or a thermal imidization method. The polyimide has excellent thermal stability, mechanical property and insulating property, and has potential application value in the fields of aerospace, petrochemical industry, microelectronic packaging, solar cells, gas separation and the like.
If introduced into the polyimide skeleton through the anhydride monomer, sulfone groups can form a conjugated rigid structure with a larger range with imide rings on two sides of the polyimide skeleton, so that the stacking density and the free volume of a high molecular chain are effectively influenced, and the key effect on the promotion of the gas permeability and the separation selectivity is achieved. In addition, the introduction of the sulfone group can remarkably improve the transparency of the PI film in the visible light range and keep the inherent heat resistance of the PI film; on the other hand, the method can also be used for developing novel PI with high transparency and high refractive index. However, there is currently very little research and development work on polyimide gas separation membranes containing sulfone groups, and most of the structures reported have sulfone groups derived from diamine monomers, not from anhydride monomers. Therefore, the invention provides a method for preparing a rigid conjugated polyimide polymer and a film containing a sulfone group structure between imide rings by adopting an anhydride monomer with the sulfone group structure.
Disclosure of Invention
The invention aims to provide a polyimide film material containing a sulfone group structure between imide rings and a preparation method thereof.
The technical scheme of the invention is as follows:
a polyimide polymer containing a sulfone group structure between imide rings has a structural general formula as follows:
Figure BDA0003708056460000011
wherein n ranges from 76 to 116;
r represents a diamine residue selected from one or more of the following groups:
Figure BDA0003708056460000012
wherein the dashed lines indicate the joints.
The polyimide film material consists of polyimide polymer with sulfonyl structure between imide rings.
A preparation method of a polyimide film material comprises the following steps:
(1) Monomer drying
Respectively drying raw materials of dianhydride monomer and diamine monomer for later use;
specifically, the dianhydride monomer is dried in a vacuum drying oven at 100 ℃ for 6 hours, and the diamine monomer is dried in a vacuum drying oven at 80 ℃ for 6 hours;
(2) Synthesis of Polyamic acid
Under ice bath and nitrogen protection conditions, dissolving a diamine monomer in an aprotic polar solvent, then adding a dianhydride monomer, and stirring at normal temperature (20-30 ℃) for 12-24 hours to obtain a polyamic acid solution;
the molar ratio of the diamine monomer to the dianhydride monomer is 1-1;
the aprotic polar solvent is selected from one or more of N, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP); the volume mass ratio of the aprotic polar solvent to the diamine monomer is 1-10: 1mL/g;
(3) Preparation of polyimide film
Casting the polyamic acid solution obtained in the step (2) on a cleaned glass plate to form a film, performing thermal imidization reaction by adopting gradient heating, wherein the temperature is increased from 40 ℃ to 250 ℃ for 6 hours, and then naturally cooling to room temperature for demoulding to obtain a polyimide film;
the solid content of the polyamic acid solution is 5-10%; when the film is cast to form a film, the thickness of the film is adjusted to be between 5 and 100 um;
specifically, the thermal imidization is carried out in a vacuum drying oven with the following temperature gradient: 1h at 40 ℃, 1h at 60 ℃, 1h at 100 ℃, 1h at 180 ℃ and 2h at 250 ℃;
(4) Post-treatment
Soaking the polyimide film obtained in the step (3) in methanol, taking out and drying to finish post-treatment;
the soaking time is 24 hours;
the drying is carried out in a vacuum drying oven to remove the organic solvent in the film, and the gradient of the temperature rise for removing the solvent in the vacuum drying oven is as follows: 1h at 80 ℃, 2h at 150 ℃, 2h at 200 ℃ and 1h at 250 ℃;
in the preparation method, the structural formula of the raw material dianhydride monomer is as follows:
Figure BDA0003708056460000021
the raw material diamine monomer is selected from one or more of the following compounds:
Figure BDA0003708056460000022
the polyimide film material can be applied to gas separation.
The invention has the following advantages:
the invention provides a polyimide film material containing a sulfone group structure among imide rings, which is characterized in that 3,3', 4' -diphenyl sulfone tetracarboxylic dianhydride (DSDA) is used as a dianhydride monomer, and the dianhydride monomer and a diamine monomer are synthesized into a flexible transparent polyimide film by adopting a solution copolycondensation method, wherein intermediate polyamic acid can be dissolved in N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP). The method for preparing the sulfonyl-containing polyimide has the characteristics of simple synthetic route, mild reaction conditions, less use of organic solvents, capability of reducing environmental pollution to the greatest extent and the like. The prepared membrane material has application potential in the fields of gas separation, high-transparency and high-refractive index material development and the like.
Drawings
FIG. 1 is an infrared spectrum of a polyimide (DSDA-MDA) prepared in example 1, having an imide ring corresponding to 1372cm -1 (symmetrical stretching vibration peak of C-N in imide Ring), 1714cm -1 (symmetric stretching vibration peak of C = O in imide ring), 1780cm -1 (asymmetric stretching vibration peak of C = O in imide ring), 1322cm -1 And 1147cm -1 (vibrational peaks of sulfone groups).
FIG. 2 is an infrared spectrum of a polyimide (DSDA-ODA) prepared in example 2, which has an imide ring corresponding to 1372cm -1 (symmetrical stretching vibration peak of C-N in imide Ring), 1714cm -1 (symmetrical stretching vibration peak of C = O in imide ring), 1780cm -1 (asymmetric stretching vibration peak of C = O in imide ring), 1322cm -1 And 1147cm -1 (vibrational peaks of sulfone groups).
FIG. 3 is a TGA spectrum of a polyimide (DSDA-ODA) prepared in example 2.
FIG. 4 is a schematic diagram of the synthesis of example 1.
FIG. 5 is a schematic diagram of the synthesis of example 2.
Detailed Description
The invention is further described below by means of specific examples, without the scope of protection of the invention being limited thereto.
Example 1:
a100 ml three-necked round-bottom flask with mechanical stirring, nitrogen inlet and outlet was placed in an ice bath, 0.0115mol of diamine monomer MDA was dissolved in 18ml of DMAc, after dissolution was complete, 0.0115mol of DSDA and a further 18ml of DMAc were added, and the solution was stirred at room temperature for 24h to form a viscous polyamic acid solution.
Taking the obtained polyamic acid solution, adding DMAC (dimethylacetamide) to dilute the solution until the solid content is 8%, casting the solution on a clean glass plate to form a film, and controlling the thickness of the poured polyamic acid solution to be about 30 mu m. And putting the glass plate paved with the polyamic acid solution into an oven, and performing thermal imidization reaction by gradient heating at the temperature of 40 ℃ for 1h,60 ℃ for 1h,100 ℃ for 1h,180 ℃ for 1h and 250 ℃ for 2h. Naturally cooling to room temperature, soaking in deionized water to remove the membrane, soaking in methanol solution for 24h, and maintaining at 250 deg.C in vacuum drying oven for a while to remove DMAc from the membrane.
Measuring the free volume fraction and gas separation performance of the film, CO 2 The permeability was 5.4Barrer.
Example 2:
a100 ml three-necked round-bottom flask with mechanical stirring, nitrogen inlet and outlet was placed in an ice bath, 0.0191mol of diamine monomer ODA was dissolved in 30ml of DMAc, after completion of the dissolution, 0.0191mol of DSDA and a further 30ml of DMAc were added, and the solution was stirred at room temperature for 24h to form a viscous polyamic acid solution.
Taking the obtained polyamic acid solution, adding DMAC (dimethylacetamide) to dilute the solution until the solid content is 8%, casting the solution on a clean glass plate to form a film, and controlling the thickness of the poured polyamic acid solution to be about 30 mu m. And putting the glass plate paved with the polyamic acid solution into an oven, and performing thermal imidization reaction by gradient heating at the temperature of 40 ℃ for 1h,60 ℃ for 1h,100 ℃ for 1h,180 ℃ for 1h and 250 ℃ for 2h. Naturally cooling to room temperature, soaking in deionized water to remove the membrane, soaking the membrane in methanol solution for 24h, and maintaining at 250 ℃ in a vacuum drying oven for a period of time to remove DMAc in the membrane.
The membranes were tested for free volume fraction and gas separation performance and the detailed data are shown in tables 1 and 2.
Table 1 density and free volume fraction of films prepared in examples 1-2
Figure BDA0003708056460000041
Table 2 gas separation test data for film preparation of example 2
Figure BDA0003708056460000042
Free volume in a polymer (FFV) generally refers to the amount of void space not occupied by polymer chain molecules. The research goal of the polyimide gas separation membrane is to increase the free volume fraction in the new polymer design and simultaneously control the free volume to keep the size sieving capability.

Claims (10)

1. A polyimide polymer containing a sulfuryl structure between imide rings has a general structural formula as follows:
Figure FDA0003708056450000011
wherein n ranges from 76 to 116;
r is selected from one or more of the following groups:
Figure FDA0003708056450000012
wherein the dashed lines indicate the joints.
2. A polyimide film material, which is characterized in that the polyimide film material is composed of the polyimide polymer containing the sulfone group structure among the imide rings as claimed in claim 1.
3. The method for preparing the polyimide film material according to claim 2, comprising the steps of:
(1) Monomer drying
Respectively drying raw materials of dianhydride monomer and diamine monomer for later use;
(2) Synthesis of Polyamic acid
Under ice bath and nitrogen protection conditions, dissolving a diamine monomer in an aprotic polar solvent, then adding a dianhydride monomer, and stirring at normal temperature for 12-24 h to obtain a polyamic acid solution;
(3) Preparation of polyimide film
Casting the polyamic acid solution obtained in the step (2) on a cleaned glass plate to form a film, performing thermal imidization reaction by adopting gradient heating, wherein the temperature is increased from 40 ℃ to 250 ℃ for 6 hours, and then naturally cooling to room temperature for demoulding to obtain a polyimide film;
(4) Post-treatment
Soaking the polyimide film obtained in the step (3) in methanol, taking out and drying to finish post-treatment;
in the preparation method, the structural formula of the raw material dianhydride monomer is as follows:
Figure FDA0003708056450000013
the raw material diamine monomer is selected from one or more of the following compounds:
Figure FDA0003708056450000021
4. the method for preparing a polyimide film material according to claim 3, wherein in the step (2), the molar ratio of the diamine monomer to the dianhydride monomer is 1 to 1.05.
5. The method for preparing a polyimide film material according to claim 3, wherein in the step (2), the aprotic polar solvent is one or more selected from the group consisting of N, N-dimethylacetamide, N-dimethylformamide, and N-methylpyrrolidone.
6. The method for preparing the polyimide film material according to claim 3, wherein in the step (3), the solid content of the polyamic acid solution is 5 to 10%; when the film is cast to form the film, the thickness of the film is adjusted to be between 5 and 100 um.
7. The method for preparing a polyimide film material according to claim 3, wherein in the step (3), the thermal imidization is performed in a vacuum drying oven with the following temperature gradient: 1h at 40 ℃, 1h at 60 ℃, 1h at 100 ℃, 1h at 180 ℃ and 2h at 250 ℃.
8. The method for preparing a polyimide film material according to claim 3, wherein in the step (4), the soaking time is 24 hours.
9. The method for preparing the polyimide film material according to claim 3, wherein in the step (4), the drying is performed in a vacuum drying oven, and the temperature gradient is as follows: 1h at 80 ℃, 2h at 150 ℃, 2h at 200 ℃ and 1h at 250 ℃.
10. The use of the polyimide film material of claim 2 in gas separation.
CN202210713882.0A 2022-06-22 2022-06-22 Polyimide film material containing sulfonyl structure between imide rings and preparation method thereof Pending CN115160565A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101700474A (en) * 2009-11-30 2010-05-05 北京市射线应用研究中心 Polyimide gas separation membrane with high molecular weight and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101700474A (en) * 2009-11-30 2010-05-05 北京市射线应用研究中心 Polyimide gas separation membrane with high molecular weight and preparation method thereof

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