CN115948054A - Green water-soluble polyimide high-strength film and preparation method thereof - Google Patents
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 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 22
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000004985 diamines Chemical class 0.000 claims abstract description 13
- 238000011282 treatment Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- MKHDOBRSMHTMOK-UHFFFAOYSA-N 5-amino-2-(4-amino-2-carboxyphenyl)benzoic acid Chemical compound OC(=O)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(O)=O MKHDOBRSMHTMOK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 4
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
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- 239000002243 precursor Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
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- 229920005575 poly(amic acid) Polymers 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 9
- 239000000243 solution Substances 0.000 abstract description 9
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- 230000015572 biosynthetic process Effects 0.000 abstract description 5
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- 230000003287 optical effect Effects 0.000 abstract 1
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- 230000000052 comparative effect Effects 0.000 description 13
- 239000000758 substrate Substances 0.000 description 6
- 239000009719 polyimide resin Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
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- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
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Abstract
The invention belongs to the technical field of high polymer material preparation, and particularly relates to a green water-soluble polyimide high-strength film and a preparation method thereof. Firstly, diamine monomer 4,4-diaminobiphenyl-2,2 dicarboxylic acid (TFDB) and dianhydride monomer which are equimolar are subjected to primary reaction in N, N-dimethylacetamide (DMAc) which is subjected to water removal and purification to form polyamide acid (PAA) solution, then the polyamide acid (PAA) solution is poured on a glass plate and placed in a muffle furnace for hot imidization to obtain a water-soluble polyimide film, and then alkaline aqueous solution is used for alkalization treatment of the film to obtain the polyimide film taking water as a solvent through film formation again. The polyimide film provided by the invention has a novel structure, has good solubility in water and organic solvents, and has good optical transmittance and excellent mechanical strength.
Description
Technical Field
The invention belongs to the technical field of high polymer material preparation, and particularly relates to a green water-soluble polyimide high-strength film and a preparation method thereof.
Background
Polyimide has been attracting attention because polyimide has a unique imide ring structure and an aromatic main chain, and is a polymer material having heat resistance, chemical resistance, and chemical resistance at the highest levels among organic materials. However, most of the polyimides are generally difficult to process and post-treat due to their insolubility and non-fusibility, and only precursor polyamic acid solution can be processed. Therefore, how to improve the solubility of polyimide is the key to further expand the application field of polyimide-related materials.
The introduction of non-planar moieties, flexible chains or bulky groups has proven to be a successful approach to increasing solubility, but the latter two approaches often result in a loss of chain stiffness, glass transition temperature, chemical resistance and thermal stability of the polyimide.
Disclosure of Invention
In order to solve the problem of PI solubility pointed out in the background art, the invention introduces carboxyl (-COOH) functional groups into the molecular chain of polyimide through molecular design to optimize the structure, and then alkalifies the functional groups into salts to achieve the purpose of improving the solubility, thereby solving the problem of processing difficulty caused by poor solubility of the polyimide in application, and further widening the application field of the polyimide.
The present invention provides a novel water-soluble polyimide film having a repeating unit represented by the following formula:
wherein X may be a six-membered aliphatic ring and/or aromatic ring, and n is a repeating structural unit, and is 10-n-woven fabric 2000.
The polyimide film preferably has the following repeating units:
wherein 10-n-type woven fabrics are 2000, and 10-m-type woven fabrics are 2000.
The polyimide of the present invention has good solubility in organic solvents, and is soluble in alkaline aqueous solutions.
The novel water-soluble polyimide polymer film provided by the invention is prepared according to the following steps:
(1) Selection of diamine and dianhydride monomers:
selecting diamine monomer with strong polar functional group (-COOH), and respectively reacting with dianhydride monomer of aliphatic ring and/or aromatic ring, wherein the dianhydride of aliphatic ring is 1,2,4,5-cyclohexane tetracarboxylic dianhydride (HPMDA), the aromatic ring dianhydride is pyromellitic dianhydride (PMDA), and the diamine is 4,4-diaminobiphenyl-2,2-dicarboxylic acid (TFDB); (all monomers are commercially available)
The structural formulas are respectively shown as follows:
the diamine monomer selected by the invention has a carboxyl functional group, the carboxyl has low free volume and high polarity, the surface area is reduced and enhanced due to carboxyl functionalization, and the carboxyl is taken as a polar group and can form a hydrogen bond between donor atoms and acceptor atoms, so that the filler is tightened and the interchain rigidity of a polymer matrix is increased, and the average interchain distance of the obtained PI is tighter. The carboxyl group also imparts extremely excellent solubility to the prepared PI.
(2) Water removal purification of the solvent DMAc:
50ml of DMAc and 0.4g of calcium hydride were added to the single-neck flask, and the flask was sealed with a balloon and stirred magnetically at room temperature. The distillation apparatus was subsequently set up and distilled at 155 ℃ under reduced pressure for about 20min to give 35ml of purified DMAc.
(3) Synthesis and preparation of Polyimide (PI)
In a three-necked flask equipped with mechanical stirring, purified DMAc was poured, diamine monomer was added at one time, dianhydride monomer was added after complete dissolution, and nitrogen was substituted three times to remove air in the apparatus, after sufficient reaction for 40min at room temperature, dianhydride monomer was added (this step was repeated 3-5 times) and the viscosity change of the polymerization solution was observed, and DMAc was added successively to adjust the solid content to 15wt%. And moving to an ice water bath for reaction for 24 hours.
The molar ratio of dianhydride to diamine is 1:1;
pouring the PAA acid solution on a glass substrate, placing the glass substrate in a muffle furnace for gradient temperature rise to carry out thermal imidization to obtain the novel polyimide film with carboxyl.
The temperature gradient of the thermal imidization of the alicyclic PI is as follows: (40 ℃ -2h,60 ℃ -2h,80 ℃ -1.5h,140 ℃ -1h,180 ℃ -1h,210 ℃ -1 h); the temperature gradient of the aromatic ring PI thermal imidization is as follows: 80-2h, 100-2h, 140-1.5h, 180-1h, 250-1h, 280-1 h; the temperature gradient of the aromatic ring and aliphatic ring cross-linking PI thermal imidization is as follows: (80-2h, 120-2h, 180-1.5h, 220-1h, 250-1h, 300-1 h).
(4) Preparation of novel water-soluble polyimide high-strength film
And (3) dissolving the polyimide film in a KOH solution with the solid content of 15wt% in 20%, uniformly dripping the polyimide film on a glass substrate after stirring magnetons for 3 hours, and placing the glass substrate in a forced air oven with the temperature of 80 ℃ for 6 hours to obtain the water-soluble polyimide high-strength film.
Advantageous effects
The water-soluble polyimide high-strength film prepared by the invention has a novel structure, has excellent solubility compared with the traditional polyimide, so that the PI has great convenience and advantages in the processing and post-treatment processes, and is more environment-friendly as water is used as a solvent and different from the traditional organic solvent.
Description of the drawings:
FIG. 1 is an infrared spectrum of a polyimide resin (PI) synthesized in examples 1 and 2.
Fig. 2 is a stress-strain curve of the polyimide resin (PI) synthesized in examples 1 and 2.
Detailed Description
In order to more clearly illustrate the present invention, the present invention is further illustrated below with reference to examples. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. The experimental materials, reagents and the like used in the following experimental examples can be obtained commercially or by known experimental methods.
The structural formula of the selected polyimide resin (PI) is shown as follows:
example 1
This example provides a polyimide resin having the following repeating units, which is designated as HPMDA-TFDB.
n is a repeating structural unit and is 10 to 2000;
the preparation method of the polyimide resin HPMDA-TFDB comprises the following steps:
(1) Water removal purification of N-N dimethylacetamide (DMAc):
50ml of DMAc were charged into a 100ml single-neck flask, a rotor and 0.4g of CaH were added 2 The mixture was put on a balloon and magnetically stirred at room temperature for 24 hours to fully react.
After stirring was completed, a vacuum distillation apparatus was used, and the boiling point of DMAc was 163 ℃ so that the temperature of vacuum distillation was 155 ℃. The front and back fractions are separated out, and the rest are collected and sealed, so that the yield is as follows: 80 percent.
(2) Preparation of polyimide:
22ml of water-removed DMAc was placed in a three-necked flask equipped with a mechanical stirring device, and 4,4-diaminobiphenyl-2,2-dicarboxylic acid TFDB (2.7226g, 10 mmol) was added, and nitrogen was substituted 3 times to ensure removal of air from the device, and stirred for 30min until complete dissolution.
The dianhydride monomer 1,2,4,5-cyclohexanetetracarboxylic dianhydride HPMDA (2.2417g, 10mmol) was added five times (2 mmol each), the viscosity was observed, and 2ml of solvent (DMAc) was added with the addition of dianhydride monomer until the final solid content was 15wt%. The product PAA acid solution was collected after stirring in an ice water bath for 18 h.
Preheating a glass sheet in advance in a muffle furnace, and then dropwise coating the PAA acid solution on the glass sheet for thermal imidization (40-2h, 60-2h, 80-1.5h, 140-1h, 180-1h and 210-1 h) to obtain the PI film.
And (3) dissolving the obtained polyimide film in a 20% KOH solution according to the solid content of 15wt%, uniformly dripping the polyimide film on a glass substrate after stirring magnetic particles for 3 hours, and placing the glass substrate in a blast oven at the temperature of 80 ℃ for 6 hours to obtain the water-soluble polyimide high-strength film.
The tensile strength of the PI film was 72.8MPa, the Young's modulus was 2.2GPa, and the elongation at break was 5.7%.
Infrared data: FTIR (KBr, v, cm) -1 )：3446，1739，1610，1368，1261，1104，823，724。
Example 2
This example is different from example 1 in that the dianhydride monomer added in step (2) was pyromellitic anhydride PMDA (2.1812g, 10mmol), and the other treatment means was the same as example 1. Thermal imidization temperatures of PMDA-TFDB (80 ℃ -2h,100 ℃ -2h,140 ℃ -1.5h,180 ℃ -1h,250 ℃ -1h,280 ℃ -1 h) due to the difference in rigidity of dianhydride monomers.
The tensile strength of the PI film was 104.3MPa, the Young's modulus was 2.7GPa, and the elongation at break was 6.8%.
Infrared data: FTIR (KBr, v, cm) -1 )：3403，1714，1602，1483，1379，1187，1140，1007，794。
Example 3
This example differs from example 1 in that the dianhydride monomers added in step (2) were 1,2,4,5-cyclohexanetetracarboxylic dianhydride HPMDA (1.1209g, 5mmol) and pyromellitic anhydride PMDA (1.0906g, 5mmol), and the other treatments were identical to example 1. The PI prepared in this example has a thermal imidization temperature of Co-PIs (80-2h, 120-2h, 180-1.5h, 220-1h, 250-1h, 300-1 h) due to copolymerization.
The tensile strength of the PI film was 98.7MPa, the Young's modulus was 2.0GPa, and the elongation at break was 5.7%.
Infrared data: FTIR (KBr, v, cm) -1 )：3178，1717，1598，1483，1377，1182，1142，1013，785。
Comparative example 1
Difference between this comparative example and example 1 the dianhydride monomer used in the synthesis of PI in step (2) was hydrogenated pyromellitic anhydride (HPMDA) and the diamine monomer was 4,4' -diamino-toluic acid (4 ATA) other treatments were consistent with example 1.
Comparative example 2
Difference between this comparative example and example 1 the dianhydride monomer used in the synthesis of PI in step (2) was cyclobutane tetracarboxylic dianhydride (CBDA), and the other treatments were the same as in example 1.
Comparative example 3
The difference between this comparative example and example 1 is that no alkalization treatment is performed after the film formation of the synthesized PI in step (2), and other treatment means are the same as those in example 1.
Comparative example 4
The comparison example and example 2 are different in that the thermal imidization process in step (2) is 300-4 h, and other treatment means and reaction monomers are the same as those in example 2.
The following performance tests were performed on the novel water-soluble Polyimide (PI) high-strength films prepared in examples 1 to 3, and the test results are shown in table 1:
and (3) testing mechanical properties: the mechanical property of the PI is tested by a WDT-10 electronic universal tester according to the national standard GB/T1040.3-2006.
And (3) testing the solubility: film samples were oven dried in an 80 ℃ oven and plated in petri dishes at 0.5 g/10 ml organic solvent.
From the results in table 1, it can be seen that: the mechanical properties of the polyimide film prepared in example 1 were reduced compared to those of the polyimide film prepared in example 2, because the polyimide film having a single aliphatic ring has lower bond strength due to lower rigidity of the main chain, resulting in a more brittle film. Compared with the mechanical properties of the PI subjected to alkalization treatment (comparative example 1) and the PI in an organic solvent (comparative examples 2 and 3), the prepared water-soluble PI film has unusual performance.
TABLE 1
| Sample (I) | Tensile Strength (MPa) | Elongation at Break (%) | Young's modulus (GPa) |
| Example 1 | 72.8 | 5.7 | 2.2 |
| Example 2 | 104.3 | 6.8 | 2.7 |
| Example 3 | 98.7 | 5.7 | 2.0 |
| Comparative example 1 | 42.6 | 8.1 | 1.9 |
| Comparative example 2 | 65.3 | 4.7 | 2.1 |
| Comparative example 3 | 72.0 | 5.1 | 2.1 |
| Comparative example 4 | 62.3 | 4.4 | 1.7 |
As can be seen from the results of Table 2, the solubility of the three polyimide films prepared is greatly superior to that of the conventional polyimide film. The three PI films have good solubility in various organic solvents, wherein the PI films can be dissolved in dimethyl sulfoxide (DMSO) at room temperature, and can be dissolved in N-N Dimethylformamide (DMF), N-N dimethylacetamide (DMAc) and methyl pyrrolidone (NMP) or alkaline aqueous solution.
TABLE 2
0.3g PI/10ml organic solvent
++: can be dissolved at room temperature; +: partially soluble at 60 ℃; insoluble at room temperature, under heating.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A green water-soluble polyimide high-strength film, characterized in that the polyimide film has the following repeating units:
wherein X is a six-membered aliphatic ring and/or aromatic ring, and n is a repeating structural unit, and is 10-n-woven fabric 2000.
2. The green water-soluble polyimide high-strength film according to claim 1, wherein the polyimide film has the following structure:
wherein 10-n-type woven fabrics are 2000, and 10-m-type woven fabrics are 2000.
3. The preparation method of the green water-soluble polyimide high-strength film is characterized by comprising the following steps:
(1) Selection of diamine and dianhydride monomers:
the diamine is 4,4-diaminobiphenyl-2,2-dicarboxylic acid (TFDB), the dianhydride of the aliphatic ring is 1,2,4,5-cyclohexane tetracarboxylic dianhydride (HPMDA), and the dianhydride of the aromatic ring is pyromellitic dianhydride (PMDA);
(2) Water removal purification of the solvent DMAc:
adding N, N-dimethylacetamide (DMAc) and calcium hydride into a single-neck flask, sealing with a balloon, stirring at room temperature to fully react, then setting up a distillation device, and carrying out reduced pressure distillation at 155 ℃ to obtain purified DMAc;
(3) Preparation of a green water-soluble polyimide film:
(a) Reacting dianhydride with an aliphatic ring and/or aromatic ring structure with diamine with a carboxyl functional group in a purified solvent to obtain a precursor polyamic acid solution of polyimide with an aliphatic ring and/or aromatic ring structure with a carboxyl;
(b) Performing thermal imidization with different temperature gradients on the polyimide precursor with the carboxyl structure obtained in the step (a) to obtain a polyimide film;
(c) And (c) carrying out alkalization treatment on the PI film obtained in the step (b) in KOH, and then forming a film again in an oven to obtain the green water-soluble polyimide high-strength film.
4. The method for preparing the green water-soluble polyimide high-strength film as claimed in claim 3, wherein the 1,2,4,5-cyclohexane tetracarboxylic dianhydride (HPMDA), pyromellitic dianhydride (PMDA), 4,4-diaminobiphenyl-2,2-dicarboxylic acid (TFDB) structural formulas of step (1) are respectively as follows:
5. the method for preparing the green water-soluble polyimide high-strength film as claimed in claim 3, wherein the mass volume ratio of the calcium hydride to the DMAc in the step (2) is 0.4g and 50ml, and the reduced pressure distillation time is 20min.
6. The method for preparing the green water-soluble polyimide high-strength film according to claim 3, wherein the molar ratio of dianhydride to diamine in step (3) (a) is 1:1.
7. The method for preparing a green water-soluble polyimide high-strength film as claimed in claim 3, wherein the monomers in step (3) (a) are added in the order of adding diamine monomer into solvent, stirring for 30min until completely dissolved, then adding dianhydride monomer in batches and observing viscosity change.
8. The method for preparing the green water-soluble polyimide high-strength film as claimed in claim 2, wherein the temperature gradient of the thermal imidization of the aliphatic ring PI in the step (3) (b) is as follows: (40-2h, 60-2h, 80-1.5h, 140-1h, 180-1h, 210-1 h); the temperature gradient of the thermal imidization of the aromatic ring PI is as follows: (80-2h, 100-2h, 140-1.5h, 180-1h, 250-1h, 280-1 h); the temperature gradient of the aromatic ring and aliphatic ring cross-linking PI thermal imidization is as follows: (80-2h, 120-2h, 180-1.5h, 220-1h, 250-1h, 300-1 h).
9. The method for preparing a green water-soluble polyimide high-strength film according to claim 2, wherein the KOH mass concentration in step (3) (c) is 20%, alkalization treatment and magneton stirring are carried out for 3h.
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| CN116462967A (en) * | 2023-04-26 | 2023-07-21 | 昶力管业(常州)有限公司 | Transparent flame-retardant Gao Wenlei-carving-resistant identification product and preparation method thereof |
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| US6894174B1 (en) * | 2003-05-15 | 2005-05-17 | Shayda Technologies, Inc. | Water-soluble polyimides and methods of making and using same |
| CN104672477A (en) * | 2015-03-01 | 2015-06-03 | 中国乐凯集团有限公司 | Preparation method and product of low-roughness polyimide film and application of product |
| CN110945053A (en) * | 2017-07-29 | 2020-03-31 | 国立研究开发法人科学技术振兴机构 | Hydrophilic polyamides or polyimides |
| CN112062960A (en) * | 2020-09-10 | 2020-12-11 | 武汉华星光电半导体显示技术有限公司 | Polyimide, polyimide film, preparation method of polyimide film and display device |
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| CN116462967A (en) * | 2023-04-26 | 2023-07-21 | 昶力管业(常州)有限公司 | Transparent flame-retardant Gao Wenlei-carving-resistant identification product and preparation method thereof |
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