CN118344588A - High-temperature-resistant low-viscosity high-solubility polyisoimide resin and preparation method thereof - Google Patents
High-temperature-resistant low-viscosity high-solubility polyisoimide resin and preparation method thereof Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims abstract description 110
- 229920005989 resin Polymers 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 29
- 239000004917 carbon fiber Substances 0.000 claims description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 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 description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 150000004984 aromatic diamines Chemical class 0.000 claims description 10
- 239000012024 dehydrating agents Substances 0.000 claims description 10
- 150000008064 anhydrides Chemical class 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- SYLFKCCCMAKZKF-UHFFFAOYSA-N 4-(4-aminophenoxy)-3-(trifluoromethyl)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1C(F)(F)F SYLFKCCCMAKZKF-UHFFFAOYSA-N 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 4
- -1 hexafluoroisopropyl Chemical group 0.000 claims description 3
- 229920005575 poly(amic acid) Polymers 0.000 claims description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012346 acetyl chloride Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
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- 239000003365 glass fiber Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- VCJUSEFXUWAMHH-UHFFFAOYSA-N 4-ethynyl-2-benzofuran-1,3-dione Chemical group C1=CC=C(C#C)C2=C1C(=O)OC2=O VCJUSEFXUWAMHH-UHFFFAOYSA-N 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 18
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- 230000009477 glass transition Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 239000000805 composite resin Substances 0.000 abstract description 2
- 239000002798 polar solvent Substances 0.000 abstract description 2
- 238000001721 transfer moulding Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 12
- 238000011056 performance test Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000011229 interlayer Substances 0.000 description 11
- 229920001721 polyimide Polymers 0.000 description 11
- 238000010008 shearing Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000004642 Polyimide Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
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- 239000008367 deionised water Substances 0.000 description 6
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
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- 150000004985 diamines Chemical class 0.000 description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
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- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
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- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- UPGRRPUXXWPEMV-UHFFFAOYSA-N 5-(2-phenylethynyl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C#CC1=CC=CC=C1 UPGRRPUXXWPEMV-UHFFFAOYSA-N 0.000 description 1
- VZUHQRBBQSLSHS-SSZFMOIBSA-N Isoimide Chemical compound C1=CC(Br)=CC=C1\N=C/1C(CCCC2)=C2C(=O)O\1 VZUHQRBBQSLSHS-SSZFMOIBSA-N 0.000 description 1
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a high-temperature-resistant low-viscosity high-solubility polyisoimide resin and a preparation method thereof, which can have good solubility in polar solvents, low melt viscosity and low processing temperature. The resin molding has good heat resistance, the glass transition temperature of the resin is more than 400 ℃, and the resin molding has good mechanical properties (the tensile strength is more than 70MPa and the bending strength is more than or equal to 130 MPa), can be molded by adopting hot molding, autoclave, resin transfer molding and other processes, and the prepared resin-based composite material can be widely applied to the aerospace field.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-temperature-resistant low-viscosity high-solubility polyisoimide resin and a preparation method and application thereof.
Background
Thermoset Polyimides (PI) are widely recognized as high performance matrix resins for their excellent thermal stability and performance mechanical/electronic properties, with wide application potential in the fields of aviation, aerospace, microelectronics, gas separation, automotive industry, etc. However, the potential applications are limited due to the processing difficulties of the materials produced by the high production molding temperatures.
Researchers are continually striving to improve these properties and find better solutions. Polyimides are typically made from soluble polyamic acid intermediates, but this process produces volatile byproducts such as water vapor at high temperatures. This results in polyimide materials having inherent defects such as high porosity and instability, which limit their application in high precision and large-size processing.
In the 70 s of the 20 th century, NASA research center developed monomeric reactant (PMR) 15 by in situ polymerization of PMR, a milestone achievement. Due to their low melt viscosity and better processing window, PMR-15 composites have been widely used in aircraft, automotive and offshore oil drilling platforms. However, the use of Norbornene (NE) terminated prepolymers is limited due to the severe thermal oxidative and storage conditions (600 ℃,200-500 psi) and brittleness of the cured PI. The aromatic cross-linked structure is formed by introducing phenylethynyl-terminated imide, so that the thermal oxidation stability and toughness of PI can be effectively improved. At the same time, at low curing temperatures of 350-370 ℃, the processing window is further expanded to about 100 ℃. However, the significant expansion of the process window comes at the cost of high performance equipment. Acetylene-terminated polyimides have been extensively studied on the basis of lower curing temperatures (180-250 ℃). Unfortunately, the melting temperature of acetylene-capped PI overlaps with the crosslinking temperature, resulting in a narrower processing window, limiting the application of Thermid 600,600.
Polyisoimide oligomers based on isomeric dianhydrides and diamines have also been found to be effective precursors for the preparation of polyimide resins. The obtained imide oligomer has better solubility and melt processability due to its asymmetric structure. The polyisoimides also exhibit excellent solubility in low boiling solvents and can be used for the simple impregnation of composites and adhesives. CN 116178716a discloses a polyisoimide which is soluble in polar high boiling solvents and has a solids content of higher than 60%, which can be used for the preparation of negative photoresist. U.S. Pat. No. 3, 6124035, 6359107B1 discloses a series of thermosetting polyimide resins endcapped with phenylethynyl groups, having glass transition temperatures (T g) up to 298, 330 and 370 ℃, respectively, prepared from isomeric biphenyldianhydrides (2, 3',4' -biphenyltetracarboxylic dianhydride, α -BPDA) having asymmetric molecular structures instead of biphenyldianhydride (3, 3',4' -biphenyltetracarboxylic dianhydride, s-BPDA) having stable melt viscosities below 300 ℃. CN104987506a discloses a soluble polyimide containing tert-butyl and benzofuran structure, which can be dissolved in various solvents, but the resin formed after high temperature curing has a glass transition temperature lower than 300 ℃, and is difficult to meet the use requirements of high temperature resistant and high strength carbon fiber composite materials. Therefore, it is of great importance to develop a polyisoimide resin which has high temperature resistance (glass transition temperature is more than 400 ℃), low viscosity (meets the requirements of various molding processes) and high solubility.
Disclosure of Invention
To this end, the object of the present invention is to provide a polyisoimide which can have good solubility in polar solvents, which has a low melt viscosity and a low processing temperature. The resin molding part has good heat resistance, can be molded by adopting hot molding, autoclave, resin transfer molding and other processes, and the prepared resin-based composite material can be widely applied to the field of aerospace.
In order to achieve the above purpose, the invention adopts the technical proposal that
The invention provides a polyisoimide resin, which has a structural formula shown in a formula I:
In the formula I, n represents the polymerization degree, and the weight average molecular weight of the polyisoimide resin shown in the formula I is 750-5000 g/mol;
R 1 is selected from the following structures (1) or (2):
r 2 is selected from the following structures (3):
R 3 is selected from the following (4) or (5):
In the polyisoimide resin shown in the formula I, the molecular weight is theoretical molecular weight, and the calculation formula is as follows:
M=m Dianhydride ×n+M Diamines ×(n+1)+2×M End capping agent -2×(n+1)×M Water and its preparation method ; wherein M is the theoretical molecular weight of the molecular structural formula shown in the formula I, and M End capping agent and M Water and its preparation method respectively represent the molar masses of the used end-capping agent and water; n is the degree of polymerization shown in formula I; m Dianhydride represents the average molar mass of the dianhydrides used, the calculation formula being M Dianhydride ＝k1×M1+k2×M2 + … …, wherein k 1、k2 … … represents the molar ratio of the different dianhydrides used and M 1、M2 … … represents the molar mass of the different dianhydrides used; m Diamines represents the average molar mass of the diamines used, calculated in the same manner as M Dianhydride .
The invention provides a preparation method of the polyisoimide resin, which comprises the following steps:
(1) Taking an organic solvent, aromatic diamine shown as R 1, aromatic dianhydride shown as R 2 and an R 3 reactive end-capping agent as raw materials to prepare polyamide acid through polymerization reaction and end-capping reaction;
(2) And (3) imidizing the polyamic acid under the action of a catalyst and a dehydrating agent to obtain the polyisoimide resin.
Preferably, the aromatic diamine is selected from 2-fluoro-4, 4 '-diaminodiphenyl ether or 2-trifluoromethyl-4, 4' -diaminodiphenyl ether.
Preferably, the aromatic dianhydride is selected from 4,4' - (hexafluoroisopropyl) diphthalic anhydride (6 FDA).
Preferably, the reactive capping agent is selected from the group consisting of ethynylphthalic anhydride and 4-phenylacetylene phthalic anhydride.
Preferably, the molar ratio of the aromatic diamine, the aromatic dianhydride and the reactive capping agent is (1.13 to 4.54): (0.13-3.54): 2, which may be 1.51：0.51：2,1.40：0.40：2,1.38：0.38：2,1.77：0.77：2,1.64：0.64：2,1.49：0.49：2,1.47：0.47：2,1.67：0.67：2,1.52：0.52：2,1.49：0.49：2,1.52：0.52：2 or 1.13:0.13:2.
Preferably, the organic solvent is selected from any one or more of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF) and N, N-dimethylacetamide (DMAc).
Preferably, the polymerization reaction and the end capping reaction are carried out at a temperature of 0-15 ℃, preferably 0 ℃; the polymerization time is 6 to 18 hours, preferably 6 hours; the capping reaction time is 6 to 16 hours, preferably 16 hours.
Preferably, in the step (1), the organic solvent is added in batches, and the addition amount of the organic solvent is controlled to be 20-30% (mass) of the solid content of the system, such as 30% in the polymerization reaction; in the end-capping reaction, the addition amount of the organic solvent is controlled to be 25 to 35% by mass, such as 30% by mass, of the solid content of the system.
Preferably, in the step (1), the polymerization reaction and the end capping reaction are both carried out under the protection of inert gas.
Preferably, in step (1), both the polymerization and the capping are carried out with stirring.
Preferably, in the step (2), the imidization reaction is performed in an ice-water bath environment.
Preferably, the dehydrating agent is selected from any one of acetyl chloride, thionyl chloride, dicyclohexylcarbodiimide and trifluoroacetic anhydride.
Preferably, the amount of the dehydrating agent is 2.5 to 5 times the amount of the aromatic diamine substance.
Preferably, the catalyst is selected from any one of triethylamine, triethanolamine, pyridine and isoquinoline.
Preferably, the catalyst is used in an amount of 0.01 to 2 times the amount of the aromatic diamine substance.
Preferably, the imidization reaction product is poured into deionized water with the volume of 4 times of that of the product to be stirred, the product is repeatedly washed and filtered by deionized water until the filtrate is neutral, and the product is subjected to vacuum treatment for 12 hours at 120 ℃ to obtain the polyisoimide resin powder.
The polyisoimide of the present invention can be dissolved in various solvents and used for preparing carbon fiber prepregs. The invention further provides application of the polyisoimide resin in composite materials with carbon fibers, glass fibers, quartz fibers or aramid fibers.
Specifically, the polyisoimide resin prepared by the invention can be dissolved in N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, chloroform, methylene dichloride, dioxane and tetrahydrofuran solvents.
The invention further provides a molding of the polyisoimide resin, which is obtained by curing the polyisoimide resin for 2 to 4 hours under the conditions that the temperature is 370 to 380 ℃ and the pressure is 4 MPa. Before the solidification, the film is heated to 280-310 ℃ to enable the resin powder to be completely melted.
The glass transition temperature of the molding of the polyisoimide resin is more than 400 ℃, and the 5% thermal decomposition temperature is more than 550 ℃.
The normal-temperature tensile strength of the polyisoimide resin molding part is more than or equal to 70MPa, and the bending strength is more than or equal to 130MPa.
Compared with the prior art, the invention has the following beneficial effects:
(1) Solubility: can be dissolved in N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), chloroform, methylene chloride, dioxane and tetrahydrofuran solvents;
(2) Workability: the melt viscosity of the resin is always less than 100 Pa.s after the resin is kept at the constant temperature of 250-280 ℃ for 2-4 hours;
(3) High strength: the normal temperature tensile strength of the molding part is more than or equal to 70MPa, and the bending strength is more than or equal to 130MPa;
(4) High temperature resistance: the glass transition temperature of the cured resin is more than 400 ℃, and the 5% thermal decomposition temperature is more than 550 ℃.
The advanced composite material prepared from the resin can be widely applied to advanced technical fields such as aerospace, space technology, precision machinery, petrochemical industry, automobiles and the like.
It should be understood that all combinations of the foregoing concepts, as well as additional concepts described in more detail below, may be considered as part of the inventive subject matter so long as such concepts are not mutually inconsistent. In addition, all combinations of claimed subject matter are considered part of the inventive subject matter.
The foregoing and other aspects, embodiments, and features of the present teachings will be more fully understood from the following description, taken together with the accompanying drawings. Other additional aspects of the invention, such as features and/or advantages of the exemplary embodiments, will be apparent from the description which follows, or may be learned by practice of the embodiments according to the teachings of the invention.
Drawings
FIG. 1 is an infrared spectrum of a polyisoimide resin prepared according to example 1 of the present invention.
FIG. 2 is a high temperature rheology chart of the polyisoimide resin prepared in example 1 of the present invention.
FIG. 3 is a Differential Scanning Calorimeter (DSC) curve of a polyisoimide resin prepared according to example 1 of the present invention.
FIG. 4 is a photograph of a molded article of a polyisoimide resin prepared in example 1 of the present invention.
FIG. 5 is a photograph of a molded laminate of a polyisoimide resin/carbon fiber composite prepared in example 1.
Detailed Description
For a better understanding of the technical content of the present invention, specific examples are set forth below, along with the accompanying drawings.
Aspects of the invention are described herein with reference to the drawings, in which there are shown various illustrative embodiments. Embodiments of the invention are not necessarily intended to include all aspects of the invention. It should be understood that the various concepts and embodiments described above, as well as those described in more detail below, may be implemented in any of a number of ways, as the disclosed concepts and embodiments are not limited to any implementation. Additionally, some aspects of the disclosure may be used alone or in any suitable combination with other aspects of the disclosure.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1
Preparation and performance test of polyisoimide resin
1. Preparation of polyisoimide resin and Structure confirmation
The polyisoimide resin is prepared as follows:
(1) To a three-necked flask equipped with mechanical stirring and nitrogen protection were added 30.5525g (0.14 mol) of 2-trifluoromethyl-4, 4 '-diaminodiphenyl ether and 0.3g of triethylamine as a catalyst, followed by addition of 66.22: 66.22g N-methylpyrrolidone (NMP) as a solvent, and after dissolution, 35.2830g (0.079 mol) of 4,4' -hexafluoroisopropyl diphthalic anhydride and 153.23gNMP. After 6 hours of reaction in an ice-water bath, 30.0758g (0.12 mol) of 4-phenylacetylene phthalic anhydride as a capping agent was added, NMP was added to a solid content of 30%, and stirring was continued for 16 hours.
(2) A dropping funnel was mounted on the three-necked flask, and 79.8144g (0.38 mol) of trifluoroacetic anhydride (a dehydrating agent) was added dropwise thereto for 4 hours.
(3) Subsequently, the gum solution was gradually dispersed into about 6L of deionized water with stirring; filtration gave a resin solid which was washed three times with water and then dried in a forced air drying oven at 120℃for 24 hours to give a polyisoimide resin.
The infrared properties of the target product were as follows (fig. 1): infrared spectral absorption peak (cm -1): 3055, 2215, 1781, 1723, 1611, 1492, 1377, 1244, 1088, 1049-1121, 916, 743. The structure is correct through verification.
The polyisoimide resin prepared in the embodiment is shown in a formula II:
In formula II, n represents the degree of polymerization, and the molecular weight of the resin is 1500g/mol.
2. Preparation of polyisoimide resin molded article and performance test
The polyisoimide powder (formula II) obtained by the method is placed in a die, the whole die is placed in a high-temperature die press, the press is heated to 300 ℃ and kept at the constant temperature for 10min, then the temperature is increased to 380 ℃ at the speed of 4 ℃/min, the pressure is increased to 4MPa for 1-2 min, and the temperature and the pressure are maintained for 2 hours. And then stopping heating, keeping the pressure of the mold, cooling, opening the mold, and taking out the black solidified resin plate when the temperature is reduced to 250 ℃.
The results of the high temperature rheology test show (FIG. 2) that the resin has a melt viscosity of minimum 3.51 Pa.s at 270 ℃ for 2 hours;
the Differential Scanning Calorimeter (DSC) curve of the resin is shown in FIG. 3; the solid product of the pure poly (iso-imide) resin molded article after curing is shown in fig. 4; the T g is 417 ℃, the 5% thermal weight loss temperature is more than 550 ℃, the tensile strength (room temperature) is 70MPa, and the bending strength (room temperature) is 136MPa.
3. Preparation of polyisoimide resin/carbon fiber composite laminate and performance test
The polyisoimide resin obtained by the method is dissolved in dimethylacetamide (the mass ratio is 60:40), and the obtained mixture is fully stirred to form a uniform solution, so that the polyisoimide prepreg is obtained.
The obtained polyisoimide prepreg is uniformly brushed on the surface of high-strength carbon fiber cloth, is put into an oven, is heated to 180 ℃ and is kept at the constant temperature for 12 hours, and is cooled to room temperature after the solvent is removed, so that the polyisoimide carbon fiber prepreg is obtained.
The surface of the obtained polyisoimide carbon fiber prepreg is sprayed with dichloromethane for softening, then the temperature is increased according to the gradient of 160 ℃/2h+260 ℃/2h+380 ℃/2h, and the molding is carried out under the condition that the mold closing pressure is controlled to be 2.5MPa, so that the polyisoimide carbon fiber composite material is obtained (the photo is shown in figure 5). The bending strength at room temperature is 1860MPa, the interlayer shearing strength at room temperature is 81MPa, the bending strength at 400 ℃ is 962MPa, and the interlayer shearing strength at 400 ℃ is 41MPa.
Example 2
Preparation and performance test of polyisoimide resin
1. Preparation of polyisoimide resin and Structure confirmation
The polyisoimide resin is prepared as follows:
(1) To a three-necked flask equipped with a mechanical stirrer and nitrogen protection, 30.5522g (0.14 mol) of 2-trifluoromethyl-4, 4 '-diaminodiphenyl ether and 0.3g of triethylamine as a catalyst were charged, then 66.22g of NMP was added as a solvent, 37.84426g (0.085 mol) of 4,4' -hexafluoroisopropyl diphthalic anhydride and 161.77g of NMP were added after dissolution, at which time the solid content of the reaction system was 30% by mass, and after 6 hours of reaction in an ice-water bath, 18.8716g (0.11 mol) of an end-capping agent ethynylphthalic anhydride was added, NMP was added to a solid content of 30%, and stirring was continued for 16 hours.
(2) A dropping funnel was mounted on the three-necked flask, and 73.5140g (0.35 mol) of trifluoroacetic anhydride (a dehydrating agent) was added dropwise thereto for 4 hours.
(3) Subsequently, the gum solution was gradually dispersed into about 6L of deionized water with stirring; filtration gave a resin solid which was washed three times with water and then dried in a forced air drying oven at 120℃for 24 hours to give a polyisoimide resin.
The target product was characterized as follows: infrared spectral absorption peak (cm -1): 3065, 2217, 1780, 1720, 1609, 1492, 1375, 1244, 1082, 1049-1121, 915, 742. The structure is correct through verification. The polyisoimide resin prepared in the embodiment is shown in a formula III:
in the formula III, n represents the polymerization degree, and the molecular weight of the polyisoimide resin shown in the formula III is 1500g/mol.
2. Preparation of polyisoimide resin molded article and performance test
The polyisoimide powder obtained by the method is placed into a die, the whole die is placed into a high-temperature die press, the press is heated to 300 ℃ and kept at the constant temperature for 10min, then the temperature is increased to 380 ℃ at 4 ℃/min, the pressure is increased to 4MPa for 1-2 min, and the temperature and the pressure are maintained for 2 hours. And then stopping heating, keeping the pressure of the mold, cooling, opening the mold, and taking out the black solidified resin plate when the temperature is reduced to 250 ℃.
The high-temperature rheological test result shows that the resin has the minimum melt viscosity of 4.76 Pa.s after being kept at the temperature of 270 ℃ for 2 hours.
The T g of the pure polyisoimide resin molded part formed after the resin is solidified is 413 ℃, the 5% thermal weight loss temperature is more than 550 ℃, the tensile strength (room temperature) is 72MPa, and the bending strength (room temperature) is 131MPa.
3. Preparation of polyisoimide resin/carbon fiber composite laminate and performance test
The polyisoimide resin obtained by the method is dissolved in dimethylacetamide (the mass ratio is 60:40), and the obtained mixture is fully stirred to form a uniform solution, so that the polyisoimide prepreg is obtained.
The obtained polyisoimide prepreg is uniformly brushed on the surface of high-strength carbon fiber cloth, is put into an oven, is heated to 180 ℃ and is kept at the constant temperature for 12 hours, and is cooled to room temperature after the solvent is removed, so that the polyisoimide carbon fiber prepreg is obtained.
Spraying dichloromethane on the surface of the obtained polyisoimide carbon fiber prepreg for softening, then heating according to a gradient of 160 ℃/2h+260 ℃/2h+380 ℃/2h, and molding under the condition that the mold closing pressure is controlled to be 2.5MPa, thereby obtaining the polyisoimide carbon fiber composite material. The bending strength at room temperature is 1740MPa, the interlayer shearing strength at room temperature is 79MPa, the bending strength at 400 ℃ is 910MPa, and the interlayer shearing strength at 400 ℃ is 42MPa.
Example 3
Preparation and performance test of polyisoimide resin
1. Preparation of polyisoimide resin and Structure confirmation
The polyisoimide resin is prepared as follows:
(1) To a three-necked flask equipped with a mechanical stirrer and nitrogen protection, 44.4823g (0.166 mol) of 2-trifluoromethyl-4, 4 '-diaminodiphenyl ether and 0.3g of triethylamine as a catalyst were charged, 96.39gNMP was then added as a solvent, 53.3099g (0.12 mol) of 4,4' -hexafluoroisopropyl-diphthalic anhydride and 229.54g of NMP were added after dissolution, at which time the solid content of the reaction system was 30% by mass, and after 6 hours of reaction in an ice-water bath, 22.7527g (0.092 mol) of 4-phenylacetylene phthalic anhydride as a capping agent was added, and stirring was continued for 16 hours.
(2) A dropping funnel was mounted on the three-necked flask, and 87.0775g (0.415 mol) of trifluoroacetic anhydride (a dehydrating agent) was added dropwise thereto for 4 hours.
(3) Subsequently, the gum solution was gradually dispersed into about 6L of deionized water with stirring; filtration gave a resin solid which was washed three times with water and then dried in a forced air drying oven at 120℃for 24 hours to give a polyisoimide resin.
The target product was characterized as follows: infrared spectral absorption peak (cm -1): 3054, 2211, 1780, 1723, 1612, 1501, 1377, 1231, 1086, 1049-1121, 916, 743. The structure is correct through verification. The polyisoimide resin prepared in the embodiment is shown in a formula IV:
In the formula IV, n represents the degree of polymerization, and the molecular weight of the polyisoimide resin is 2500g/mol.
2. Preparation of polyisoimide resin molded article and performance test
The polyisoimide powder obtained by the method is placed into a die, the whole die is placed into a high-temperature die pressing machine, the pressing machine is heated to 300 ℃ and kept at the constant temperature for 10min, then the temperature is increased to 380 ℃ at 4 ℃/min, the pressure is increased to 4MPa for 1-2 min, and the temperature and the pressure are maintained for 2 hours. And then stopping heating, keeping the pressure of the mold, cooling, opening the mold, and taking out the black solidified resin plate when the temperature is reduced to 250 ℃.
The high-temperature rheological test result shows that the resin has the minimum melt viscosity of 6.39 Pa.s after being kept at the temperature of 270 ℃ for 2 hours.
The T g of the pure polyisoimide resin molded part formed after the resin is solidified is 410 ℃, the 5% thermal weight loss temperature is more than 550 ℃, the tensile strength (room temperature) is 84MPa, and the bending strength (room temperature) is 153MPa.
3. Preparation of polyisoimide resin/carbon fiber composite laminate and performance test
The polyisoimide resin obtained by the method is dissolved in dimethylacetamide (the mass ratio is 60:40), and the obtained mixture is fully stirred to form a uniform solution, so that the polyisoimide prepreg is obtained.
The obtained polyisoimide prepreg is uniformly brushed on the surface of high-strength carbon fiber cloth, is put into an oven, is heated to 180 ℃ and is kept at the constant temperature for 12 hours, and is cooled to room temperature after the solvent is removed, so that the polyisoimide carbon fiber prepreg is obtained.
Spraying dichloromethane on the surface of the obtained polyisoimide carbon fiber prepreg for softening, then heating according to a gradient of 160 ℃/2h+260 ℃/2h+380 ℃/2h, and molding under the condition that the mold closing pressure is controlled to be 2.5MPa, thereby obtaining the polyisoimide carbon fiber composite material. The bending strength at room temperature is 1806MPa, the interlayer shearing strength at room temperature is 81MPa, the bending strength at 400 ℃ is 932MPa, and the interlayer shearing strength at 400 ℃ is 40.5MPa.
Example 4
Preparation and performance test of polyisoimide resin
1. Preparation of polyisoimide resin and Structure confirmation
The polyisoimide resin is prepared as follows:
(1) To a three-necked flask equipped with a mechanical stirrer and nitrogen gas protection, 45.6009g (0.17 mol) of 2-trifluoromethyl-4, 4 '-diaminodiphenyl ether and 0.3g of triethylamine as a catalyst were charged, 98.83: 98.83gNMP as a solvent was then added, 65.1959g (0.147 mol) of 4,4' -hexafluoroisopropyl-diphthalic anhydride and 270.49g of NMP were added after dissolution, the solid content of the reaction system was 30% by mass, after 6 hours of reaction in an ice-water bath, 11.5393g (0.046 mol) of 4-phenylacetylene phthalic anhydride as a blocking agent was added, and stirring was continued for 16 hours.
(2) A three-necked flask was equipped with a dropping funnel, and 89.263g (0.425 mol) of trifluoroacetic anhydride (a dehydrating agent) was added dropwise thereto for 4 hours.
(3) Subsequently, the gum solution was gradually dispersed into about 6L of deionized water with stirring; filtration gave a resin solid which was washed three times with water and then dried in a forced air drying oven at 120℃for 24 hours to give a polyisoimide resin.
The target product was characterized as follows: infrared spectral absorption peak (cm -1): 3054, 2211, 1780, 1723, 1612, 1501, 1378, 1231, 1086, 1049-1121, 916, 743. The structure is correct through verification. The polyisoimide resin prepared in the embodiment is shown in a formula IV:
In the formula IV, n represents the degree of polymerization, and the molecular weight of the polyisoimide resin is 5000g/mol.
2. Preparation of polyisoimide resin molded article and performance test
The polyisoimide powder obtained by the method is placed into a die, the whole die is placed into a high-temperature die pressing machine, the pressing machine is heated to 300 ℃ and kept at the constant temperature for 10min, then the temperature is increased to 380 ℃ at 4 ℃/min, the pressure is increased to 4MPa for 1-2 min, and the temperature and the pressure are maintained for 2 hours. And then stopping heating, keeping the pressure of the mold, cooling, opening the mold, and taking out the black solidified resin plate when the temperature is reduced to 250 ℃.
The high-temperature rheological test result shows that the resin has the minimum melt viscosity of 8.72 Pa.s after being kept at the temperature of 270 ℃ for 2 hours.
The T g of the pure polyisoimide resin molded part formed after the resin is solidified is 398 ℃, the 5% thermal weight loss temperature is more than 550 ℃, the tensile strength (room temperature) is 93MPa, and the bending strength (room temperature) is 156MPa.
3. Preparation of polyisoimide resin/carbon fiber composite laminate and performance test
The polyisoimide resin obtained by the method is dissolved in dimethylacetamide (the mass ratio is 60:40), and the obtained mixture is fully stirred to form a uniform solution, so that the polyisoimide prepreg is obtained.
The obtained polyisoimide prepreg is uniformly brushed on the surface of high-strength carbon fiber cloth, is put into an oven, is heated to 180 ℃ and is kept at the constant temperature for 12 hours, and is cooled to room temperature after the solvent is removed, so that the polyisoimide carbon fiber prepreg is obtained.
Spraying dichloromethane on the surface of the obtained polyisoimide carbon fiber prepreg for softening, then heating according to a gradient of 160 ℃/2h+260 ℃/2h+380 ℃/2h, and molding under the condition that the mold closing pressure is controlled to be 2.5MPa, thereby obtaining the polyisoimide carbon fiber composite material. The bending strength at room temperature is 1819MPa, the interlayer shearing strength at room temperature is 74MPa, the bending strength at 400 ℃ is 960MPa, and the interlayer shearing strength at 400 ℃ is 39MPa.
Comparative example 1
To a three-necked flask equipped with mechanical stirring and nitrogen protection were added 10.9116g (0.0204 mol) of 2-fluoro-4, 4' -diaminodiphenyl ether and 0.3g of triethylamine as a catalyst, 67.41gNMP was further added to dissolve the components, and 9.3132g (0.037 mol) of 2, 3',4' -biphenyltetracarboxylic dianhydride was further added and stirred for 5 hours. 9.1132g (0.0036 mol) of 4-phenylethynyl phthalic anhydride was added to the solution, NMP was added, and the solid content of the solution was adjusted to 30%. Stir at room temperature overnight. A three-necked flask was equipped with a water separator and a condenser, 20g of xylene was added, and the system was heated to 200℃and reacted for 12 hours. Stopping heating, and gradually dispersing into water and ethanol mixed solution at about 80 ℃ under stirring after the temperature of the system is reduced to room temperature; the resin solid was obtained by filtration, washed three times with water, then dried in a forced air drying oven at 100℃for 2 hours, and then dried in vacuo at 220℃for 4 hours to obtain a polyisoimide resin.
The polyisoimide resin prepared in the comparative example is shown in a formula VII:
In the formula VII, n represents the degree of polymerization, and the molecular weight of the polyisoimide resin represented by the formula VII is 1500g/mol.
The polyisoimide powder obtained by the method is put into a mould, the temperature is raised to 300 ℃, and the temperature is kept for 10 minutes to ensure the melting of the resin. Subsequently, the temperature was raised to 371℃and a pressure of 4MPa was applied to cure for 1 hour. And cooling to about 260 ℃ and opening the die to obtain the compression molding part of the polyisoimide resin.
The high-temperature rheological test result shows that the resin has the melt viscosity lower than 100 Pa.s after being kept at the temperature of 270 ℃ for 2 hours.
The T g of the pure polyisoimide resin molded part formed after the resin is solidified is 321 ℃, and the 5% thermal weight loss temperature is more than 550 ℃. The tensile strength (room temperature) was 42MPa and the flexural strength (room temperature) was 111MPa.
The polyisoimide resin obtained by the method is dissolved in dimethylacetamide (the mass ratio is 60:40), and the obtained mixture is fully stirred to form a uniform solution, so that the polyisoimide prepreg is obtained.
The obtained polyisoimide prepreg is uniformly brushed on the surface of high-strength carbon fiber cloth, is put into an oven, is heated to 180 ℃ and is kept at the constant temperature for 12 hours, and is cooled to room temperature after the solvent is removed, so that the polyisoimide carbon fiber prepreg is obtained.
Spraying dichloromethane on the surface of the obtained polyisoimide carbon fiber prepreg for softening, then heating according to a gradient of 160 ℃/2h+260 ℃/2h+380 ℃/2h, and molding under the condition that the mold closing pressure is controlled to be 2.5MPa, thereby obtaining the polyisoimide carbon fiber composite material. The bending strength at room temperature is 1421MPa, the interlayer shearing strength at room temperature is 53MPa, the bending strength at 400 ℃ is 680MPa, and the interlayer shearing strength at 400 ℃ is 25MPa.
Table 1 shows the main properties of the polyisoimide resins prepared in each example and comparative example. The solubility results of the polyisoimide resins prepared in the examples and comparative examples are given in Table 2.
| Sequence number | Tg | Tensile Strength | Flexural Strength | Bending strength of composite material | Interlayer shear strength of composite material |
| Example 1 | 417℃ | 70MPa | 136MPa | 1860MPa | 81MPa |
| Example 2 | 419℃ | 72MPa | 131MPa | 1740MPa | 79MPa |
| Example 3 | 410℃ | 84MPa | 153MPa | 1806MPa | 81MPa |
| Example 4 | 398℃ | 93MPa | 156MPa | 1819MPa | 74MPa |
| Comparative example 1 | 321℃ | 42MPa | 111MPa | 1421MPa | 53MPa |
Table 1 table 2
Note that: ++ denotes readily soluble, + denotes dissolved, -denotes insoluble, THF is tetrahydrofuran, DMAc is N, N-dimethylacetamide, NMP is N-methylpyrrolidone, DMF is N, N-dimethylformamide.
While the invention has been described with reference to preferred embodiments, it is not intended to be limiting. Those skilled in the art will appreciate that various modifications and adaptations can be made without departing from the spirit and scope of the present invention. Accordingly, the scope of the invention is defined by the appended claims.
Claims (10)
1. The polyisoimide resin is characterized by having a structure shown in a formula 1:
In the formula I, n represents the polymerization degree, and the weight average molecular weight of the polyisoimide resin shown in the formula I is 750-5000 g/mol;
Wherein, R 1 is selected from one of the structures of (1) and (2):
r 2 is the structure of (3):
R 3 is selected from one of the structures (4) and (5):
2. a method for producing the polyisoimide resin set forth in claim 1, comprising the steps of:
(1) Taking an organic solvent, aromatic diamine shown as R 1, aromatic dianhydride shown as R 2 and an R 3 reactive end-capping agent as raw materials to prepare polyamide acid through polymerization reaction and end-capping reaction;
(2) And (3) imidizing the polyamic acid under the action of a catalyst and a dehydrating agent to obtain the polyisoimide resin.
3. The process according to claim 2, wherein the aromatic diamine is selected from the group consisting of 2-fluoro-4, 4 '-diaminodiphenyl ether and 2-trifluoromethyl-4, 4' -diaminodiphenyl ether; the aromatic dianhydride is 4,4' - (hexafluoroisopropyl) diphthalic anhydride; the reactive end-capping agent is selected from ethynyl phthalic anhydride or 4-phenylacetylene phthalic anhydride.
4. The process according to claim 2, wherein the molar ratio of the aromatic diamine, the aromatic dianhydride and the reactive end-capping agent is (1.13 to 4.54): (0.13-3.54): 2.
5. The process according to claim 2, wherein the polymerization and capping reactions are carried out at a temperature of 0 to 15 ℃, preferably 0 ℃; the polymerization time is 6 to 18 hours, preferably 6 hours; the capping reaction time is 6 to 16 hours, preferably 16 hours.
6. The process according to claim 2, wherein the polymerization and the capping are carried out under inert gas atmosphere; the polymerization reaction and the end capping reaction are carried out under the stirring condition; the imidization reaction is carried out in an ice-water bath environment.
7. The method according to claim 2, wherein the dehydrating agent is selected from any one of acetyl chloride, thionyl chloride, dicyclohexylcarbodiimide and trifluoroacetic anhydride; the amount of the dehydrating agent is 2.5 to 5 times the amount of the aromatic diamine substance.
8. The preparation method according to claim 2, wherein the catalyst is selected from any one of triethylamine, triethanolamine, pyridine and isoquinoline; the amount of the catalyst is 0.01 to 2 times the amount of the aromatic diamine substance.
9. A composite material comprising the polyisoimide resin according to claim 1 and a fiber, wherein the fiber is a carbon fiber, a glass fiber, a quartz fiber or an aramid fiber.
10. A molded article of the polyisoimide resin described in claim 1, which is obtained by curing the polyisoimide resin at a temperature of 370 to 380℃and a pressure of 4MPa for 2 to 4 hours.
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