CN116675954A - Phosphorus and nitrogen-containing ionic liquid/epoxy resin composite material and preparation method thereof - Google Patents
Phosphorus and nitrogen-containing ionic liquid/epoxy resin composite material and preparation method thereof Download PDFInfo
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- CN116675954A CN116675954A CN202310966443.5A CN202310966443A CN116675954A CN 116675954 A CN116675954 A CN 116675954A CN 202310966443 A CN202310966443 A CN 202310966443A CN 116675954 A CN116675954 A CN 116675954A
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 80
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 70
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 26
- 239000011574 phosphorus Substances 0.000 title claims abstract description 26
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 10
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 claims abstract description 44
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 24
- IWDFHWZHHOSSGR-UHFFFAOYSA-N 1-ethylimidazole Chemical compound CCN1C=CN=C1 IWDFHWZHHOSSGR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 229920000049 Carbon (fiber) Polymers 0.000 description 33
- 239000004917 carbon fiber Substances 0.000 description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000004744 fabric Substances 0.000 description 12
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009863 impact test Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
A phosphorus and nitrogen-containing ionic liquid/epoxy resin composite material and a preparation method thereof relate to the technical field of composite materials, realize improvement of mechanical properties and flame retardance of epoxy composite materials, simplify the process and realize mass production. The phosphorus and nitrogen-containing ionic liquid/epoxy resin composite material comprises: 1-3 parts of phosphorus-nitrogen-containing ionic liquid, 100 parts of epoxy resin and 25 parts of curing agent. Dissolving phenylphosphoric acid in a solvent at room temperature, dropwise adding 1-ethylimidazole into the phenylphosphoric acid solution under magnetic stirring for reaction, and then removing the solvent by rotary evaporation and vacuum drying the solution to obtain yellowish transparent phosphorus and nitrogen-containing ionic liquid; uniformly mixing epoxy resin and a curing agent at a specific temperature, adding the phosphorus-nitrogen-containing ionic liquid, uniformly stirring again, vacuumizing, rapidly pouring the mixed sample into a preheated mold, and heating and curing to obtain the phosphorus-nitrogen-containing ionic liquid/epoxy resin composite material.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a phosphorus and nitrogen-containing ionic liquid/epoxy resin composite material and a preparation method thereof.
Background
Ionic Liquids (IL) are a new green material that is widely used in various manufacturing fields due to its good thermal stability, high gas solubility and nonflammability, and they have achieved remarkable achievements in enhancing polymer properties.
Epoxy resin (EP) is a three-dimensional network structure thermosetting polymer formed by reacting epoxy prepolymer with curing agent, and can be widely applied to the fields of aerospace, automobile industry, electronics, electricity, civil engineering and construction and the like as the epoxy resin (EP) has low volume shrinkage, strong adhesiveness, good chemical stability and high mechanical strength, is easy to process and form, and can be used as an adhesive, a coating or a resin-based composite material and the like. However, EP is generally brittle and has insufficient toughness, and the inherent flammability of EP threatens human safety, greatly limiting the use of EP in many fields. Therefore, it is imperative to improve the flame retardant property and mechanical property of EP.
Many methods for modifying epoxy resins have been proposed in the prior art. For example, in patent document CN114891227a, "a preparation method of halogen-free flame-retardant modified epoxy resin" (publication day 2022, 8, 12), phosphorus-containing cage-type oligomeric silsesquioxane DOPO-POSS, bisphenol a epoxy vinyl ester slurry and curing agent are adopted to prepare halogen-free flame-retardant modified epoxy resin, so that the flame-retardant efficiency of the epoxy resin is improved, but the mechanical properties of the epoxy composite material are affected, and the application of the epoxy composite material in a plurality of fields is limited. Patent document CN115894860a, "an epoxy resin composition prepared from the same (publication day: 2022, 8, 12), discloses an epoxy resin composition prepared from the same, and a preparation method thereof, which improves thermal and mechanical properties of the epoxy resin, but has complex preparation process and large addition amount, and is difficult to realize mass production.
In summary, how to improve the mechanical properties and flame retardance of the epoxy composite material at the same time, simplify the process, and realize mass production has become a technical problem to be solved in the art.
Disclosure of Invention
In order to simultaneously improve the mechanical property and the flame retardance of the epoxy composite material, simplify the process and realize mass production, the invention provides a phosphorus and nitrogen-containing ionic liquid/epoxy resin composite material and a preparation method thereof.
The invention firstly provides a phosphorus and nitrogen-containing ionic liquid/epoxy resin composite material, which comprises the following components in parts by mass:
1-3 parts of phosphorus-nitrogen-containing ionic liquid, 100 parts of epoxy resin and 25 parts of curing agent;
wherein, the structural formula of the phosphorus-nitrogen-containing ionic liquid is as follows:
。
preferably, the epoxy resin is bisphenol a epoxy resin.
Preferably, the curing agent is an amine curing agent or an anhydride curing agent.
The invention also provides a preparation method of the phosphorus-nitrogen-containing ionic liquid/epoxy resin composite material, which comprises the following steps:
s1, dissolving phenyl phosphoric acid in a solvent at room temperature to obtain a phenyl phosphoric acid solution, dropwise adding 1-ethylimidazole into the phenyl phosphoric acid solution under magnetic stirring for reaction, then rotationally evaporating the solution to remove the solvent, and drying in vacuum to obtain a light yellow transparent liquid, namely a phosphorus-nitrogen-containing ionic liquid;
s2, uniformly mixing epoxy resin and a curing agent at a specific temperature, adding the phosphorus-nitrogen-containing ionic liquid obtained in the step S1, uniformly stirring again, vacuumizing, and rapidly pouring the mixed sample into a preheated mold for heating and curing when the mixture is free of bubbles in vacuum to obtain the phosphorus-nitrogen-containing ionic liquid/epoxy resin composite material.
Preferably, the molar ratio of the phenylphosphoric acid to the 1-ethylimidazole is 1:2.
preferably, the solvent in step S1 is absolute ethanol.
Preferably, the temperature of the rotary evaporation is 30-120 ℃; the temperature of the vacuum drying is 20-60 ℃.
Preferably, the reaction time in the step S1 is 1-6 hours.
Preferably, the specific temperature in the step S2 is 80 ℃ to 100 ℃.
Preferably, the temperature of the preheating is 120 ℃, and the time of the preheating is 20 min; the heating and curing specifically comprises the following steps: curing for 2h at 120℃and then heating to 150℃for 2h.
Compared with the prior art, the invention has the following specific beneficial effects:
1. the invention provides a phosphorus-nitrogen-containing ionic liquid/epoxy resin composite material, wherein an imidazole structure in the phosphorus-nitrogen-containing ionic liquid can play a role in promoting solidification, and meanwhile, the epoxy resin fracture is accompanied with the destruction and regeneration of a series of ionic bonds on a molecular scale, so that a large amount of energy is dissipated, the fracture toughness is enhanced, and compared with the common E51 epoxy resin on the market, the flexural strength, the flexural modulus, the elongation at break, the impact strength and the flame retardant property are all remarkably improved;
2. the phosphorus and nitrogen elements in the phosphorus-nitrogen-containing ionic liquid can generate phosphorus-oxygen free radicals and nitrogen when the epoxy resin composite material burns, and the flame is quenched, so that excellent flame retardant property is realized;
3. the preparation method provided by the invention is simple, convenient to operate and suitable for industrial mass production.
Drawings
FIG. 1 is an infrared spectrum of an ionic liquid prepared in example 1;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the ionic liquid prepared in example 1;
FIG. 3 is an XPS diagram of the ionic liquid prepared in example 1;
FIG. 4 is a bar graph of flexural strength of ionic liquid/epoxy composites of varying levels of phosphorous and nitrogen;
FIG. 5 is a bar graph of flexural modulus of ionic liquid/epoxy resin composites of varying levels of phosphorous and nitrogen;
FIG. 6 is a graph showing stress-strain curves of ionic liquid/epoxy resin composites with different contents of phosphorus and nitrogen;
FIG. 7 is a bar graph of impact strength of ionic liquid/epoxy composites with varying levels of phosphorous and nitrogen;
FIG. 8 is an SEM image of impact test fracture surfaces of ionic liquid/epoxy resin composites of varying content of phosphorous and nitrogen;
FIG. 9 is a bar graph of flexural strength of various levels of phosphorus and nitrogen containing ionic liquid/epoxy carbon fiber composite material panels;
FIG. 10 is a bar graph of flexural modulus of various levels of phosphorus and nitrogen containing ionic liquid/epoxy carbon fiber composite material plaques.
Detailed Description
In order to make the technical solution of the present invention clearer, the technical solution of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the present invention, and it should be noted that the following embodiments are only used for better understanding of the technical solution of the present invention, and should not be construed as limiting the present invention.
Example 1.
S1, dissolving 0.01mol of phenylphosphoric acid (PPA) in a solvent at room temperature to obtain a phenylphosphoric acid solution, dropwise adding 0.02mol of 1-ethylimidazole (MZ) into the phenylphosphoric acid solution under magnetic stirring for reaction, then rotationally evaporating the solution at 60 ℃ to remove the solvent, and vacuum drying at 60 ℃ for 1h to obtain light yellow transparent phosphorus and nitrogen-containing ionic liquid (PIL);
FIG. 1 is an infrared spectrum of PPA, MZ and PIL described in this example, and it can be seen that PPA is 1439cm -1 ，1144cm -1 ，938cm -1 Characteristic peaks appear at the positions, and the characteristic peaks are respectively attributed to stretching vibration of P-Ph, P=O and P-OH; MZ at 1647cm -1 And 1512cm -1 The characteristic peak appearing is attributed to the stretching vibration of the imidazole ring; in the synthesized PIL infrared spectrum, original P-OH disappears and NH at 1545 is newly appeared + This demonstrates successful synthesis of PIL.FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of PIL obtained in this example, wherein the signal peak at about 8.07ppm is NH + In addition to the signal peaks of (a), the chemical shift and integrated area of all other signal peaks correspond to protons of the chemical structure of PIL. From the above results and analysis, it was revealed that the target compound was successfully synthesized. FIG. 3 is an X-ray photoelectron spectrum of PIL prepared in this example, which reveals the presence of element C, N, O, P in PIL; for XPS C1s spectra, PIL shows two peaks at 285.1, 283.8eV, corresponding to bonds of C-N/c=n and C-C, respectively; for XPS N1s spectra, PIL shows one peak at 400.5eV, corresponding to a bond of C-N/c=n; for XPS P1s spectra, PIL shows two peaks at 531.6 and 530.3eV, corresponding to P-O and p=o bonds, respectively. This also indicates successful synthesis of PIL. The above proves that the novel ionic liquid with the following structural formula is successfully synthesized in the embodiment:
。
the synthetic route of the ionic liquid is as follows:
。
s2, uniformly mixing 100 parts of bisphenol A epoxy resin and 25 parts of molten diaminodiphenyl methane (DDM) at 100 ℃, adding 1 part of the phosphorus-nitrogen-containing ionic liquid obtained in the step S1, uniformly stirring again, vacuumizing, preheating a mold at 120 ℃ for 20min, rapidly pouring a mixed sample into the mold when the mixture is free of bubbles in vacuum, curing for 2h at 120 ℃, and then heating to 150 ℃ for 2h to obtain the phosphorus-nitrogen-containing ionic liquid/epoxy resin composite material.
Example 2.
S1, dissolving 0.01mol of phenylphosphoric acid (PPA) in a solvent at room temperature to obtain a phenylphosphoric acid solution, dropwise adding 0.02mol of 1-ethylimidazole (MZ) into the phenylphosphoric acid solution under magnetic stirring for reaction, then rotationally evaporating the solution at 40 ℃ to remove the solvent, and drying in vacuum at 50 ℃ for 2 hours to obtain light yellow transparent phosphorus and nitrogen-containing ionic liquid (PIL);
s2, uniformly mixing 100 parts of bisphenol A epoxy resin and 25 parts of molten diaminodiphenyl methane (DDM) at 90 ℃, adding 2 parts of the phosphorus-nitrogen-containing ionic liquid obtained in the step S1, uniformly stirring again, vacuumizing, preheating a mold at 120 ℃ for 20min, rapidly pouring a mixed sample into the mold when the mixture is free of bubbles in vacuum, curing for 2h at 120 ℃, and then heating to 150 ℃ for 2h to obtain the phosphorus-nitrogen-containing ionic liquid/epoxy resin composite material.
Example 3.
S1, dissolving 0.01mol of phenylphosphoric acid (PPA) in a solvent at room temperature to obtain a phenylphosphoric acid solution, dropwise adding 0.02mol of 1-ethylimidazole (MZ) into the phenylphosphoric acid solution under magnetic stirring for reaction, then rotationally evaporating the solution at 100 ℃ to remove the solvent, and vacuum drying at 30 ℃ for 5 hours to obtain light yellow transparent phosphorus and nitrogen-containing ionic liquid (PIL);
s2, uniformly mixing 100 parts of bisphenol A epoxy resin and 25 parts of molten diaminodiphenyl methane (DDM) at 80 ℃, adding 3 parts of the phosphorus-nitrogen-containing ionic liquid obtained in the step S1, uniformly stirring again, vacuumizing, preheating a mold at 120 ℃ for 20min, rapidly pouring a mixed sample into the mold when the mixture is free of bubbles in vacuum, curing for 2h at 120 ℃, and then heating to 150 ℃ for 2h to obtain the phosphorus-nitrogen-containing ionic liquid/epoxy resin composite material.
Comparative example 1.
S1, dissolving 0.01mol of phenylphosphoric acid (PPA) in a solvent at room temperature to obtain a phenylphosphoric acid solution, dropwise adding 0.02mol of 1-ethylimidazole (MZ) into the phenylphosphoric acid solution under magnetic stirring for reaction, then rotationally evaporating the solution at 60 ℃ to remove the solvent, and vacuum drying at 60 ℃ for 1h to obtain light yellow transparent phosphorus and nitrogen-containing ionic liquid (PIL);
s2, uniformly mixing 100 parts of bisphenol A epoxy resin with 25 parts of molten diaminodiphenyl methane (DDM) at 100 ℃, vacuumizing, preheating a mold at 120 ℃ for 20min, rapidly pouring a mixed sample into the mold when the mixture is free of bubbles in vacuum, curing for 2h at 120 ℃, and then heating to 150 ℃ for 2h to obtain the epoxy resin composite material without the ionic liquid.
Respectively testing the flexural strength of the phosphorus-containing and nitrogen-containing ionic liquid/epoxy resin composite materials with different contents and the epoxy resin without the ionic liquid in comparative example 1, wherein the measured flexural strength bar graph is shown in fig. 4, and the flexural modulus bar graph is shown in fig. 5; the elongation at break is tested, and the stress-strain curve is shown in figure 6; impact tests were performed to obtain a bar graph of impact strength as shown in fig. 7, and SEM images of impact test fracture surfaces of epoxy composites of different contents as shown in fig. 8.
The phosphorus and nitrogen-containing ionic liquid/epoxy resin composite materials with different contents prepared in examples 1-3 and comparative examples are respectively tested for fire resistance, and limiting oxygen indexes and UL-94 results are shown in Table 1.
TABLE 1
| Sample of | LOI(%) | UL-94 |
| EP (epoxy resin) | 24.5 | - |
| 1.0PIL | 31.6 | V-0 |
| 2.0PIL | 31.8 | V-0 |
| 3.0PIL | 32.6 | V-0 |
As can be seen from the test results, compared with the common E51 epoxy resin on the market, the phosphorus-nitrogen-containing ionic liquid/epoxy composite material prepared by the invention has the advantages that the bending strength, the elongation at break and the flame retardant property are obviously improved, the impact strength is obviously improved when the ionic liquid is added in 2-3 parts, however, the material is easier to deform due to plastic deformation, the bending modulus is correspondingly slightly reduced, the reducing trend is very small, and the influence on the epoxy resin is small. As can be seen from SEM images of impact test fracture surfaces of epoxy composite materials with different ionic liquid contents, the fracture surfaces of the pure epoxy resin are smooth and have obvious brittle fracture characteristics, and with the addition of the ionic liquid, ductile pits with different sizes appear on the fracture surfaces of the material, so that the toughness of the material is improved, and the impact resistance is obviously improved.
Example 4.
S1, dissolving 0.01mol of phenylphosphoric acid (PPA) in a solvent at room temperature to obtain a phenylphosphoric acid solution, dropwise adding 0.02mol of 1-ethylimidazole (MZ) into the phenylphosphoric acid solution under magnetic stirring for reaction, then rotationally evaporating the solution at 60 ℃ to remove the solvent, and vacuum drying at 60 ℃ for 1h to obtain light yellow transparent phosphorus and nitrogen-containing ionic liquid (PIL);
s2, uniformly mixing 100 parts of bisphenol A epoxy resin and 25 parts of molten diaminodiphenyl methane (DDM) at 100 ℃, adding 1 part of the phosphorus-nitrogen-containing ionic liquid obtained in the step S1, uniformly stirring again, and vacuumizing to remove bubbles;
s3, manufacturing carbon fiber plates by adopting 3k carbon fiber cloth with the strength grade of T300, wherein the size of each layer of carbon fiber cloth is 150 multiplied by 120mm, paving 6 layers of carbon fiber cloth on each plate, and paving in a vacuum bag;
s4, introducing the resin in the step S2 into the carbon fiber with the aid of a vacuum pump, sealing and keeping a vacuum state, then placing the carbon fiber into an oven, modulating the temperature to 120 ℃ for 2 hours, and then heating to 150 ℃ for 2 hours to finish curing, and removing a vacuum bag to obtain the phosphorus-nitrogen-containing ionic liquid/epoxy resin carbon fiber composite material.
Example 5.
S1, dissolving 0.01mol of phenylphosphoric acid (PPA) in a solvent at room temperature to obtain a phenylphosphoric acid solution, dropwise adding 0.02mol of 1-ethylimidazole (MZ) into the phenylphosphoric acid solution under magnetic stirring for reaction, then rotationally evaporating the solution at 60 ℃ to remove the solvent, and vacuum drying at 60 ℃ for 1h to obtain light yellow transparent phosphorus and nitrogen-containing ionic liquid (PIL);
s2, uniformly mixing 100 parts of bisphenol A epoxy resin and 25 parts of molten diaminodiphenyl methane (DDM) at 100 ℃, adding 2 parts of the phosphorus-nitrogen-containing ionic liquid obtained in the step S1, uniformly stirring again, and vacuumizing to remove bubbles;
s3, manufacturing carbon fiber plates by adopting 3k carbon fiber cloth with the strength grade of T300, wherein the size of each layer of carbon fiber cloth is 150 multiplied by 120mm, paving 6 layers of carbon fiber cloth on each plate, and paving in a vacuum bag;
s4, introducing the resin in the step S2 into the carbon fiber with the aid of a vacuum pump, sealing and keeping a vacuum state, then placing the carbon fiber into an oven, modulating the temperature to 120 ℃ for 2 hours, and then heating to 150 ℃ for 2 hours to finish curing, and removing a vacuum bag to obtain the phosphorus-nitrogen-containing ionic liquid/epoxy resin carbon fiber composite material.
Example 6.
S1, dissolving 0.01mol of phenylphosphoric acid (PPA) in a solvent at room temperature to obtain a phenylphosphoric acid solution, dropwise adding 0.02mol of 1-ethylimidazole (MZ) into the phenylphosphoric acid solution under magnetic stirring for reaction, then rotationally evaporating the solution at 60 ℃ to remove the solvent, and vacuum drying at 60 ℃ for 1h to obtain light yellow transparent phosphorus and nitrogen-containing ionic liquid (PIL);
s2, uniformly mixing 100 parts of bisphenol A epoxy resin and 25 parts of molten diaminodiphenyl methane (DDM) at 100 ℃, adding 3 parts of the phosphorus-nitrogen-containing ionic liquid obtained in the step S1, uniformly stirring again, and vacuumizing to remove bubbles;
s3, manufacturing carbon fiber plates by adopting 3k carbon fiber cloth with the strength grade of T300, wherein the size of each layer of carbon fiber cloth is 150 multiplied by 120mm, paving 6 layers of carbon fiber cloth on each plate, and paving in a vacuum bag;
s4, introducing the resin in the step S2 into the carbon fiber with the aid of a vacuum pump, sealing and keeping a vacuum state, then placing the carbon fiber into an oven, modulating the temperature to 120 ℃ for 2 hours, and then heating to 150 ℃ for 2 hours to finish curing, and removing a vacuum bag to obtain the phosphorus-nitrogen-containing ionic liquid/epoxy resin carbon fiber composite material.
Comparative example 2.
S1, dissolving 0.01mol of phenylphosphoric acid (PPA) in a solvent at room temperature to obtain a phenylphosphoric acid solution, dropwise adding 0.02mol of 1-ethylimidazole (MZ) into the phenylphosphoric acid solution under magnetic stirring for reaction, then rotationally evaporating the solution at 60 ℃ to remove the solvent, and vacuum drying at 60 ℃ for 1h to obtain light yellow transparent phosphorus and nitrogen-containing ionic liquid (PIL);
s2, uniformly mixing 100 parts of bisphenol A epoxy resin with 25 parts of molten diaminodiphenyl methane (DDM) at 100 ℃, and vacuumizing to remove bubbles;
s3, manufacturing carbon fiber plates by adopting 3k carbon fiber cloth with the strength grade of T300, wherein the size of each layer of carbon fiber cloth is 150 multiplied by 120mm, paving 6 layers of carbon fiber cloth on each plate, and paving in a vacuum bag;
s4, introducing the resin in the step S2 into the carbon fiber with the aid of a vacuum pump, sealing and keeping a vacuum state, then placing the carbon fiber into an oven, modulating the temperature to 120 ℃ for 2 hours, and then heating to 150 ℃ for 2 hours to finish curing, and removing a vacuum bag to obtain the epoxy resin carbon fiber composite material without the ionic liquid.
The prepared material is cut into 120mm multiplied by 12.5mm multiplied by 3mm sample bars, the flexural strength of the sample plates of the phosphorus-and nitrogen-containing ionic liquid/epoxy resin carbon fiber composite materials with different contents prepared in examples 4-6 is respectively tested, the measured flexural strength bar graph is shown in figure 9, and the flexural modulus bar graph is shown in figure 10. Compared with the common epoxy resin carbon fiber composite material on the market, the phosphorus and nitrogen-containing ionic liquid/epoxy resin carbon fiber composite material prepared by the invention has obviously improved bending strength under the condition of low addition.
It will be apparent that the above embodiments are merely examples for clarity of illustration and that other forms of modification or variation may be made in light of the above description. Thus, obvious variations or modifications may be made by those skilled in the art to which the invention pertains.
Claims (10)
1. The phosphorus and nitrogen-containing ionic liquid/epoxy resin composite material is characterized by comprising the following components in parts by mass:
1-3 parts of phosphorus-nitrogen-containing ionic liquid, 100 parts of epoxy resin and 25 parts of curing agent;
wherein, the structural formula of the phosphorus-nitrogen-containing ionic liquid is as follows:
。
2. the phosphorous and nitrogen containing ionic liquid/epoxy resin composite according to claim 1, wherein the epoxy resin is bisphenol a epoxy resin.
3. The phosphorous and nitrogen-containing ionic liquid/epoxy resin composite material according to claim 1, wherein the curing agent is an amine curing agent or an anhydride curing agent.
4. A method for preparing the phosphorus-nitrogen-containing ionic liquid/epoxy resin composite material according to any one of claims 1 to 3, which comprises the following steps:
s1, dissolving phenyl phosphoric acid in a solvent at room temperature to obtain a phenyl phosphoric acid solution, dropwise adding 1-ethylimidazole into the phenyl phosphoric acid solution under magnetic stirring for reaction, then rotationally evaporating the solution to remove the solvent, and drying in vacuum to obtain light yellow transparent phosphorus and nitrogen-containing ionic liquid;
s2, uniformly mixing epoxy resin and a curing agent at a specific temperature, adding the phosphorus-nitrogen-containing ionic liquid obtained in the step S1, uniformly stirring again, vacuumizing, and pouring the mixed sample into a preheated mold for heating and curing when the mixture is free of bubbles in vacuum to obtain the phosphorus-nitrogen-containing ionic liquid/epoxy resin composite material.
5. The method for preparing the phosphorus-nitrogen-containing ionic liquid/epoxy resin composite material according to claim 4, wherein the molar ratio of the phenyl phosphoric acid to the 1-ethylimidazole is 1:2.
6. the method for preparing a phosphorus-nitrogen-containing ionic liquid/epoxy resin composite material according to claim 4, wherein the solvent in the step S1 is absolute ethyl alcohol.
7. The method for preparing the phosphorus-nitrogen-containing ionic liquid/epoxy resin composite material according to claim 4, wherein the temperature of rotary evaporation is 30-120 ℃; the temperature of the vacuum drying is 20-60 ℃.
8. The method for preparing a phosphorus-nitrogen-containing ionic liquid/epoxy resin composite material according to claim 4, wherein the reaction time in the step S1 is 1-6 h.
9. The method for preparing a phosphorus-nitrogen-containing ionic liquid/epoxy resin composite material according to claim 4, wherein the specific temperature in the step S2 is 80-100 ℃.
10. The method for preparing the phosphorus-nitrogen-containing ionic liquid/epoxy resin composite material according to claim 4, wherein the preheating temperature is 120 ℃, and the preheating time is 20 min; the heating and curing process specifically comprises the following steps: curing for 2h at 120℃and then heating to 150℃for 2h.
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| CN117106332A (en) * | 2023-10-23 | 2023-11-24 | 中国林业科学研究院木材工业研究所 | Flame-retardant amino resin coating for repairing cracks of carbon layer as well as preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435649A (en) * | 2013-07-31 | 2013-12-11 | 宁波大学 | Bidentate phosphine functionalization ionic liquid and synthetic method thereof |
| CN114561083A (en) * | 2022-03-10 | 2022-05-31 | 南京工业大学 | Preparation method of piperazinyl phenylphosphate flame-retardant epoxy resin composite material |
| CN115536601A (en) * | 2022-10-14 | 2022-12-30 | 重庆交通大学 | Curing agent capable of resisting flame, strengthening and toughening epoxy resin, epoxy resin material and application |
| CN116478508A (en) * | 2023-05-04 | 2023-07-25 | 长春工业大学 | Ionic liquid modified epoxy resin, carbon fiber pultrusion composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103435649A (en) * | 2013-07-31 | 2013-12-11 | 宁波大学 | Bidentate phosphine functionalization ionic liquid and synthetic method thereof |
| CN114561083A (en) * | 2022-03-10 | 2022-05-31 | 南京工业大学 | Preparation method of piperazinyl phenylphosphate flame-retardant epoxy resin composite material |
| CN115536601A (en) * | 2022-10-14 | 2022-12-30 | 重庆交通大学 | Curing agent capable of resisting flame, strengthening and toughening epoxy resin, epoxy resin material and application |
| CN116478508A (en) * | 2023-05-04 | 2023-07-25 | 长春工业大学 | Ionic liquid modified epoxy resin, carbon fiber pultrusion composite material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117106332A (en) * | 2023-10-23 | 2023-11-24 | 中国林业科学研究院木材工业研究所 | Flame-retardant amino resin coating for repairing cracks of carbon layer as well as preparation method and application thereof |
| CN117106332B (en) * | 2023-10-23 | 2023-12-29 | 中国林业科学研究院木材工业研究所 | Flame-retardant amino resin coating for repairing cracks of carbon layer as well as preparation method and application thereof |
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